loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures...

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S1 Supporting Information Homochiral 3D framework of mechanically interlocked 1D loops with solvent-dependent spin-state switching behaviors Xiao-Peng Sun, Zheng Tang, Zi-Shuo Yao,* and Jun Tao* Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, People’s Republic of China E-mail: [email protected] (J. Tao), [email protected] (Z.-S. Yao) Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2019

Transcript of loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures...

Page 1: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S1

Supporting Information

Homochiral 3D framework of mechanically interlocked 1D

loops with solvent-dependent spin-state switching behaviors

Xiao-Peng Sun Zheng Tang Zi-Shuo Yao and Jun Tao

Key Laboratory of Cluster Science of Ministry of Education School of Chemistry and

Chemical Engineering Liangxiang Campus Beijing Institute of Technology Beijing 102488

Peoplersquos Republic of China

E-mail taojunbiteducn (J Tao) zishuoyaobiteducn (Z-S Yao)

Electronic Supplementary Material (ESI) for ChemCommThis journal is copy The Royal Society of Chemistry 2019

S2

TABLE OF CONTENTS

Experimental Details∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4minusS6

Materials and methods ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4

Synthetic procedures∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4

Single-crystal X-ray diffractometry∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S6

Additional Tables ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S7minusS10

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S7

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙S7

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S6 Structural parameters for the mechanical interactions at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S9

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S9

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S10

Additional Figures∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S11minusS22

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states ∙∙∙∙S11

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S11

Figure S3 Elemental mapping photographs and SEM image of single crystal of 1middotCH3CN∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S12

Figure S4 Elemental mapping photographs and SEM image of single crystal of 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S12

Figure S5 Thermogravimetric plots of 1middotCH3CN and 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S13

Figure S6 The general view of internal angles and dimensions in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S13

Figure S7 A possible interlocking process of 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S14

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S14

Figure S9 The view of the 1D open channels in the title 3D MIS framework ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S15

Figure S10 The stick and its simplified views of the linear poly[n]catenane structure in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S15

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions and the

perspective view of the three kinds of interactions in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S16

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis and in the ac plane in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S16

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis and

in the ac plane in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S17

S3

Figure S14 The SHG signals of 1middotCH3CN 1middotCH3OH R-L2 and KDP ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S17

Figure S15 View of the spin-state ordering of 1middotCH3OH at 160 K ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S16 Schematic representation of spin-state conversions of FeII ions in 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1middotH2O ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S20 Normalized variable temperature χMT versus T plots for 1middotCH3CN 1 1middotH2O 1middotCH3OH

1middotC2H5OH and 1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S21 The corresponding d(χMT)dT versus T plots for 1middotCH3CN 1middotCH3OH 1middotC2H5OH and

1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S22 IR spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S23 UV-vis spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S24 1H NMR spectra of ligand R-L2∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S22

References∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S23

S4

Experimental Details

Materials and methods

All chemical reagents were commercially available and used as purchased Powder X-ray diffraction

(PXRD) data were collected on a PANalytical diffractometer with Cu Kα (λ = 154056 Aring) radiation

The C H and N microanalyses were measured on a EUROVECTER EA3000 analyzer Fourier

transform infrared (FT-IR) spectra were performed on a Nicolet IS10 FT-IR spectrometer in the

range of 4000minus400 cmminus1 with KBr pellets Thermogravimetric (TG) analyses were recorded on a

TG-DTA 6200 instrument under a flowing nitrogen atmosphere in the temperature range 20minus700

degC at a heating rate of 10 degC minminus1 The 1H NMR spectrum was measured by a Bruker Avance 400

MHz spectrometer Magnetic susceptibility measurements of the polycrystalline samples were

measured on a Quantum Design MPMS XL7 magnetometer operating in the successive

coolingheating cycle with a scan rate of 1 K minminus1 Field-emission scanning electron microscopy

(FE-SEM) images were tested on a JSM-7500F scanning electron microscope with an accelerating

voltage of 50 kV UV-Vis spectra were obtained from a TU-1950 UV-Vis spectrophotometer with

BaSO4 as reference Solid-state circular dichroism (CD) spectra were carried out on a Jasco-810

spectropolarimeter with respective bulk sample using dried KBr pellets and the weight ratio are

adopted as 1middotCH3CN KBr = 1800 1middotCH3OH KBr = 1600 R-L2 KBr = 1600 Second

harmonic generation (SHG) signals of title compounds and KDP (particle size range of 30minus70 μm)

were performed on a Q-switched NdYAG solid-state laser at room temperature with a wavelength

of 1064 nm

Synthetic procedures

Synthesis of R-22-bis(methoxymethoxy)-66-bis(4-pyridylethynyl)-11-binaphth-yl (R-L2) The

ligand R-L2 was synthesized according to the published references12 Elemental analysis () calcd

for C38H28N2O4 C 7915 H 489 N 486 Found C 7923 H 487 N 483 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ

765minus763 (d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d

2H ArH) δ 515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3) IR

(KBr pellet cmminus1) 2208 (m) 2068 (w) 1927 (w) 1735 (w) 1620 (m) 1594 (s) 1536 (w) 1473

(m) 1405 (m) 1370 (w) 1348 (m) 1301 (w) 1244 (m) 1194 (m) 1150 (s) 1069 (s) 1026 (s) 968

S5

(w) 921 (w) 889 (w) 874 (w) 819 (s) 729 (w) 692 (m) 669 (w) 626 (w) 591 (w) 556 (m) 542

(s) 500 (m) 448 (w) 427 (m)

Preparation of [Fe(NCBH3)2(R-L2)2]middot6CH3CN (1middotCH3CN) An acetonitrile solution (60 mL) of

FeSO4middot7H2O (00278 g 01 mmol) and NaNCBH3 (00157 g 025 mmol) in the presence of 55 mg

ascorbic acid was added to the bottom of a test tube 40 mL acetonitrile was added as the buffer

layer and then upon which another acetonitrile solution (50 mL) containing R-L2 (00288 g 005

mmol) was carefully layered The test tube was sealed and kept undisturbedly and orange crystals

were obtained in half a day Yield 25 mg ( 65 based on the ligand R-L2) Elemental analyses

() calcd for C90H80N12FeB2O8 C 7042 H 525 N 1095 Found C 7053 H 517 N 1062

The final formula of 1middotCH3CN was confirmed as [Fe(NCBH3)2(R-L2)2]middot6CH3CN by

thermogravimetric analysis IR (KBr pellet cmminus1) 2341 (m) 2207 (m) 2182 (m) 1605 (s) 1536

(w) 1474 (m) 1349 (m) 1303 (w) 1241 (m) 1217 (w) 1199 (w) 1150 (m) 1115 (w) 1071 (m)

1014 (s) 968 (w) 922 (w) 890 (w) 826 (s) 733 (w) 695 (w) 669 (w) 598 (w) 557 (w) 542 (m)

502 (w) 432 (w)

Yellow crystals of 1middotCH3OH were obtained via the solvent-treating process by immersing the

crystals of 1middotCH3CN in pure methanol for one day in a 15 mL sample-tube during which the

methanol solution was replaced with pure methanol every three hours Elemental analyses () calcd

for C86H94N6FeB2O16 C 6685 H 613 N 544 Found C 6698 H 607 N 546

Thermogravimetric and elemental analyses jointly fix the final formula of 1middotCH3OH as

[Fe(NCBH3)2(R-L2)2]middot8CH3OH IR (KBr pellet cmminus1) 2346 (w) 2337 (w) 2207 (m) 2183 (w)

1605 (s) 1535 (w) 1473 (m) 1350 (m) 1304 (w) 1241 (m) 1218 (w) 1200 (w) 1151 (s) 1114

(w) 1070 (m) 1015 (s) 968 (w) 920 (w) 890 (w) 827 (s) 734 (w) 694 (w) 669 (w) 599 (w)

556 (w) 542 (m) 501 (m) 430 (w)

The products 1middotH2O 1middotC2H5OH and 1middotC3H7OH were obtained following the procedure

preparing 1middotCH3OH except for the use of distilled water ethanol and n-propanol as solvents

respectively Crystals of 1 were prepared by placing crystals of 1middotCH3CN in vacuum oven at 80 degC

overnight

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 2: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S2

TABLE OF CONTENTS

Experimental Details∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4minusS6

Materials and methods ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4

Synthetic procedures∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S4

Single-crystal X-ray diffractometry∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S6

Additional Tables ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S7minusS10

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S7

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙S7

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙S8

Table S6 Structural parameters for the mechanical interactions at variable temperatures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S9

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S9

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S10

Additional Figures∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S11minusS22

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states ∙∙∙∙S11

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S11

Figure S3 Elemental mapping photographs and SEM image of single crystal of 1middotCH3CN∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S12

Figure S4 Elemental mapping photographs and SEM image of single crystal of 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S12

Figure S5 Thermogravimetric plots of 1middotCH3CN and 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S13

Figure S6 The general view of internal angles and dimensions in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S13

Figure S7 A possible interlocking process of 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S14

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S14

Figure S9 The view of the 1D open channels in the title 3D MIS framework ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S15

Figure S10 The stick and its simplified views of the linear poly[n]catenane structure in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S15

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions and the

perspective view of the three kinds of interactions in 1 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S16

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis and in the ac plane in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S16

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis and

in the ac plane in 1∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S17

S3

Figure S14 The SHG signals of 1middotCH3CN 1middotCH3OH R-L2 and KDP ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S17

Figure S15 View of the spin-state ordering of 1middotCH3OH at 160 K ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S16 Schematic representation of spin-state conversions of FeII ions in 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1middotH2O ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S20 Normalized variable temperature χMT versus T plots for 1middotCH3CN 1 1middotH2O 1middotCH3OH

1middotC2H5OH and 1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S21 The corresponding d(χMT)dT versus T plots for 1middotCH3CN 1middotCH3OH 1middotC2H5OH and

1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S22 IR spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S23 UV-vis spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S24 1H NMR spectra of ligand R-L2∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S22

References∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S23

S4

Experimental Details

Materials and methods

All chemical reagents were commercially available and used as purchased Powder X-ray diffraction

(PXRD) data were collected on a PANalytical diffractometer with Cu Kα (λ = 154056 Aring) radiation

The C H and N microanalyses were measured on a EUROVECTER EA3000 analyzer Fourier

transform infrared (FT-IR) spectra were performed on a Nicolet IS10 FT-IR spectrometer in the

range of 4000minus400 cmminus1 with KBr pellets Thermogravimetric (TG) analyses were recorded on a

TG-DTA 6200 instrument under a flowing nitrogen atmosphere in the temperature range 20minus700

degC at a heating rate of 10 degC minminus1 The 1H NMR spectrum was measured by a Bruker Avance 400

MHz spectrometer Magnetic susceptibility measurements of the polycrystalline samples were

measured on a Quantum Design MPMS XL7 magnetometer operating in the successive

coolingheating cycle with a scan rate of 1 K minminus1 Field-emission scanning electron microscopy

(FE-SEM) images were tested on a JSM-7500F scanning electron microscope with an accelerating

voltage of 50 kV UV-Vis spectra were obtained from a TU-1950 UV-Vis spectrophotometer with

BaSO4 as reference Solid-state circular dichroism (CD) spectra were carried out on a Jasco-810

spectropolarimeter with respective bulk sample using dried KBr pellets and the weight ratio are

adopted as 1middotCH3CN KBr = 1800 1middotCH3OH KBr = 1600 R-L2 KBr = 1600 Second

harmonic generation (SHG) signals of title compounds and KDP (particle size range of 30minus70 μm)

were performed on a Q-switched NdYAG solid-state laser at room temperature with a wavelength

of 1064 nm

Synthetic procedures

Synthesis of R-22-bis(methoxymethoxy)-66-bis(4-pyridylethynyl)-11-binaphth-yl (R-L2) The

ligand R-L2 was synthesized according to the published references12 Elemental analysis () calcd

for C38H28N2O4 C 7915 H 489 N 486 Found C 7923 H 487 N 483 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ

765minus763 (d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d

2H ArH) δ 515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3) IR

(KBr pellet cmminus1) 2208 (m) 2068 (w) 1927 (w) 1735 (w) 1620 (m) 1594 (s) 1536 (w) 1473

(m) 1405 (m) 1370 (w) 1348 (m) 1301 (w) 1244 (m) 1194 (m) 1150 (s) 1069 (s) 1026 (s) 968

S5

(w) 921 (w) 889 (w) 874 (w) 819 (s) 729 (w) 692 (m) 669 (w) 626 (w) 591 (w) 556 (m) 542

(s) 500 (m) 448 (w) 427 (m)

Preparation of [Fe(NCBH3)2(R-L2)2]middot6CH3CN (1middotCH3CN) An acetonitrile solution (60 mL) of

FeSO4middot7H2O (00278 g 01 mmol) and NaNCBH3 (00157 g 025 mmol) in the presence of 55 mg

ascorbic acid was added to the bottom of a test tube 40 mL acetonitrile was added as the buffer

layer and then upon which another acetonitrile solution (50 mL) containing R-L2 (00288 g 005

mmol) was carefully layered The test tube was sealed and kept undisturbedly and orange crystals

were obtained in half a day Yield 25 mg ( 65 based on the ligand R-L2) Elemental analyses

() calcd for C90H80N12FeB2O8 C 7042 H 525 N 1095 Found C 7053 H 517 N 1062

The final formula of 1middotCH3CN was confirmed as [Fe(NCBH3)2(R-L2)2]middot6CH3CN by

thermogravimetric analysis IR (KBr pellet cmminus1) 2341 (m) 2207 (m) 2182 (m) 1605 (s) 1536

(w) 1474 (m) 1349 (m) 1303 (w) 1241 (m) 1217 (w) 1199 (w) 1150 (m) 1115 (w) 1071 (m)

1014 (s) 968 (w) 922 (w) 890 (w) 826 (s) 733 (w) 695 (w) 669 (w) 598 (w) 557 (w) 542 (m)

502 (w) 432 (w)

Yellow crystals of 1middotCH3OH were obtained via the solvent-treating process by immersing the

crystals of 1middotCH3CN in pure methanol for one day in a 15 mL sample-tube during which the

methanol solution was replaced with pure methanol every three hours Elemental analyses () calcd

for C86H94N6FeB2O16 C 6685 H 613 N 544 Found C 6698 H 607 N 546

Thermogravimetric and elemental analyses jointly fix the final formula of 1middotCH3OH as

[Fe(NCBH3)2(R-L2)2]middot8CH3OH IR (KBr pellet cmminus1) 2346 (w) 2337 (w) 2207 (m) 2183 (w)

1605 (s) 1535 (w) 1473 (m) 1350 (m) 1304 (w) 1241 (m) 1218 (w) 1200 (w) 1151 (s) 1114

(w) 1070 (m) 1015 (s) 968 (w) 920 (w) 890 (w) 827 (s) 734 (w) 694 (w) 669 (w) 599 (w)

556 (w) 542 (m) 501 (m) 430 (w)

The products 1middotH2O 1middotC2H5OH and 1middotC3H7OH were obtained following the procedure

preparing 1middotCH3OH except for the use of distilled water ethanol and n-propanol as solvents

respectively Crystals of 1 were prepared by placing crystals of 1middotCH3CN in vacuum oven at 80 degC

overnight

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 3: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S3

Figure S14 The SHG signals of 1middotCH3CN 1middotCH3OH R-L2 and KDP ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S17

Figure S15 View of the spin-state ordering of 1middotCH3OH at 160 K ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S16 Schematic representation of spin-state conversions of FeII ions in 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1middotCH3OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S18

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1middotH2O ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S19

Figure S20 Normalized variable temperature χMT versus T plots for 1middotCH3CN 1 1middotH2O 1middotCH3OH

1middotC2H5OH and 1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S21 The corresponding d(χMT)dT versus T plots for 1middotCH3CN 1middotCH3OH 1middotC2H5OH and

1middotC3H7OH ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S20

Figure S22 IR spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S23 UV-vis spectra of 1middotCH3CN 1middotCH3OH and ligand R-L2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S21

Figure S24 1H NMR spectra of ligand R-L2∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S22

References∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙S23

S4

Experimental Details

Materials and methods

All chemical reagents were commercially available and used as purchased Powder X-ray diffraction

(PXRD) data were collected on a PANalytical diffractometer with Cu Kα (λ = 154056 Aring) radiation

The C H and N microanalyses were measured on a EUROVECTER EA3000 analyzer Fourier

transform infrared (FT-IR) spectra were performed on a Nicolet IS10 FT-IR spectrometer in the

range of 4000minus400 cmminus1 with KBr pellets Thermogravimetric (TG) analyses were recorded on a

TG-DTA 6200 instrument under a flowing nitrogen atmosphere in the temperature range 20minus700

degC at a heating rate of 10 degC minminus1 The 1H NMR spectrum was measured by a Bruker Avance 400

MHz spectrometer Magnetic susceptibility measurements of the polycrystalline samples were

measured on a Quantum Design MPMS XL7 magnetometer operating in the successive

coolingheating cycle with a scan rate of 1 K minminus1 Field-emission scanning electron microscopy

(FE-SEM) images were tested on a JSM-7500F scanning electron microscope with an accelerating

voltage of 50 kV UV-Vis spectra were obtained from a TU-1950 UV-Vis spectrophotometer with

BaSO4 as reference Solid-state circular dichroism (CD) spectra were carried out on a Jasco-810

spectropolarimeter with respective bulk sample using dried KBr pellets and the weight ratio are

adopted as 1middotCH3CN KBr = 1800 1middotCH3OH KBr = 1600 R-L2 KBr = 1600 Second

harmonic generation (SHG) signals of title compounds and KDP (particle size range of 30minus70 μm)

were performed on a Q-switched NdYAG solid-state laser at room temperature with a wavelength

of 1064 nm

Synthetic procedures

Synthesis of R-22-bis(methoxymethoxy)-66-bis(4-pyridylethynyl)-11-binaphth-yl (R-L2) The

ligand R-L2 was synthesized according to the published references12 Elemental analysis () calcd

for C38H28N2O4 C 7915 H 489 N 486 Found C 7923 H 487 N 483 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ

765minus763 (d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d

2H ArH) δ 515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3) IR

(KBr pellet cmminus1) 2208 (m) 2068 (w) 1927 (w) 1735 (w) 1620 (m) 1594 (s) 1536 (w) 1473

(m) 1405 (m) 1370 (w) 1348 (m) 1301 (w) 1244 (m) 1194 (m) 1150 (s) 1069 (s) 1026 (s) 968

S5

(w) 921 (w) 889 (w) 874 (w) 819 (s) 729 (w) 692 (m) 669 (w) 626 (w) 591 (w) 556 (m) 542

(s) 500 (m) 448 (w) 427 (m)

Preparation of [Fe(NCBH3)2(R-L2)2]middot6CH3CN (1middotCH3CN) An acetonitrile solution (60 mL) of

FeSO4middot7H2O (00278 g 01 mmol) and NaNCBH3 (00157 g 025 mmol) in the presence of 55 mg

ascorbic acid was added to the bottom of a test tube 40 mL acetonitrile was added as the buffer

layer and then upon which another acetonitrile solution (50 mL) containing R-L2 (00288 g 005

mmol) was carefully layered The test tube was sealed and kept undisturbedly and orange crystals

were obtained in half a day Yield 25 mg ( 65 based on the ligand R-L2) Elemental analyses

() calcd for C90H80N12FeB2O8 C 7042 H 525 N 1095 Found C 7053 H 517 N 1062

The final formula of 1middotCH3CN was confirmed as [Fe(NCBH3)2(R-L2)2]middot6CH3CN by

thermogravimetric analysis IR (KBr pellet cmminus1) 2341 (m) 2207 (m) 2182 (m) 1605 (s) 1536

(w) 1474 (m) 1349 (m) 1303 (w) 1241 (m) 1217 (w) 1199 (w) 1150 (m) 1115 (w) 1071 (m)

1014 (s) 968 (w) 922 (w) 890 (w) 826 (s) 733 (w) 695 (w) 669 (w) 598 (w) 557 (w) 542 (m)

502 (w) 432 (w)

Yellow crystals of 1middotCH3OH were obtained via the solvent-treating process by immersing the

crystals of 1middotCH3CN in pure methanol for one day in a 15 mL sample-tube during which the

methanol solution was replaced with pure methanol every three hours Elemental analyses () calcd

for C86H94N6FeB2O16 C 6685 H 613 N 544 Found C 6698 H 607 N 546

Thermogravimetric and elemental analyses jointly fix the final formula of 1middotCH3OH as

[Fe(NCBH3)2(R-L2)2]middot8CH3OH IR (KBr pellet cmminus1) 2346 (w) 2337 (w) 2207 (m) 2183 (w)

1605 (s) 1535 (w) 1473 (m) 1350 (m) 1304 (w) 1241 (m) 1218 (w) 1200 (w) 1151 (s) 1114

(w) 1070 (m) 1015 (s) 968 (w) 920 (w) 890 (w) 827 (s) 734 (w) 694 (w) 669 (w) 599 (w)

556 (w) 542 (m) 501 (m) 430 (w)

The products 1middotH2O 1middotC2H5OH and 1middotC3H7OH were obtained following the procedure

preparing 1middotCH3OH except for the use of distilled water ethanol and n-propanol as solvents

respectively Crystals of 1 were prepared by placing crystals of 1middotCH3CN in vacuum oven at 80 degC

overnight

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 4: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S4

Experimental Details

Materials and methods

All chemical reagents were commercially available and used as purchased Powder X-ray diffraction

(PXRD) data were collected on a PANalytical diffractometer with Cu Kα (λ = 154056 Aring) radiation

The C H and N microanalyses were measured on a EUROVECTER EA3000 analyzer Fourier

transform infrared (FT-IR) spectra were performed on a Nicolet IS10 FT-IR spectrometer in the

range of 4000minus400 cmminus1 with KBr pellets Thermogravimetric (TG) analyses were recorded on a

TG-DTA 6200 instrument under a flowing nitrogen atmosphere in the temperature range 20minus700

degC at a heating rate of 10 degC minminus1 The 1H NMR spectrum was measured by a Bruker Avance 400

MHz spectrometer Magnetic susceptibility measurements of the polycrystalline samples were

measured on a Quantum Design MPMS XL7 magnetometer operating in the successive

coolingheating cycle with a scan rate of 1 K minminus1 Field-emission scanning electron microscopy

(FE-SEM) images were tested on a JSM-7500F scanning electron microscope with an accelerating

voltage of 50 kV UV-Vis spectra were obtained from a TU-1950 UV-Vis spectrophotometer with

BaSO4 as reference Solid-state circular dichroism (CD) spectra were carried out on a Jasco-810

spectropolarimeter with respective bulk sample using dried KBr pellets and the weight ratio are

adopted as 1middotCH3CN KBr = 1800 1middotCH3OH KBr = 1600 R-L2 KBr = 1600 Second

harmonic generation (SHG) signals of title compounds and KDP (particle size range of 30minus70 μm)

were performed on a Q-switched NdYAG solid-state laser at room temperature with a wavelength

of 1064 nm

Synthetic procedures

Synthesis of R-22-bis(methoxymethoxy)-66-bis(4-pyridylethynyl)-11-binaphth-yl (R-L2) The

ligand R-L2 was synthesized according to the published references12 Elemental analysis () calcd

for C38H28N2O4 C 7915 H 489 N 486 Found C 7923 H 487 N 483 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ

765minus763 (d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d

2H ArH) δ 515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3) IR

(KBr pellet cmminus1) 2208 (m) 2068 (w) 1927 (w) 1735 (w) 1620 (m) 1594 (s) 1536 (w) 1473

(m) 1405 (m) 1370 (w) 1348 (m) 1301 (w) 1244 (m) 1194 (m) 1150 (s) 1069 (s) 1026 (s) 968

S5

(w) 921 (w) 889 (w) 874 (w) 819 (s) 729 (w) 692 (m) 669 (w) 626 (w) 591 (w) 556 (m) 542

(s) 500 (m) 448 (w) 427 (m)

Preparation of [Fe(NCBH3)2(R-L2)2]middot6CH3CN (1middotCH3CN) An acetonitrile solution (60 mL) of

FeSO4middot7H2O (00278 g 01 mmol) and NaNCBH3 (00157 g 025 mmol) in the presence of 55 mg

ascorbic acid was added to the bottom of a test tube 40 mL acetonitrile was added as the buffer

layer and then upon which another acetonitrile solution (50 mL) containing R-L2 (00288 g 005

mmol) was carefully layered The test tube was sealed and kept undisturbedly and orange crystals

were obtained in half a day Yield 25 mg ( 65 based on the ligand R-L2) Elemental analyses

() calcd for C90H80N12FeB2O8 C 7042 H 525 N 1095 Found C 7053 H 517 N 1062

The final formula of 1middotCH3CN was confirmed as [Fe(NCBH3)2(R-L2)2]middot6CH3CN by

thermogravimetric analysis IR (KBr pellet cmminus1) 2341 (m) 2207 (m) 2182 (m) 1605 (s) 1536

(w) 1474 (m) 1349 (m) 1303 (w) 1241 (m) 1217 (w) 1199 (w) 1150 (m) 1115 (w) 1071 (m)

1014 (s) 968 (w) 922 (w) 890 (w) 826 (s) 733 (w) 695 (w) 669 (w) 598 (w) 557 (w) 542 (m)

502 (w) 432 (w)

Yellow crystals of 1middotCH3OH were obtained via the solvent-treating process by immersing the

crystals of 1middotCH3CN in pure methanol for one day in a 15 mL sample-tube during which the

methanol solution was replaced with pure methanol every three hours Elemental analyses () calcd

for C86H94N6FeB2O16 C 6685 H 613 N 544 Found C 6698 H 607 N 546

Thermogravimetric and elemental analyses jointly fix the final formula of 1middotCH3OH as

[Fe(NCBH3)2(R-L2)2]middot8CH3OH IR (KBr pellet cmminus1) 2346 (w) 2337 (w) 2207 (m) 2183 (w)

1605 (s) 1535 (w) 1473 (m) 1350 (m) 1304 (w) 1241 (m) 1218 (w) 1200 (w) 1151 (s) 1114

(w) 1070 (m) 1015 (s) 968 (w) 920 (w) 890 (w) 827 (s) 734 (w) 694 (w) 669 (w) 599 (w)

556 (w) 542 (m) 501 (m) 430 (w)

The products 1middotH2O 1middotC2H5OH and 1middotC3H7OH were obtained following the procedure

preparing 1middotCH3OH except for the use of distilled water ethanol and n-propanol as solvents

respectively Crystals of 1 were prepared by placing crystals of 1middotCH3CN in vacuum oven at 80 degC

overnight

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 5: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S5

(w) 921 (w) 889 (w) 874 (w) 819 (s) 729 (w) 692 (m) 669 (w) 626 (w) 591 (w) 556 (m) 542

(s) 500 (m) 448 (w) 427 (m)

Preparation of [Fe(NCBH3)2(R-L2)2]middot6CH3CN (1middotCH3CN) An acetonitrile solution (60 mL) of

FeSO4middot7H2O (00278 g 01 mmol) and NaNCBH3 (00157 g 025 mmol) in the presence of 55 mg

ascorbic acid was added to the bottom of a test tube 40 mL acetonitrile was added as the buffer

layer and then upon which another acetonitrile solution (50 mL) containing R-L2 (00288 g 005

mmol) was carefully layered The test tube was sealed and kept undisturbedly and orange crystals

were obtained in half a day Yield 25 mg ( 65 based on the ligand R-L2) Elemental analyses

() calcd for C90H80N12FeB2O8 C 7042 H 525 N 1095 Found C 7053 H 517 N 1062

The final formula of 1middotCH3CN was confirmed as [Fe(NCBH3)2(R-L2)2]middot6CH3CN by

thermogravimetric analysis IR (KBr pellet cmminus1) 2341 (m) 2207 (m) 2182 (m) 1605 (s) 1536

(w) 1474 (m) 1349 (m) 1303 (w) 1241 (m) 1217 (w) 1199 (w) 1150 (m) 1115 (w) 1071 (m)

1014 (s) 968 (w) 922 (w) 890 (w) 826 (s) 733 (w) 695 (w) 669 (w) 598 (w) 557 (w) 542 (m)

502 (w) 432 (w)

Yellow crystals of 1middotCH3OH were obtained via the solvent-treating process by immersing the

crystals of 1middotCH3CN in pure methanol for one day in a 15 mL sample-tube during which the

methanol solution was replaced with pure methanol every three hours Elemental analyses () calcd

for C86H94N6FeB2O16 C 6685 H 613 N 544 Found C 6698 H 607 N 546

Thermogravimetric and elemental analyses jointly fix the final formula of 1middotCH3OH as

[Fe(NCBH3)2(R-L2)2]middot8CH3OH IR (KBr pellet cmminus1) 2346 (w) 2337 (w) 2207 (m) 2183 (w)

1605 (s) 1535 (w) 1473 (m) 1350 (m) 1304 (w) 1241 (m) 1218 (w) 1200 (w) 1151 (s) 1114

(w) 1070 (m) 1015 (s) 968 (w) 920 (w) 890 (w) 827 (s) 734 (w) 694 (w) 669 (w) 599 (w)

556 (w) 542 (m) 501 (m) 430 (w)

The products 1middotH2O 1middotC2H5OH and 1middotC3H7OH were obtained following the procedure

preparing 1middotCH3OH except for the use of distilled water ethanol and n-propanol as solvents

respectively Crystals of 1 were prepared by placing crystals of 1middotCH3CN in vacuum oven at 80 degC

overnight

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 6: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S6

Single-crystal X-ray diffractometry (SCXRD)

Variable-temperature single-crystal X-ray diffraction (SCXRD) experiments at 100 K 160 K 240

K for 1middotCH3CN and 1middotCH3OH were performed on a Bruker D8 VENTURE PHOTON II

diffractometer equipped with a microfocus radiation source (Cu-Kα λ = 154178 Aring) The title

mechanically interlocked structures were solved by the direct method and refined by full-matrix

least-squares on F2 with SHELXL software package3 In the final refinement the reflection

contributions of highly disordered solvent molecules were removed using the OLEX2 solvent

MASK routine (similar to PLATONSQUEEZE)4 All hydrogen atoms were fixed in the calculated

positions and refined using a riding model The weak diffraction intensity to the resolution higher

than 10 Aring of single crystal is responsible for the corresponding alert the value of

sin(theta_max)wavelength is less than 0550 or 0575 For 1middotCH3CN the O8minusC78 section was

refined isotropically and split as O8AminusC78A O8BminusC78B at 100 160 and 240 K and C72 at 240

K was also refined isotropically Other non-hydrogen atoms were refined anisotropically The

contributions of 6680 (100 K) 6744 (160 K) 7280 (240 K) electrons were removed from the unit-

cell contents The crystal data and structure refinement results revealed that the presence of 75~80

acetonitrile molecules per formula unit However TG and elemental analyses showed that the

number of acetonitrile molecules might be 6 for the empirical formula of [Fe(NCBH3)2(R-

L2)2]middot6CH3CN (C90H80N12FeB2O8) This might be attributed to the weathering of the test samples

For 1middotCH3OH C156 at 160 K was refined isotropically and other non-hydrogen atoms were refined

anisotropically The contributions of 8480 (100 K) 8683 (160 K) 7746 (240 K) electrons were

removed from the unit-cell contents corresponding to 105~12 methanol molecules per formula

unit However TG and elemental analyses showed the number of methanol molecules might be 8

for the empirical formula of [Fe(NCBH3)2(R-L2)2]middot8CH3OH (C86H94N6FeB2O16) This also might

be attributed to the weathering of the test samples The final formulas were determined by the

combination of SCXRD analyses elemental data and TG data Crystallographic parameters and

structural refinement results were summarized in Table S1 Selected bond lengths and angles are

listed in Table S7 and Table S8 CCDC 1942449 (100 K) 1966026 (160 K) 1942451 (240 K) for

1middotCH3CN and 1942452 (100 K) 1942453 (160 K) 1942454 (240 K) for 1middotCH3OH contain the

supplementary crystallographic data and can be obtained free of charge from the Cambridge

Crystallographic Data Centre via httpwwwccdccamacukdata_requestcif

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 7: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S7

Additional Tables

Table S1 Crystallographic data and refinement parameters for 1middotCH3CN and 1middotCH3OH (The formula and formula weight containing six acetonitrile molecules for 1middotCH3CN and eight methanol molecules for 1middotCH3OH at 100 K 240 K and sixteen methanol molecules at 160 K)

Compound 1middotCH3CN 1middotCH3OHTK 100 K 160 K 240 K 100 K 160 K 240 K

formula C90H80N12FeB2O8 C90H80N12FeB2O8 C90H80N12FeB2O8 C86H94N6FeB2O16 C172H188N12Fe2B4O32 C86H94N6FeB2O16

Mrg molminus1 153514 153514 153514 154516 309033 154516

space group C2 C2 C2 C2 P21 C2

crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic

aAring 319544(10) 32027(15) 32761(8) 318352(13) 18080(6) 3245(2)

bAring 164618(5) 1664(1) 16907(4) 166477(6) 16715(6) 16983(9)

cAring 178159(5) 17903(8) 18032(4) 179355(6) 32015(8) 18105(14)

αdeg 90 90 90 90 90 90

βdeg 104814(2) 105183(14) 106009(9) 105495(2) 106028(12) 10685(4)

γdeg 90 90 90 90 90 90

VAring3 90601(5) 9208(8) 9600(4) 91600(6) 9299(5) 9550(11)

Z 4 4 4 4 2 4

Dcalcdg cmndash3 0941 0926 0887 0935 0921 0896

μmmndash1 1704 1677 1608 1686 1661 1617

F(000) 2668 2668 2660 2688 2688 2688

R1 (I ge 2σ(I))a 00695 00655 00774 00712 00597 00619

wR2 (all data)b 01967 01920 02429 02000 01619 01763

Flack parameter 0091(9) 0129(7) 0100(10) 0002(8) 0056(4) 0075(7)

CCDC 1942449 1966026 1942451 1942452 1942453 1942454

a b1198771 = sum||119865119900| ‒ |119865119888||sum|119865119900| 1199081198772 = sum[119908(1198652

119900 ‒ 1198652119888)2]sum[119908(1198652

119900)2]12

Table S2 Internal angles and dimensions in 1middotCH3CN and 1middotCH3OH at variable temperatures

T internal angles (deg) diagonal dimensions (Aring)

(K) angLFeL angFeLFe FeFe LL

1middotCH3CN 240 6887(1) 69636(11) 110557(12) 110869(12) 224057(47) 154747(25)

160 67362(10) 67949(10) 112218(12) 112442(12) 222711(74) 149258(46)

100 67172(8) 67003(9) 112177(10) 11259(1) 222456(24) 148906(3)

1middotCH3OH 240 70520(12) 70711(12) 109317(14) 109428(14) 222002(134) 157245(82)

160 72177(5) 73543(5)

68019(5) 67454(5)

107309(6) 106961(6)

111590(7) 112912(7)

217953(41)

224452(44)

160856(44)

150663(41)

100 69325(7) 69346(7) 110554(8) 110727 (8) 221765(18) 153396(4)

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 8: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S8

Table S3 The distance between the neighboring 1D corner-sharing looped structures in 1middotCH3CN and

1middotCH3OH at variable temperatures

T (K) θ (deg) sin θ c (Aring) d (Aring)

1middotCH3CN 240 29683 04952 114739 568

160 29517 04927 112515 554

100 29064 04858 112727 548

1middotCH3OH 240 28917 04835 111972 541

160 28950 04840 108652 526

28458 04765 113271 540

100 28328 04745 111917 531

Table S4 The included angle in 1middotCH3CN and 1middotCH3OH at variable temperatures

T (K) included angle (deg)

1middotCH3CN 240 56462(20)

160 56592(14)

100 56104(10)

1middotCH3OH 240 57343(16)

160 56802(10)

100 56974(7)

Table S5 The size of 1D open channels in 1middotCH3CN and 1middotCH3OH at variable temperatures

T K void channel percent void unit cell volume Aring3 dimension Aring times Aring

1middotCH3CN 240 355 34123 96805 times 68592

160 337 30991 97091 times 65995

100 325 29449 91951 times 60637

1middotCH3OH 240 365 34869 102412 times 65241

160 349 32434 101658 times 61033

100 346 31653 103348 times 58719

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 9: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S9

Table S6 Structural parameters for the mechanical interactions at variable temperatures

T K CminusHπ interactions Aring (A) ππ interactions Aring (B) CminusHπ interactions Aring (C)

1middotCH3CN 240 29479(5) 32904(6) 44842(9) 31659(6) 37271(7)

160 27692(10) 33768(13) 44639(18) 30338(12) 38222(13)

100 27362(1) 32892(1) 44284(1) 30537(1) 38535(1)

1middotCH3OH 240 28272(19) 29128(21) 40960(28) 40722(28) 40863(30)

160 27687(9) 27941(9)

28988(9) 36223(11)

44709(15) 30518(9) 33978(7)

39328(9) 40587(13)

100 27780(1) 28074(1) 38592(1) 44635(1) 46462(2)

Table S7 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3CN

1middotCH3CN 100 K 160 K 240 K

Fe1minusN1 1890(14) 1829(11) 2010(15)

Fe1minusN2 1960(15) 1997(11) 2071(15)

Fe1minusN3 2003(11) 2063(10) 2177(13)

Fe1minusN4 1989(9) 2009(9) 2242(12)

Fe1minusN5 2000(8) 2004(7) 2195(11)

Fe1minusN6 2012(9) 2039(8) 2221(10)

N1minusFe1minusN3 918(5) 924(5) 904(5)

N1minusFe1minusN4 897(5) 900(4) 899(6)

N1minusFe1minusN5 895(5) 907(4) 895(5)

N1minusFe1minusN6 916(5) 895(4) 892(5)

N2minusFe1minusN3 898(5) 906(4) 880(6)

N2minusFe1minusN4 887(4) 870(4) 918(6)

N2minusFe1minusN5 888(5) 890(4) 897(6)

N2minusFe1minusN6 901(5) 907(4) 917(5)

N3minusFe1minusN6 890(4) 914(4) 887(4)

N4minusFe1minusN5 880(4) 875(3) 861(4)

N4minusFe1minusN6 912(4) 913(3) 925(4)

N5minusFe1minusN3 917(4) 898(4) 927(5)

langdFe1minusNranga 1976 1990 2153

ΣFe1b 1290 1430 1800

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 10: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S10

Table S8 Selected Bond Lengths (Aring) and Angles (deg) for 1middotCH3OH

1middotCH3OH 100 K 160 K 240 K

Fe1minusN1 Fe2minusN7 1996(8) 2085(2) 19395(19) 2061(9)

Fe1minusN2 Fe2minusN8 1968(9) 2084(2) 19268(19) 2180(9)

Fe1minusN3 Fe2minusN9 2000(7) 2187(2) 20217(19) 2205(7)

Fe1minusN4 Fe2minusN10 2025(9) 2198(2) 20113(19) 2196(7)

Fe1minusN5 Fe2minusN11 2021(7) 2173(2) 20026(18) 2198(6)

Fe1minusN6 Fe2minusN12 2047(8) 2183(2) 20073(19) 2208(6)

N1minusFe1minusN3 N7minusFe2minusN9 911(3) 8674(8) 9278(8) 926(3)

N1minusFe1minusN4 N7minusFe2minusN10 893(3) 9072(9) 8985(8) 905(3)

N1minusFe1minusN5 N7minusFe2minusN11 902(3) 9274(9) 9021(8) 893(3)

N1minusFe1minusN6 N7minusFe2minusN12 868(3) 9116(9) 8953(8) 877(3)

N2minusFe1minusN3 N8minusFe2minusN9 883(3) 9183(8) 8780(8) 865(3)

N2minusFe1minusN4 N8minusFe2minusN10 913(4) 9079(9) 8967(8) 905(3)

N2minusFe1minusN5 N8minusFe2minusN11 901(3) 8937(9) 9232(8) 908(3)

N2minusFe1minusN6 N8minusFe2minusN12 929(3) 8674(9) 8794(8) 922(3)

N4minusFe1minusN5 N10minusFe2minusN11 900(3) 9154(8) 9000(7) 899(2)

N4minusFe1minusN6 N10minusFe2minusN12 905(3) 8791(8) 9099(7) 921(3)

N5minusFe1minusN3 N11minusFe2minusN9 910(3) 8645(8) 8777(7) 916(2)

N6minusFe1minusN3 N12minusFe2minusN9 885(3) 9427(8) 9126(7) 866(2)

langdFe1minusNrang langdFe2minusNranga 2009 2152 1984 2175

ΣFe1 ΣFe2b 142 257 150 203

alangdFeminusNrang the average FeminusN bond lengths bΣFe the sum of the deviations of NminusFeminusN angles from 90deg56

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 11: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S11

Additional Figures

Figure S1 The remarkable color variation of 1middotCH3CN and 1middotCH3OH between HS and LS states

Figure S2 Comparison of the PXRD patterns of 1middotCH3CN and 1middotCH3OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 12: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S12

Figure S3 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3CN

Figure S4 Elemental mapping photographs (C N O B and Fe) and SEM image of single crystal of

1middotCH3OH

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 13: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S13

Figure S5 Thermogravimetric plots of 1middotCH3CN (left) and 1middotCH3OH (right) corresponding to six

acetonitrile (calcd 1604 ) and eight methanol molecules (calcd 1659 ) respectively

Figure S6 The general view of internal angles and dimensions in 1 (the internal angles and dimensions

are marked) Color codes Fe sky blue N blue C grey O red B yellow Hydrogen atoms are omitted

for clarity

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 14: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S14

Figure S7 A possible interlocking process of 1 The identical 1D loops are shown in two different colors

for better view

Figure S8 The constructing of the right triangle to calculate the distance between the neighboring 1D

corner-sharing looped structures in 1

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 15: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S15

Figure S9 The view of the 1D open channels (pink) in the title 3D MIS framework Color codes Fe

sky blue N C B O and H atoms are grey-coloured to assist the viewer

Figure S10 The stick (top) and its simplified views (bottom) of the linear poly[n]catenane structure in

1 Hydrogen atoms and the MOMO groups are omitted for clarity

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 16: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S16

Figure S11 The mechanically interlocked loops with three kinds of mechanical interactions showing the

ABACmiddotmiddotmiddot manner (a) and perspective view of the three kinds of interactions (b) in 1 Hydrogen atoms

and the MOMO groups are omitted for clarity

Figure S12 Topological representation of the interlocked right-handed helical chains viewed along b-

axis (a b) and in the ac plane (c) in 1 The yellow tubes represent the helical axes and the identical 1D

loops are marked in red and blue for better view

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 17: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S17

Figure S13 The interlocking of four neighboring right-handed helical chains viewed along b-axis (a d)

and in the ac plane (b c) in 1 The yellow tubes represent the helical axes and the identical 1D loops are

marked in red and blue for better view

Figure S14 The SHG signals of 1CH3CN 1CH3OH R-L2 and KDP

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 18: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S18

Figure S15 View of the spin-state ordering of 1CH3OH at 160 K corresponding to the magnetic phases

of HS05LS05 (HS-Fe1 ions yellow balls LS-Fe2 ions purple balls)

Figure S16 Schematic representation of the spin-state conversions of FeII ions in 1CH3OH from 240

K to 100 K in a single layer corresponding to the magnetic phases sequence of HS10 harr HS05LS05 harr

LS10 (HS-Fe ions yellow balls LS-Fe ions purple balls)

Figure S17 Enlarged view of the hysteresis loop of 6 K of 1CH3OH in the first-step spin transition (

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 19: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S19

= 176 K = 182 K) TC1darr TC1uarr

Figure S18 Comparison of the PXRD patterns of 1C2H5OH and 1C3H7OH measured from respective

bulk polycrystalline-sample and the simulated result based on single-crystal structure

Figure S19 Powder X-ray diffraction of desolvated phase 1 and 1H2O

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 20: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S20

Figure S20 Normalized variable temperature χMT versus T plots for 1CH3CN 1 1H2O 1CH3OH

1C2H5OH and 1C3H7OH

Figure S21 The corresponding d(χMT)dT versus T plots for 1CH3CN ( = = 180 K) 1CH3OH TCdarr TCuarr

( = 176 K = 182 K = = 143 K) 1C2H5OH ( = = 177 K) and 1C3H7OH (TC1darr TC1uarr TC2darr TC2uarr TCdarr TCuarr

= = 159 K) TCdarr TCuarr

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 21: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S21

Figure S22 IR spectra of 1CH3CN 1CH3OH and ligand R-L2

Figure S23 UV-vis spectra of 1CH3CN 1CH3OH and ligand R-L2 in the solid state The strong

absorption band of ligand R-L2 was obtained between 270 and 380 nm while the broader absorption

bands in the range of 260minus500 nm were found in 1CH3CN and 1CH3OH

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 22: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S22

Figure S24 1H NMR spectra of ligand R-L2 (inset the structure of ligand R-L2) 1H NMR (400 MHz

CDCl3 ppm) δ 861minus859 (m 4H ArH) δ 814 (d 2H ArH) δ 798minus796 (d 2H ArH) δ 765minus763

(d 2H ArH) δ 740minus738 (m 4H ArH) δ 735minus733 (dd 2H ArH) δ 715minus713 (d 2H ArH) δ

515minus513 (d 2H minusCH2minus) δ 503minus501 (d 2H minusCH2minus) δ 318 (s 6H minusCH3)

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567

Page 23: loops with solvent-dependent spin-state switching behaviors ...mechanically interlocked structures were solved by the direct method and refined by full-matrix least-squares on F 2

S23

References

(1) J Bunzen T Bruhn G Bringmann and A Luumltzen J Am Chem Soc 2009 131 3621ndash3630

(2) C Guumltz R Hovorka C Stobe N Struch F Topić G Schnakenburg K Rissanen and A Luumltzen

Eur J Org Chem 2014 2014 206ndash216

(3) G M Sheldrick Acta Crystallogr Sect C 2015 71 3minus8

(4) O V Dolomanov L J Bourhis R J Gildea J A K Howard and H Puschmann J Appl Cryst

2009 42 339ndash341

(5) P Guionneau M Marchivie G Bravic J-F Leacutetard D Chasseau J Mater Chem 2002 12

2546minus2551

(6) Q Yang X Cheng C Gao B Wang Z Wang S Gao Cryst Growth Des 2015 15 2565minus2567