| 光谱学与光谱分析 |
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| Crystal Structures and Luminescence Property of d10 Transition Metal Complexes |
| CHI Yu-xian1,NIU Shu-yun1*,JIN Jing1,YANG Guang-di2,YE Ling2 |
1. School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China
2. Key of Supramolecular Structure and Materials of Ministry of Education, Jilin University, Changchun 130023, China |
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Abstract Five Zn(Ⅱ) and Cd(Ⅱ) coordination complexes, [Zn(NA)2(H2O)4](1), [Zn(INA)2(H2O)4](2), [Zn(2,2’-bipy)2(SCN)2](3), [Cd(INA)2(H2O)4](4) and [Cd(phen)2(NO3)2](5) (HNA=nicotinic acid, HINA=isonicotinic acid,2,2’-bipy=2,2’-bipyridine, phen=1,10-phenanthroline), were synthesized through constant temperature magnetic stirrer or hydrothermal method, and their single-crystal structures were determined by X-ray diffraction. The authors measured the IR, UV-Vis-NIR and fluorescence spectra of the complexes and analyzed their photophysical properties. At room temperature in the solid state the five complexes can show strong fluorescence, i.e., λemmax=362 nm (λex=330 nm), (1); λemmax=424 nm (λex=330 nm), (2); λemmax=442 nm (λex=380 nm), (3); λemmax=424 nm (λex=330 nm), (4); λemmax=456 nm (λex=360 nm), (5), and complex (5) can emit phosphorescence upon excitation at 360 nm (λplmax=546 nm, τ= 10 ms). But the organic ligands are different, which lead to the luminescence property of complexes originating from different charge transfer. Compared with the relevant ligands (λemmax=380 nm, HNA; λemmax=541 nm,2,2’-bipy), the fluorescence emissions of complex (1) and (3) show a blue-shift which mainly comes from the ILCT (intraligand charge transfer) and at the same time exists L→M(4S) transfer. The emissions of complex (2) and (4) come from LMCT (ligand-to-metal charge transfer) and show red-shift compared to that of free ligand (λemmax=337 nm, HINA). For complex (5), the appearance and position of its emission are different from those of the ligand (λemmax=381 nm, phen), which is attributed to LLCT (ligand-to-ligand charge transfer) and LMCT.
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Received: 2007-06-18
Accepted: 2007-09-28
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Corresponding Authors:
NIU Shu-yun
E-mail: syniu@sohu.com
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