三个基于Cu_2X_2(X^-=Cl^-、Br^-和I^-)结构单元双核Cu(Ⅰ)配合物的合成、晶体结构、电子吸收和发射光谱(英文)  

Three Dinuclear Cu+Complexes Based on Cu_2X_2(X^-=Cl^-、Br^-and I^-): Syntheses, Crystal Structures, Absorption and Emission Spectra

作　　者：孙晓美[1] 宁为华[1] 刘建兰[1] 刘少贤[1] 郭平春[1] 任小明[1,2] 

机构地区：[1]南京工业大学应用化学系,南京210009 [2]南京大学配位化学研究所配位化学国家重点实验室,南京210093

出　　处：《无机化学学报》2013年第10期2176-2182,共7页Chinese Journal of Inorganic Chemistry

基　　金：the Science and Technology Department of Jiangsu Province (grantnos.BK2010551);National Natural Science Foundation of China for financial support( grantnos.21071080)~~

摘　　要：合成并表征了3个含Cu2X2结构单元的双核Cu髣配合物[Cu2(μ-X)2(deebq)2](其中deebq=2,2′-联喹啉-4,4′-二甲酸乙酯;X=Cl(1),Br(2)or I(3))。化合物1~3同构,其晶体属三斜晶系,空间群为P1,具有相似的晶胞参数和晶体堆积结构。Cu2X2双核单元具有反演中心对称性,每个Cu+与deebq配体中2个N原子、2个μ2桥联的卤素X-阴离子配位,形成扭曲的四面体配位环境。通过deebq配体中苯环间π…π堆积,相邻双核分子形成超分子一维链,超分子链间存在弱范德瓦尔斯引力。在二氯甲烷溶液中,3个化合物都存在1个宽而不对称的电荷迁移吸收带(500~630 nm区域),其强度和位置不受桥联X-配体影响。因此,电荷迁移带归属为由Cu+中心到deebq配体的电荷转移。在二氯甲烷溶液中,3个化合物发射强荧光,发射带中心波长位于400 nm处,该发射带归属为deebq配体内的π-π*电子跃迁。在固体以及二氯甲烷溶液中,都没观察到从金属中心到配体的MLCT发射带。Three dinuclear Cu＋ complexes [Cu2（/x-X）2（deebq）2] （where deebq=4,4＇-diethylester-2,2＇-biquinoline; X=CI （1）, Br （2） or I （3））, have been synthesized and characterized spectroscopically. The isostructural 1-3 crystallize in triclinic system with space group P1, and show quite similar lattice parameters and packing structures. Two Cu＋ ions in a dinuclear unit are related to each other via an inversion center; each Cu＋ ion are coordinated by two N atoms form one deebq ligand and two X- anions, which act as a/x2-bridge mode to link two Cu＋ ions, to form a distorted tetrahedral coordination geometry. The dinuclear units are aligned into a supramolecular chain via the intermolecular π...π interactions between the neighboring phenyl rings in deebq ligands, and the supramolecular chains are held together through weakly intermolecular van der Waals forces.Three complexes exhibit a broad and asymmetric absorption band in the 500-630 nm range in CH2C12, this band is almost independent on the bridged X- ligand and not observed in the absorption spectrum of deebq in CH2C12, thus, it is assigned to MLCT from Cu~ center to deebq ligand. Complexes 1-3 emitted intense fluorescence with the center around 400 nm, this emission band is attributed to the π-π＊ electronic transition of deebq ligand. No MLCT emission was observed in the CHEC12 solution and the solid state for three complexes. CCDC： $88543, 1; 888542, 2; 888541, 3.

关 键 词：2 2＇-联喹啉-4 4＇-二甲酸乙酯 双核配合物 晶体结构 MLCT 吸收光谱 发射光谱 

分 类 号：O614.121[理学—无机化学]