Supporting Information
A trigonal prismatic copper(I)―bipyrazolato cage: synthesis, crystal
structure and luminescence
Lu-Hui Li, Jin-Xue Zhang, Shao-Kang Jia, Guang Yang*
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou450001,
Henan, P. R. China
E-Mail: yang@zzu.edu.cn
Figure S1 The ball-and-stick diagram of the asymmetric unitof [Cu2(H2L)2Cl4].
Figure S2 Packing diagram of Cu6L3, showing the intermolecular C-H···π interactions.
Figure S3 The IR spectrum of H2L.
40
4000
3000
Figure S5 The IR spectrum of [Cu2(H2L)2Cl4].
70
60
55
Wavenumbers (cm-1)
2000
1291.91
1408.32
35
1000
713.53
646.50
616.06
586.33
517.60
478.88
1193.84
1181.58
1138.21 1116.63
1074.30
1030.69
1001.95
983.84
928.80
790.14
780.47
1226.77
75
852.19
1606.13
1578.33
1555.68
85
1449.53
80
2904.03
90
697.69
50
1482.04
3058.53
65
766.51
3219.83
%T
Figure S4 The1H NMR spectrum of H2L.
100
95
45
4000
3000
10
2000
774.61
757.94
718.20
1016.13
40
909.95
1155.02
1072.62
1058.88
1028.23
598.59
520.36
453.39
1325.73
1237.66
1277.65
1577.54
1529.79
1426.77
1492.20
1603.57
80
843.09
1945.45
1878.04
90
695.96
30
1442.90
70
2907.49
2838.59
3061.27
3027.71
60
1466.38
50
3426.60
%T
100
20
-0
Wavenumbers (cm-1)
1000
Figure S6 The IR spectrum of Cu6L3⊃ THF.
(a) λem = 500 nm, T = 77 K;
(b) λem = 580 nm, T = 77 K
Figure S7 Phosphorescence decay curves for Cu6L3.
Cu6L13
Cu6L23
Cu6L3⊃THF
Ag6L23⊃S8
Ag6L23⊃C6H12
Figure S8 The structures of several trigonal prismatic M6L3 cages (Cu6L13, Cu6L3⊃THF,
Cu6L23,Ag6L23⊃S8, Ag6L23⊃C6H12,).
Cmethylene―Cmethylene
4
4
pz―C pz
intratrimerC
intertrimer C
4
4
pz―C pz
Figure S9 The model used for comparison of M6L3 cages.
Thermogravimetric Analysis (TGA)
Thermal analysis was conducted on a NETZSCHSTA 409 PC system under air with
a flow rate of 60 mL min-1 at a scanning rate of 10 °C min-1.
A thermal analysis on Cu6L3 (2) was scanned from 30 °C to 840°C under air (Fig.6).
The first weight loss starts at 210 °C and ends at 345 °C, accounting for 5.97 % of the
total mass. From then on, the sample experienced weight losses of 67.29 % and 4.03 %
in the temperature range of 345 °C – 490 °C, and 630 °C – 725 °C, respectively. The
final residue at 804 °C might be CuO, based on the residual weight percentage
(observed 22.71 %; calculated 22.80 %, assuming each cage has one THF in its
cavity).
Figure S10 The TG curve of CuI6L3.