两种异烟酰腙及其铜配合物的合成、结构表征和量化计算

摘要

合成了4-乙酰基吡啶缩异烟酰腙(HL,1)和2-乙酰基吡啶缩异烟酰腙(HZ,2)两种 Schiff碱及其相应的铜配合物[Cu(H2 O)L]NO3��2H2 O(1a)和[Cu(CH3 COO)Z](2a),用元素分析和光谱分析进行了表征．荧光测试表明,金属配位的结果使配体的荧光增强．测定了1的二水合物(HL��2 H2 O)的单晶结构,该晶体属三斜晶系Pī空间群,晶胞参数为a＝0．68735(16)nm,b＝0．75662(18)nm,c＝1．4246(3)nm,α＝86．933(3)°,β＝82．983(3)°,γ＝70．871(3)°,Z＝2,Mr＝276．30,Dc＝1．320 g��cm－3,F(000)＝292．应用Gaussian 09程序,采用密度泛函方法(DFT),在B3LYP/6-31G(d)水平对酰腙配体进行了量化计算．%Two dual pyridyl Schiff base,4-acetylpyridine isonicotinoyl hydrazone (HL,1 ) and 2-acetylpyridine isonicotinoyl hydrazone (HZ,2),and their copper(II)complexes [Cu(H2 O)L]NO3��2H2O (1a)and [Cu(CH3COO)Z](2a)were synthesized and characterized by elemental analysis and spectra analysis,whose results showed that the luminescence of these Schiff base was greatly improved because of the coordination of Cu(II)ion.X-ray diffraction single crystal analysis showed that the crystal of HL��2 H2 O belonged to the triclinic system,space group Pīwith cell parameters a=0.687 35(16)nm,b=0.756 62 (18)nm,c=1.424 6 (3)nm,α=86.933 (3)°,β=82.983 (3)°,γ=70.871(3)°,Z=2,Mr=276.30,Dc=1.320 g��cm-3 ,F(000)=292.The quantum chemical calculation for two acylhydrazone ligands was performed by means of Gaussian 09 program at B3LYP/6-31G(d) basis set.