Electronic Supplementary Information · 1 Supplementary Information A Series of Goblet-like...

1

Supplementary Information

A Series of Goblet-like Heterometallic Pentanuclear

[LnIIICuII4] Clusters Featuring Ferromagnetic Coupling and

Single-Molecule Magnet Behavior

Qilong Zhu,a Shengchang Xiang,b Tianlu Sheng,a Daqiang Yuan,a Chaojun Shen,a

Chunhong Tan,a Shengmin Hua and Xintao Wu*a

a State Key Lab of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Cheinese Academy of Science, Fuzhou, Fujian 350002, P. R. China b College of Chemistry and Materials, Fujian Normal University, Fuzhou, Fujian 350007, P. R. China

• Corresponding author:

E-mail: wxt@ fjirsm.ac.cn.

Tel: +86-591-83719238; Fax: +86-591-83719238

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

2

Materials and Methods:

All reagents used were received from commercial suppliers without further

purification. Elemental analyses (C, H, and N) were performed with a Vario MICRO

CHNOS Elemental Analyzer. The infrared spectra with KBr pellets were recorded on

a Perkin-Elmer Spectrum One FT-IR Spectrometer. Thermal analyses were performed

on a NETZSCH STA 449C instrument with a heating rate of 10 °C min-1 under

nitrogen flow. Powder XRD patterns were acquired on a DMAX-2500 diffractometer

using Cu Kα radiation at ambient environment. The calculated patterns were

generated with PowderCell. Magnetic susceptibility was measured on polycrystalline

samples by using a Quantum Design MPMS-XL SQUID magnetometer.

Preparation of {[LnCu4(bic)2(μ3-OH)4(H2O)8](ClO4)2(NO3)}·6H2O (Ln = 1·Gd,

2·Tb, 3·Sm, 4·Eu):

These compounds were prepared by a similar experimental procedure except that

appropriate lanthanide(III) perchlorate hydrates were used. A typical procedure for the

preparation of 1·Gd is described. Bis(2-carboxyethyl)isocyanurate (0.054 g, 0.20

mmol) was added to an aqueous solution (10 mL) of Cu(NO3)2·3H2O (0.194 g, 0.80

mmol) and Gd(ClO4)3·6H2O (0.141 g, 0.25 mmol) to give a blue solution. A white

precipitate was formed when the NaOH (0.5 M) solution was added slowly. Vigorous

stirring readily dissolved it. The addition of NaOH solution and stirring were

continued until irreversible precipitation occurred. The solution was filtered and

exposed to air for slow evaporation. Blue crystals were obtained about a week later.

The crystals were isolated by filtration, washed with water, and dried in the air.

1·Gd: Yield: 0.126 g (82 % based on H2bic). Elemental analysis (%) calcd for

GdCu4C18H50N7O43Cl2: C 14.08, H 3.28, N 6.39; found: C 14.01, H 3.19, N 6.33; IR

(Kbr, cm-1): 3465 (vs, br), 2834 (w), 1726 (m), 1629 (vs), 1572 (s), 1488 (m), 1435 (s),

1385 (vs), 1342 (w), 1303 (w), 1276 (m), 1121 (s), 993 (w), 767 (m), 685 (w), 626

(m), 535 (w).

2·Tb: Yield: 0.132 g (86 % based on H2bic). Elemental analysis (%) calcd for

TbCu4C18H50N7O43Cl2: C 14.07, H 3.28, N 6.38; found: C 14.05, H 3.15, N 6.31; IR


1384 (vs), 1342 (w), 1299 (w), 1277 (m), 1121 (s), 993 (w), 767 (m), 688 (w), 625

(m), 532 (w).


3

3·Sm: Yield: 0.132 g (79 % based on H2bic). Elemental analysis (%) calcd for

SmCu4C18H50N7O43Cl2: C 14.15, H 3.30, N 6.42; found: C 14.13, H 3.22, N 6.40; IR


1385 (vs), 1340 (w), 1300 (w), 1276 (m), 1121 (s), 993 (w), 767 (m), 686 (w), 626

(m), 534 (w).

4·Eu: Yield: 0.132 g (84 % based on H2bic). Elemental analysis (%) calcd for

EuCu4C18H50N7O43Cl2: C 14.13, H 3.29, N 6.41; found: C 14.14, H 3.23, N 6.39; IR


1385 (s), 1338 (w), 1398 (w), 1277 (m), 1121 (s), 993 (w), 767 (m), 688 (w), 626 (m),

531 (w).

X-ray Crystallographic Analyses:

Data collection was performed on Rigaku Mercury CCD diffractometer with

graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation at room temperature. The

collected data were reduced using the program CrystalClear (Rigaku and MSC, 1999)

and an empirical absorption correction (multiscan) was applied. The structures 1-4

were solved by direct methods and refined by the full-matrix least squares on F2 using

the SHELXTL-97 program.1 All non-hydrogen atoms were refined with anisotropic

displacement parameters. Hydrogen atoms attached to carbon and nitrogen atoms

were placed in geometrically idealized positions and included as riding atoms (C-H

bond fixed at 0.97 Å); and those on coordination water molecules were located in a

difference Fourier map and refined with O-H distance restraints of 0.85(1), while

those on free water molecules could not be reliably located but are included in the

formula. Crystallographic and refinement details of 1-4 are summarized in Table S1.

Selected bond lengths and angles for 1-4 are listed in Table S2.


4

Table S1. Crystallographic data for compounds 1−4.

1 2 3 4

formula GdCu4C18H50

N7O43Cl2 TbCu4C18H50

N7O43Cl2 SmCu4C18H50

N7O43Cl2 EuCu4C18H50

N7O43Cl2

Mr [g mol−1] 1534.96 1536.63 1528.06 1529.67

crystal system Orthorhombic Orthorhombic Orthorhombic Orthorhombic space group Pnma Pnma Pnma Pnma a (Å) 14.565(5) 14.564(5) 14.5762(4) 14.5743(4) b (Å) 20.273(7) 20.278(6) 20.2376(6) 20.2763(6) c (Å) 16.053(6) 16.024(5) 15.9957(5) 16.0214(5)

α (˚) 90.00 90.00 90.00 90.00

β (˚) 90.00 90.00 90.00 90.00

γ (˚) 90.00 90.00 90.00 90.00

V (Å3) 4740(3) 4732(2) 4718.5(2) 4734.5(2) Z 4 4 4 4

Dc (g cm−3) 2.151 2.157 2.151 2.146

μ (mm-1) 3.388 3.487 3.242 3.316

F (000) 3060 3064 3052 3056 measured reflections

35828 35602 35469 35994

independent reflections

5556 5548 5555 5576

Rint 0.0514 0.0407 0.0244 0.0305 GOF on F2 1.180 1.172 1.084 1.105 R1,a wR2b (I>2σ(I)) 0.0443, 0.1126 0.0384, 0.1032 0.0338, 0.0991 0.0322, 0.0854 R1,a wR2b (all data) 0.0529, 0.1232 0.0453, 0.1120 0.0348, 0.0999 0.0329, 0.0860

[a] R1 = (||Fo| – |Fc||)/|Fo|, [b] wR2 = {w[(Fo2 – Fc

2)2]/�w[(Fo2)2]}1/2.


5

Table S2. Selected bond distances, Cu···Cu, Ln···Cu [Å] and Dihedral angles [°] for 1−4.

1·Gd 2·Tb 3·Sm 4·Eu

Cu1-O5 1.944(3) 1.948(3) 1.945(3) 1.946(2) Cu1-O8 1.966(3) 1.960(3) 1.958(2) 1.959(2) Cu1-O11 2.372(5) 2.371(4) 2.368(4) 2.373(3) Cu1-O17 2.588(5) 2.580(5) 2.578(3) 2.583(3) Cu2-O8 1.951(3) 1.949(3) 1.954(2) 1.950(2) Cu2-O4 1.957(3) 1.962(3) 1.961(2) 1.960(2) Cu2-O6 1.963(3) 1.966(3) 1.960(2) 1.960(2) Cu2-O9 1.984(3) 1.986(2) 1.980(2) 1.981(2) Cu2-O10 2.407(4) 2.409(3) 2.401(3) 2.405(3) Cu2-O17 2.501(2) 2.499(2) 2.495(2) 2.499(1) Cu3-O7 1.934(3) 1.936(3) 1.933(3) 1.934(2) Cu3-O9 1.946(3) 1.948(3) 1.944(2) 1.946(2) Cu3-O17 2.444(5) 2.451(5) 2.450(3) 2.434(3) Ln1-O14 2.425(5) 2.408(4) 2.392(4) 2.431(3) Ln1-O13 2.423(5) 2.410(5) 2.391(4) 2.437(4) Ln1-O8 2.438(3) 2.425(3) 2.407(2) 2.438(2) Ln1-O15 2.445(4) 2.438(3) 2.427(3) 2.460(3) Ln1-O9 2.478(3) 2.461(3) 2.447(2) 2.480(2) Ln1-O12 2.473(5) 2.466(5) 2.457(5) 2.477(4) Cu1···Cu2 3.103(1) 3.101(1) 3.096(1) 3.099(1) Cu2···Cu3 3.052(1) 3.053(1) 3.050(1) 3.050(1) Ln1···Cu1 3.496(1) 3.481(1) 3.465(1) 3.494(1) Ln1···Cu2 3.548(1) 3.537(1) 3.522(1) 3.553(1) Ln1···Cu3 3.532(1) 3.524(1) 3.508(1) 3.538(1) aαOLnO, OCu1O 1.29(8) 1.31(8) 0.66(7) 1.40(6) aαOLnO, OCu2O 3.65(8) 3.67(6) 3.94(7) 3.33(6) aαOLnO, OCu3O 5.76(10) 5.88(8) 5.69(8) 5.66(6) bαCu1Cu2Cu3,

Cu1Cu2aCu3 2.06(3) 2.11(3) 2.26(3) 1.97(2)

[a] the dihedral angles α between the two planes OLnO and OCuO. [b] the dihedral angles α

between the two planes Cu1Cu2Cu3 and Cu1Cu2aCu3.


6

Fig. S1 Representation of the goblet-like cation cluster in compounds 1-4.

Fig. S2 Photograph of the single crystal 1.


7

Fig. S3 Coordination polyhedron for GdIII ion and the [GdCu4] tetragonal pyramid in

the cluster cation of 1·Gd. Symmetry code: a: x, −y+3/2, z.

Fig. S4 Three-dimensional hydrogen-bonded coordination network of 1·Gd viewed

down the b-axis.


8

Fig. S5 PXRD patterns of compounds 1-4.

Fig. S6 TGA curves of compounds 1-4.


9

(a)

(b)


10

(c)

(d)

Fig. S7 χm and χm−1 vs. T plots under 1 kOe for compounds 1-4.


11

Fig. S8. Isothermal M vs. H/T plots at 2, 4 and 6 K for 2·Tb (a) and 3·Sm (b).


12

Fig. S9 Temperature dependence of ac susceptibilities of 2·Tb (a) and 3·Sm (b) under

a zero Oe dc field with an oscillating field of 3 Oe in frequencies of 111−911 Hz.


13

Fig. S10 Frequency dependence of the out-of-phase susceptibilities of 2·Tb (a) and

3·Sm (b) at 2.0 K with an oscillating field of 3 Oe in dc fields of 500−3500 Oe.


14

Fig. S11 Temperature dependence of ac susceptibilities of 3·Sm under a 3 kOe dc

field with an oscillating field of 3 Oe in frequencies of 100−1500 Hz.

[1] SHELXTL, version 5.10; Siemens Analytical X-ray Instruments Inc.: Madison, WI, 1994.


15

Fig. S12 The fitting plots of the Arrhenius law of 2·Tb (black) and 3·Sm (red) under

a 3 kOe dc field.


Electronic Supplementary Information · 1 Supplementary Information A Series of Goblet-like...

Documents

Transcript of Electronic Supplementary Information · 1 Supplementary Information A Series of Goblet-like...