希夫碱配合物M3L3(NO3)6(H3O)2的合成与光谱性质

以4-氨基-1,2,4-三氮唑与对二甲氨基苯甲醛为原料， 在冰醋酸催化下合成了配体4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛（L）。 然后利用L与过渡金属硝酸盐［M(NO3)2·xH2O(M=Cu,　Co,　Zn,　Cd; x=3～6)］在无水乙醇中反应， 制得固态配合物M3L6(NO3)6(H2O)2。 通过元素分析、 红外光谱、 紫外光谱、 荧光光谱等手段对合成的配体及配合物进行了表征。 实验结果表明, 该物质是一种多晶粉末状的发光材料,　在紫外光的激发下,　在乙醇溶液体系中的荧光发射峰在416 nm处,　为蓝色荧光, 色纯度高,　荧光量子效率高, 而配合物M3L6(NO3)6(H2O)2的荧光发射峰则红移至445 nm左右， 同时荧光强度显著增强。　M3L6(NO3)6(H2O)2中与M(Ⅱ)发生配位作用的基团是配体中三氮唑环上的氮原子。

Synthesis and Spectra of Transition Metals Complexes RE3L3(NO3)6(H3O)2

Schiff base 4-(p-dimethylaminobenzaldehydeamino)-4H-1,2,4-triazole(L) was synthesized from 4-amino-1,2,4-triazole and p-dimethylaminobenzaldehyde using acetic acid as the catalyst. The solid complexes RE3L6(NO3)6(H2O)2 (RE=Cu, Co, Zn, Cd; x=3-6) were synthesized with 4-(p-dimethylaminobenzaldehydeamino)-4H-1,2,4-triazole and nitrate of transition metals in ethanol and characterized by elemental analysis, infrared spectroscopy, UV spectrum, and fluorescence spectrum. Experimental results showed that the free ligand is a thermally stable material, and its ethanol solution emitted intense blue fluorescence at the peak wavelength of 416 nm. The absorption band at about 406 nm can be assigned to the intrinsic absorption of CN. Compared with the fluorescence emission of free ligand in ethanol solution, the emission of the complex of RE3L6(NO3)6(H2O)2 was red-shifted to 445 nm and narrow in solution. RE(Ⅱ) was coordinated with N atomy of triazole in 4-(p-dimethylaminobenzaldehydeamino)-4H-1,2,4-triazole.