Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
SUPPLEMENTARY DATA
Two mixed-valence copper(I,II) imidazolate coordination polymers: Metal valence tuning
approach for new topological structures
Xiao-Chun Huang,a,b Jie-Peng Zhang,a Yan-Yong Lina and Xiao-Ming Chen
School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China
Synthesis of 1: A mixture of Cu(NO3)2∙3H2O (0.242 g, 1 mmol), Him (0.102 g, 1.5
mmol), aqueous ammonia (25%, 4 mL) and water (6 mL) was stirred for 15 min in air,
then transferred and sealed in a 23-mL Teflon reactor, which was heated in an oven to
130C for 80 h. The oven was cooled to room temperature at a rate of 5C h-1. The
resulting dark-green needle crystals of 1 were filtered, washed, and dried in air (yield ca.
70% based on Cu). Elemental analysis calcd (%) for 1 C9H9Cu2N6: C 32.93, H 2.76, N
25.60; found: C 32.89, H 2.81, N 25.54. IR data (KBr, cm-1): 3129m, 3109m, 2583w,
2504w, 1609m, 1469s, 1311s, 1233s, 1165w, 1082vs, 948s, 847s, 753s, 664s.
Synthesis of 2: A mixture of Cu(NO3)2∙3H2O (0.363 g, 1.5 mmol), Him (0.136 g, 2 mmol),
aqueous ammonia (25%, 6 mL) and water (4 mL) was stirred for 15 min in air, then
transferred and sealed in a 23-mL Teflon reactor, which was heated in an oven to 140C
for 80 h. The oven was cooled to room temperature at a rate of 5C h-1. The resulting
mauve plate-like crystals of 2 were filtered, washed, and dried in air (yield ca. 60% based
on Cu). Elemental analysis calcd (%) for 2 C12H12Cu3N8: C 31.41, H 2.64, N 24.42;
found: C 31.38, H 2.71, N 24.44. IR data (KBr, cm-1): 3142m, 3117m, 2582w, 2505w,
1580m, 1484s, 1310s, 1239s, 1172w, 1085vs, 951s, 828s, 762s, 749s, 669s.
1
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
(a)
(b)
Figure S1. The infinite CuI chain (a) in 1 (b) in 2.
(a)
(b)
Figure S2. The schematic diagram of 2D net (one layer) (a) and 3D NbO net (three
layers stacking in ABC pattern) (b) in 2. Purple spheres represent for CuII atoms, blue
spheres for CuI atoms and black spheres for im fragments.
2
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
2.0
1.5
10  M / cm mol
3
1.0
3
 eff /  B
-1
3.5
0.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0
50
100
150
200
250
300
T/K
0.0
0
50
100
150
200
250
300
T/K
(a)
1.8
1.6
1.4
0.18
0.16
 M / cm mol
1.0
3
 eff /  B
-1
1.2
0.8
0.6
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
0.4
0
50
100
0.2
150
200
250
300
T/K
0.0
0
50
100
150
200
250
300
T/K
(b)
Figure S3. Temperature dependent eff and magnetic susceptibility (inset) for 1 (a) and 2
(b) at 10 kOe. The eff values at 300 K are 1.836 B.M. per Cu2 unit for 1 and 1.691 B.M.
per Cu3 unit for 2.
3