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
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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