配合物[M(AAABA)_2(py)_2(H_2O)_2,M=Zn、Mn]的合成、晶体结构、荧光性质和理论研究

Syntheses,Crystal Structures,Luminescent Property and Theoretical Study of the Complexes [M(AAABA)_2(py)_2(H_2O)_2,M=Zn,Mn]

合成了乙酰丙酮缩邻氨基苯甲酸Schiff碱(HAAABA)(HAAABA=acety lacetone-o-aminobenzoic acid),获得了其锌和锰的配合物单晶[M(AAABA)2(py)2(H2O)2,M=Zn,1;Mn,2]。产物经IR、核磁共振谱、元素分析、X-射线单晶结构分析等表征。两晶体均属于单斜晶系,空间群为P21/n。用Guassian03W程序,在B3LYP/6-31G等水平上对标题化合物进行了几何全优化,并对其成键情况、自然键轨道(NBO)及键能进行了分析。在DMF中测定了Schiff碱配体及其锌配合物的荧光性质。

Acetylacetone-o-aminobenzoic acid （HAAABA） and its complexes [M（AAABA）2（py）2（H2O）2, M=Zn, 1; Mn, 2] were synthesized and characterized by IR, 1H NMR, element analysis and X-ray single crystal structure analysis. The crystal structure analysis indicates that two complexes crystallize in monoclinic system, space group of P21/n. Crystallographic data for complex 1 are a=0.986 44（6） nm, b=1.4488 1（8） nm, c=1.246 95（7） nm,β=109.643 0（1）°, Z=2, V=1.678 39（17） nm3, Mr=696.05, Dc=1.377 g·cm-3,μ（Mo Kα）=0.788 mm-1, F（000）=728, R=0.040 8 and wR= 0.1222. Crystallographic data for complex 2 are a=0.996 11（12） nm, b=1.453 46（17） nm, c=1.253 21（15） nm,β= 110.109（2）°, Z=2, V=1.703 8（4） nm3, Mr=685.62, Dc=1.336 4（3） g·cm-3,μ=1.324 mm-1, F（000）=718, R=0.041 6 and wR=0.088 8. The theoretical studies of title complexes as a structure unit were carried out at MPW1PW91/6- 31G, B3LYP/6-31G and HF/6-31G levels with Guassian 03W program, and the atomic charges, natural bond orbital analysis and bond energies were also discussed. The luminescent property in DMF of the complex 1 and Schiff base ligand were studied. CCDC： 724591, 1; 608876, 2.