69451 Weinheim, Germany - Wiley-VCH · S1 Crystal-to-Crystal Transformation between Three Cu(I)...

Supporting Information

© Wiley-VCH 2007

69451 Weinheim, Germany

S1

Crystal-to-Crystal Transformation between Three Cu(I) Coordination Polymers and Structural Evidence for Luminescence

Thermochromism

Tae Ho Kim1, Yong Woon Shin2, Jong Hwa Jung1, Jae Sang Kim1, and Jineun Kim1*

1 Department of Chemistry (BK21) and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, S. Korea

2 Test & Analytical Laboratory, Korea Food & Drug Administration, Busan 608-829, South Korea

Table of Contents: Title and table of contents································································ S1 General······················································································· S3 Scheme S1. Synthesis of 1,4-bis((methylthio)propanoyl)piperazine (L).··········· S3 Preparations of 1, 2, 3, and 3’ ··························································· S4 Figure S1. Ortep diagram of L. ··························································· S5 Table S1. Crystal data and structure refinement for L. ································ S5 Figure S2. Photograph of crystals 1, 2, and 3 with/without UV irradiation. ······· S6 Figure S3. SEM images of 1, 2, and 3’. ················································· S7 Figure S4. Ortep (a) and packing (b) diagrams of 1. ·································· S8 Table S2. Crystal data and structure refinement for 1.································· S9 Figure S5. Ortep (a) and packing (b) diagrams of 2. ·································· S10 Table S3. Crystal data and structure refinement for 2.································· S11 Figure S6. Ortep (a) and packing (b) diagrams of 3. ·································· S12 Table S4. Crystal data and structure refinement for 3.································· S13 Figure S7. Conformation of L. ··························································· S14 Figure S8. Packing arrangements of Cu4I4. ············································· S14 Table S4. Bond distances of 2 at four different temperatures. ························ S15 Table S5. Bond distances of 3 at four different temperatures. ························ S17 Figure S9. Photoluminescence spectra of before (a) and after (b) heating at

180 °C. ·············································································· S19

Figure S10. Powder XRD Patterns of 1.················································· S20 Figure S11. Powder XRD Patterns of 2.················································· S21

S2

Figure S12. Powder XRD Patterns of 3’ (a and b) and 3 (c).························· S22 Figrue S13. Thermogravimetric analysis (TGA) and differential thermal

analysis (DTA) traces for 1.······················································ S23 Figrue S14. Thermogravimetric analysis (TGA) and differential thermal

analysis (DTA) traces for 2.······················································ S23 Figrue S15. Thermogravimetric analysis (TGA) and differential thermal

analysis (DTA) traces for 3’.····················································· S24

S3

General The 1H and 13C NMR spectra were recorded with a Bruker Advance-300(300 MHz) NMR spectrometer.

The FT-IR spectra of the coordination polymers were measured with a Shimadzu FT-IR 8100

spectrometer. The elemental analysis was carried out on a LECO CHNS-932 elemental analyzer.

Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were performed under N2(g)

at a scan rate of 10 °C min-1 using a TA SDT Q600 thermal analyzer. For field emission scanning electron

microscope (FE-SEM) a piece of compounds was placed on a carbon tape after gold coating, the

specimen was then examined with Philips XL30 S FEG.

Scheme S1

SO

OHi ii

i. SOCl2, triethyl amineii. triethyl amine, thiomorpholine

SN

O

L

S

2-(cyclohexylthio)-1-thiomorpholinoethane (L). Thionyl chloride (2.38 g, 20.0 mmol) was added

dropwise to 2-cyclohexylthioacetic acid (3.48 g, 20.0 mmol) in the pesence of triethylamine (2.02 g, 20.0

mmol) in chloroform. The mixture was refluxed for 2 h and cooled down to room temperature. Then,

thiomorpholine (2.38 g, 20.0 mmol) and triethylamine (2.02 g, 20.0 mmol) in chloroform were added

dropwise to the resulting acid chloride solution, cooled by salt and ice water. The solution was stirred for

2 h, and then water was added. Organic layer was collected and water layer was extr

acted with chloroform. The combined organic layers dried with anhydrous sodium sulfate were

evaporated to give crude oil. Column chromatography (silica gel, ethyl acetate/hexane = 20/80 (v/v), Rf

0.2) gave pure product (4.18 g, 78%). 1H NMR (300 MHz, CDCl3): δ 3.857 (d, 4H, CH2NCH2), 3.326 (s,

2H, COCH2S), 2.805 (m, 1H SCH), 2.702 (d, 4H, CH2SCH2), 1.756 (m, 10H, CH(CH2)5). 13C NMR (75.4

MHz, CDCl3): δ 168.50, 44.33, 33.39, 32.08, 27.80, 27.39, 25.92, 25.74. IR(KBr, ν, cm-1): 2926 s, 2851 s,

1641 s, 1445 s, 1366 m, 1288 m, 1135 s, 1038 w, 999 w, 958 s, 917 m, 818 w, 738 w, 659 w. Mass

spectrum m/z 259 (M, 11 %), 145 (100), 130 (25), 117 (57), 102(15), 83 (20).

S4

Preparations of 1, 2, 3, and 3’

[Cu2I2L2]n (1): An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed to mix with an

acetonitrile (1 mL) solution of CuI (0.019 g , 0.10 mmol), followed by sonication. Yellowish-colored

precipitates were filtered and washed with diethyl ether/acetonitrile (1/1) solution (0.026 g, 58%). Single

crystals suitable for X-ray analysis were obtained by slow evaporation. m.p. 173-175 °C. IR(KBr, ν, cm-

1): 2931 s, 2852 s, 1660 s, 1424 s, 1367 m, 1287 m, 1177 s, 1039 w, 997 w, 956 s, 882 m, 817 w, 730 w,

649 w. [Cu2I2L2]n Anal. Calcd. for C24H42N2O2S4Cu2I2: C 32.04, H 4.70, N 3.11, S 14.25. Found: C 31.97,

H 4.66, N 3.27, S 14.39%.

[Cu4I4L2]n (2): An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed to mix with an

acetonitrile (1 mL) solution of CuI (0.038 g , 0.20 mmol), followed by diethyl ether diffusion and

sonication. White precipitates were filtered and washed with diethyl ether/acetonitrile (1/1) solution

(0.033 g, 52%). Single crystals suitable for X-ray analysis were obtained by diethyl ether diffusion. m.p.

202-204 °C. IR(KBr, ν, cm-1): 2921 s, 2847 m, 1642 s, 1440 s, 1364 w, 1294 m, 1253 w, 1130 w, 1044 w,

960 m, 923 w, 733 w, 651 w. [Cu4I4L2]n Anal. Calcd. for C24H42N2O2S4Cu4I4: C 22.51, H 3.31, N 2.19, S

10.02. Found: C 22.33, H 3.66, N 2.14, S 9.71%.

{[Cu4I4L2]·CH3CN·n-C6H12}n (3) An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed

to mix with an acetonitrile (1 mL) solution of CuI (0.038 g , 0.20 mmol), followed by diethyl ether/n-

Hexane (1/1) diffusion and sonication. White precipitates were filtered and washed with diethyl ether/n-

Hexane/acetonitrile (1/1/1) solution (0.044 g, 69%). Single crystals suitable for X-ray analysis were

obtained from boundary surface between n-hexane and acetonitrile solution (Figure S1b) .

[Cu4I4L2]n (3’): 3’ was obtained by desolvating the white precipitates 3 under vacuum for 1 hr. m.p. 176-

178 °C. IR(KBr, ν, cm-1): 2920 s, 2847 m, 1652 s, 1445 s, 1366 w, 1303 m, 1253 w, 1118 w, 1043 w, 958

m, 916 w, 729 w, 651 w. [Cu4I4L2]n Anal. Calcd. for C24H42N2O2S4Cu4I4: C 22.51, H 3.31, N 2.19, S

10.02. Found: C 22.55, H 3.46, N 2.35, S 10.29%.

S5

Figure S1. Ortep diagram of L. Table S1. Crystal data and structure refinement for L. ---------------------------------------------------------------------------------------------------------- Empirical formula C12H21NOS2 Formula weight 259.42 Temperature 173(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 14.0036(6) Å α= 90°. b = 9.3364(4) Å β= 94.4060(10)°. c = 10.2501(4) Å γ = 90°. Volume 1336.17(10) Å3 Z 4 Density (calculated) 1.290 g/cm3 Absorption coefficient 0.379 mm-1 F(000) 560 Crystal size 0.35 x 0.25 x 0.15 mm3 Theta range for data collection 2.62 to 28.27°. Index ranges -18<=h<=17, -11<=k<=12, -9<=l<=13 Reflections collected 8357 Independent reflections 3165 [R(int) = 0.0286] Completeness to theta = 28.27° 95.3 % Absorption correction Empirical ψ-scan Max. and min. transmission 0.2846 and 0.2228 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3165 / 0 / 145 Goodness-of-fit on F2 1.058 Final R indices [I>2sigma(I)] R1 = 0.0338, wR2 = 0.0848 R indices (all data) R1 = 0.0452, wR2 = 0.0910 Largest diff. peak and hole 0.323 and -0.245 e.Å-3 ----------------------------------------------------------------------------------------------------------

S6

Figure S2. Photograph of crystals 1, 2, and 3 with/without UV irradiation; yellow crystal 1 and white crystal 2 (top), orange luminescent 2 (bottom) (a), green luminescent 3 grown from boundary surface between n-hexane layer and acetonitrile solution (b), block crystal 2 and plate (urchin shape) crystal 3 (top), orange luminescent 2 and green luminescent 3 (bottom) (c).

(b)

(a) (c)

UV irradiation UV irradiation

S7

(a)

(b) (c) Figure S3. SEM images of 1, 2, and 3’; rhombohedron-shape block 1 (a), hexagonal-shape block 2 (b), and plate 3’ (c).

S8

(a)

(b)

Figure S4. Ortep (a) and packing (b) diagrams of 1. Hydrogen atoms are omitted.

S9

Table S2. Crystal data and structure refinement for 1. ---------------------------------------------------------------------------------------------------------- Empirical formula C12H21NOS2CuI

Formula weight 449.86

Temperature 173(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)/c

Unit cell dimensions a = 10.4687(5) Å α= 90°.

b = 8.7776(4) Å β= 103.5330(10)°.

c = 17.4451(8) Å γ = 90°.

Volume 1558.52(13) Å3

Z 4

Density (calculated) 1.917 g/cm3

Absorption coefficient 3.639 mm-1

F(000) 888

Crystal size 0.20 x 0.16 x 0.05 mm3

Theta range for data collection 2.00 to 28.32°.

Index ranges -11<=h<=13, -11<=k<=9, -22<=l<=23

Reflections collected 9544

Independent reflections 3657 [R(int) = 0.0549]

Completeness to theta = 28.32° 94.4 %

Absorption correction Empirical ψ-scan

Max. and min. transmission 0.3505 and 0.2406

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 3657 / 0 / 163

Goodness-of-fit on F2 1.024

Final R indices [I>2sigma(I)] R1 = 0.0305, wR2 = 0.0594

R indices (all data) R1 = 0.0489, wR2 = 0.0646

Largest diff. peak and hole 0.981 and -0.645 e.Å-3 ----------------------------------------------------------------------------------------------------------

S10

(a)

(b) Figure S5. Ortep (a) and packing (b) diagrams of 2. Hydrogen atoms are omitted.

S11

Table S3. Crystal data and structure refinement for 2. ---------------------------------------------------------------------------------------------------------- Empirical formula C24H42N2O2S4Cu4I4




Crystal system Orthorhombic

Space group Pbca

Unit cell dimensions a = 13.5252(6) Å α= 90°.

b = 20.7188(9) Å β= 90°.

c = 27.2475(12) Å γ = 90°.

Volume 7635.5(6) Å3

Z 8



F(000) 4864



Index ranges -18<=h<=17, -18<=k<=27, -35<=l<=34




Absorption correction Empirical ψ-scan

Max. and min. transmission 0.2967 and 0.1943







S12

(a)

(b)

Figure S6. Ortep (a) and packing (b) diagrams of 3. Hydrogen atoms and solvates are omitted.

S13

Table S4. Crystal data and structure refinement for 3. ---------------------------------------------------------------------------------------------------------- Empirical formula C32H59N3O2S4Cu4I4




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 11.3013(4) Å α= 93.8340(10)°.

b = 14.1099(4) Å β= 102.1980(10)°.

c = 15.2300(5) Å γ = 100.4750(10)°.

Volume 2320.14(13) Å3

Z 2



F(000) 1360



Index ranges -14<=h<=15, -18<=k<=18, -20<=l<=20




Absorption correction SADABS







S14

(a) (b) Figure S7. Conformation of L; Syn arrangement in 2 (a), Anti arrangement in 3 (b).

(a) (b)

(c) (d)

Figure S8. Packing arrangements of Cu4I4; view down b-axis of 2 (a), view down a-axis of 3 (b), view down c-axis of 2 (c), view down c-axis of 3 (d). All atoms of L except S are omitted for clarity.

S15

Table S5. Bond distances of 2 at four different temperatures.

Atom1 Atom2 d-123K d-173K d-223K d-298K (d-298K) -

(d-123K)

C2 C3 1.523 1.55 1.546 1.599 0.076

C14 C15 1.495 1.494 1.516 1.561 0.066

Cu1 Cu3 2.773 2.788 2.805 2.833 0.06

Cu1 Cu2 2.74 2.751 2.764 2.789 0.049

C4 C5 1.518 1.496 1.491 1.567 0.049

N1 C12 1.454 1.468 1.476 1.489 0.035

Cu2 Cu3 2.711 2.718 2.727 2.74 0.029

Cu2 Cu4 2.608 2.611 2.617 2.631 0.023

C7 C8 1.509 1.523 1.529 1.53 0.021

Cu3 I1 2.719 2.723 2.729 2.736 0.017

Cu1 I1 2.663 2.665 2.669 2.679 0.016

Cu4 I4 2.668 2.675 2.678 2.684 0.016

O2 C20 1.221 1.236 1.231 1.237 0.016

Cu3 I3 2.731 2.738 2.744 2.745 0.014

Cu3 Cu4 2.741 2.74 2.745 2.755 0.014

C16 C17 1.544 1.555 1.551 1.555 0.011

Cu2 I1 2.686 2.688 2.692 2.696 0.01

C11 C12 1.512 1.517 1.522 1.522 0.01

Cu2 I2 2.654 2.656 2.658 2.663 0.009

Cu2 I4 2.709 2.713 2.716 2.717 0.008

S1 C6 1.851 1.846 1.854 1.859 0.008

N2 C20 1.36 1.355 1.371 1.368 0.008

C13 C18 1.508 1.509 1.509 1.515 0.007

C21 C22 1.522 1.518 1.525 1.529 0.007

Cu1 I2 2.703 2.708 2.711 2.709 0.006

C9 C10 1.516 1.5 1.507 1.522 0.006

Cu1 I3 2.705 2.705 2.707 2.709 0.004

Cu4 I3 2.679 2.679 2.679 2.68 0.001

Cu1 S1 2.295 2.295 2.295 2.294 -0.001

Cu2 S2 2.284 2.284 2.283 2.282 -0.002

Cu3 S3 2.321 2.319 2.317 2.319 -0.002

Cu1 Cu4 2.629 2.622 2.621 2.625 -0.004

S16

Cu3 I4 2.625 2.622 2.622 2.621 -0.004

Cu4 I2 2.718 2.714 2.715 2.713 -0.005

C23 C24 1.523 1.53 1.519 1.518 -0.005

Cu4 S4 2.29 2.289 2.287 2.283 -0.007

S3 C18 1.839 1.835 1.833 1.831 -0.008

S2 C10 1.811 1.815 1.811 1.802 -0.009

S4 C23 1.808 1.801 1.798 1.797 -0.011

N2 C24 1.477 1.46 1.46 1.464 -0.013

S3 C19 1.829 1.827 1.829 1.814 -0.015

O1 C8 1.234 1.226 1.224 1.218 -0.016

C13 C14 1.55 1.539 1.535 1.533 -0.017

S1 C7 1.83 1.827 1.826 1.809 -0.021

C19 C20 1.514 1.503 1.501 1.491 -0.023

S4 C22 1.813 1.81 1.799 1.788 -0.025

N1 C9 1.471 1.454 1.436 1.446 -0.025

N2 C21 1.464 1.446 1.437 1.433 -0.031

C17 C18 1.51 1.494 1.495 1.475 -0.035

C1 C2 1.551 1.489 1.475 1.509 -0.042

S2 C11 1.811 1.807 1.795 1.763 -0.048

C1 C6 1.523 1.526 1.519 1.471 -0.052

N1 C8 1.365 1.345 1.348 1.313 -0.052

C5 C6 1.508 1.503 1.505 1.455 -0.053

C3 C4 1.497 1.492 1.5 1.427 -0.07

C15 C16 1.481 1.477 1.478 1.398 -0.083

S17

Table S6. Bond distances of 3 at four different temperatures.

Atom1 Atom2 d-123K d-173K d-223K d-298K (d-298K) -

(d-123K)

Cu1 I2 2.632 2.767 2.768 2.765 0.133

Cu3 I3 2.639 2.717 2.724 2.731 0.092

S1 C6 1.846 1.835 1.835 1.904 0.058

Cu1 Cu2 2.765 2.775 2.787 2.815 0.05

Cu1 Cu4 2.703 2.718 2.732 2.747 0.044

Cu2 Cu4 2.771 2.781 2.793 2.814 0.043

Cu2 I3 2.649 2.686 2.689 2.692 0.043

Cu2 Cu3 2.698 2.709 2.723 2.735 0.037

Cu3 Cu4 2.723 2.734 2.747 2.76 0.037

C1 C2 1.529 1.533 1.526 1.562 0.033

C19 C20 1.527 1.538 1.522 1.558 0.031

Cu1 Cu3 2.643 2.65 2.659 2.672 0.029

N1 C9 1.456 1.469 1.465 1.477 0.021

C16 C17 1.526 1.526 1.535 1.546 0.02

C9 C10 1.53 1.516 1.523 1.549 0.019

N2 C24 1.457 1.45 1.457 1.47 0.013

O1 C8 1.227 1.225 1.224 1.238 0.011

Cu4 I4 2.684 2.684 2.688 2.694 0.01

S2 C11 1.811 1.808 1.802 1.82 0.009

C13 C14 1.513 1.512 1.514 1.521 0.008

N2 C21 1.46 1.465 1.466 1.467 0.007

Cu2 I4 2.668 2.67 2.675 2.672 0.004

Cu3 S3 2.297 2.299 2.302 2.301 0.004

Cu1 S1 2.309 2.308 2.31 2.311 0.002

Cu4 I2 2.649 2.653 2.654 2.648 -0.001

Cu4 S4 2.308 2.306 2.309 2.306 -0.002

C5 C6 1.523 1.522 1.53 1.521 -0.002

Cu4 I1 2.667 2.667 2.668 2.663 -0.004

S3 C19 1.82 1.812 1.816 1.816 -0.004

C7 C8 1.518 1.524 1.505 1.514 -0.004

S3 C18 1.829 1.829 1.832 1.824 -0.005

C23 C24 1.516 1.515 1.521 1.51 -0.006

S18

Cu2 S2 2.309 2.308 2.309 2.303 -0.006

S4 C23 1.809 1.808 1.808 1.802 -0.007

C11 C12 1.517 1.519 1.511 1.509 -0.008

C15 C16 1.517 1.517 1.513 1.508 -0.009

Cu3 I4 2.775 2.774 2.773 2.764 -0.011

S1 C7 1.815 1.811 1.811 1.799 -0.016

N1 C8 1.374 1.367 1.369 1.355 -0.019

C3 C4 1.527 1.527 1.516 1.507 -0.02

O2 C20 1.236 1.213 1.208 1.213 -0.023

C21 C22 1.526 1.518 1.51 1.5 -0.026

S2 C10 1.811 1.807 1.807 1.783 -0.028

Cu1 I1 2.767 2.728 2.733 2.736 -0.031

C13 C18 1.522 1.515 1.518 1.491 -0.031

Cu2 I1 2.682 2.648 2.65 2.651 -0.031

C14 C15 1.538 1.526 1.523 1.507 -0.031

C4 C5 1.514 1.518 1.512 1.482 -0.032

N1 C12 1.455 1.462 1.45 1.418 -0.037

C17 C18 1.52 1.523 1.513 1.482 -0.038

N2 C20 1.357 1.352 1.359 1.318 -0.039

S4 C22 1.809 1.802 1.794 1.769 -0.04

C2 C3 1.521 1.506 1.498 1.475 -0.046

C1 C6 1.517 1.514 1.517 1.464 -0.053

Cu3 I2 2.709 2.637 2.638 2.634 -0.075

Cu1 I3 2.726 2.63 2.631 2.624 -0.102

S19

0.0

0.2

0.4

0.6

0.8

1.0

λ / nm

3526 538

400 450 500 550 600

Iem

2

(a)

400 450 500 550 6000.2

0.4

0.6

0.8

1.0

Iem

λ / nm

1 2 3

538 nm

(b) Figure S9. Photoluminescence spectra of before (a) and after (b) heating at 180 °C.

S20

10 20 30 40 50 60

Inte

nsity

(c)

2Theta / degree

10 20 30 40 50 60

(b)

Figure S10. Powder XRD Patterns of 1; frame image (a), measured (b), and calculated (c).

2.6° 37.7°

(a)

S21

10 20 30 40 50 60

In

tens

ity

2Theta / degree

(c)

10 20 30 40 50 60

(b)

Figure S11. Powder XRD Patterns of 2; frame image (a), measured (b), and calculated (c).

2.6° 37.7°

(a)

S22

10 20 30 40 50 60

(c)

Inte

nsity

2Theta / degree

10 20 30 40 50 60

(b)

Figure S12. Powder XRD Patterns of 3’ (a and b) and 3 (c); frame image (a), measured (b), and calculated (c).

2.6° 37.7°

(a)

S23

0 200 400 600 800 1000

10

20

30

40

50

60

70

80

90

100

-60

-50

-40

-30

-20

-10

0

10 Temperature D

ifference [μV / m

g]

Wei

ght [

%]

Temperature [oC]

178

Figure S13. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 1. (black solid line : TGA, red dash line : DTA)

0 200 400 600 800 1000

10

20

30

40

50

60

70

80

90

100

-40

-30

-20

-10

0

10

Temperature D

ifference [μV / mg]

W

eigh

t [%

]

Temperature [oC]

203

Figure S14. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 2. (black solid line : TGA, red dash line : DTA)

S24

0 200 400 600 800 1000

10

20

30

40

50

60

70

80

90

100

-50

-40

-30

-20

-10

0

10 Temperature D

ifference [μV / mg]

Wei

ght [

%]

Temperature [oC]

178

Figure S15. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 3’. (black solid line : TGA, red dash line : DTA)

69451 Weinheim, Germany - Wiley-VCH · S1 Crystal-to-Crystal Transformation between Three Cu(I)...

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