N,N′-亚水杨基皮考林酰肼合铜的晶体结构及荧光性质  

Crystal Structure and Fluorescence Character of Copper Complex Containing N,N′-Salicylidene pyridine formylhydrazide

作　　者：吴文士[1] 冯云龙[2] 蓝心仁[1] 黄婷婷[1] 

机构地区：[1]华侨大学材料学院,泉州362011 [2]浙江师范大学物理化学研究所

出　　处：《应用化学》2004年第2期135-139,共5页Chinese Journal of Applied Chemistry

基　　金：福建省自然科学基金资助项目 (E0 2 10 0 2 6)

摘　　要：在DMF和CH3 OH中 ,以N ,N′ 亚水杨基皮考林酰肼 (简写为H2 sphz)和高氯酸铜合成了双核配合物[Cu2 (sphz) (DMF) 3 H2 O]·(ClO4) 2 。X射线衍射实验结果表明 ,标题配合物晶体属于单斜晶系 ,空间群为P2 1/c,分子式C2 2 H3 2 Cl2 Cu2 N6O14 ,晶体学参数a =1 0 81 2 0 ( 3 )nm ,b=2 .5 71 87( 7)nm ,c=1 1 777( 3 )nm ,β=1 0 4 1 472( 5 )°,V =3 1 75 7( 2 )nm3 ,Z =4,Dc=1 679Mg/m3 ,F( 0 0 0 ) =1 640 ,μ(MoKα) =1 5 82mm-1,R =0 0 3 5 8,Rw=0 1 0 0 7。2个铜 (Ⅱ )原子 ,一个呈畸变的NO3 平面体正方形配位构型 ,一个具有畸变的N2 O3 四角锥配位构型 ,晶体内每 2个分子通过分子间氢键作用形成缔合分子对。红外光谱表明 ,配体在形成配合物后 ,ν(CO)和ν(CN )红移。电子光谱表明 ,存在d d 和π π 跃迁。荧光光谱表明 ,配合物金属对配体n π 激发 ( 3 1 0nm)引起的发射峰有较大的影响。The title complex \[Cu 2(sphz)(DMF) 3H 2O\]·(ClO 4) 2(C 22H 32Cl 2Cu 2N 6O 14), where H 2sphz is N,N′-salicylidene pyridine formylhydrazide, has been synthesized from H 2sphz and copper perchlorate in a mixture of DMF and methanol. Crystal data of the complex were found:space group P2 1/c, a= 1.081 20(3) nm, b=2.571 87(7) nm, c=1.177 7(3) nm, β=104.147 2(5)°, V=3.175 7(2) nm 3, Z=4, D c=1.679 Mg/m 3, F(000)=1 640, μ(Mo Kα)=1.582 mm -1, R=0.035 8 for 5 234 observed reflections(I≥2σ(I)), R w=0.100 7, GOF=1.076. One copper(Ⅱ) ion in complex is coordinated with a pyridine nitrogen atom, a diazine nitrogen atom, two DMF oxygen atoms and a water oxygen atom, forming a distorted square pyramidal arrangement of N 2O 3. Another copper(Ⅱ) ion in complex is coordinated with a diazine nitrogen atom, a carbonyl oxygen atom, a phenoxy oxygen atom and a DMF oxygen atom, forming a distorted square arrangement of NO 3. Every two molecules in the crystal are linked in pairs through the intermolecular hydrogen bonding. ν(CO) and ν(CN) are shifted to lower frequencies in IR spectra; π-π * charge transitions and d-π * charge-transitions are observed in their electronic spectra. The emission lines( λ exc=310 nm) are shifted to higher frequencies in fluorescence spectra.

关 键 词：晶体结构 N N'-亚水杨基皮考林酰肼合铜 荧光性质 

分 类 号：O627[理学—有机化学]