过渡金属吡啶配离子的TCNQ电荷转移盐的合成和物理性质

Synthesis and Physical Properties of TCNQ Charge transfer Salts of Transition metal Pyridine Complex Cations

合成了通式为［Ｍ（Ｐｙ）ｍ］［ＴＣＮＱ］ｎ（Ｍ＝Ｍｎ，ｍ＝４；Ｍ＝Ｃｏ，Ｎｉ，Ｃｕ，ｍ＝２；ＴＣＮＱ＝７，７，８，８－四氰基对苯醌二甲烷，ｎ＝２，３）的８个过渡金属吡啶配离子的ＴＣＮＱ电荷转移盐，通过元素分析、红外光谱、顺磁共振谱、光电子能谱、磁化率和电导率对这些电荷转移盐进行了表征．结果表明，在这些电荷转移盐分子中存在ＴＣＮＱ－和ＴＣＮＱ０，且ＴＣＮＱ－与ＴＣＮＱ０相互作用形成结构单元［ＴＣＮＱ］２－ｎ（ｎ＝２，３），各个结构单元沿一维方向堆积形成分子柱，部分电荷从［ＴＣＮＱ］２－ｎ向［Ｍ（Ｐｙ）ｍ］２＋转移，导致化合物中的金属表现为混合价态．其中３个电荷转移盐具有良好的导电性．

Eight TCNQ charge transfer salts of transition metal pyridine complex cations with the general formula [M(Py) m ] n (M=Mn, m =4; M=Co, Ni, Cu, m =2; TCNQ= 7,7,8,8 tetracyanoquinodimethane, n =2,3) have been synthesized and characterized by elemental analysis, IR spectrum, ESR spectrum, X ray photoelectron spectrum, magnetic susceptibility and electrical conductivity. The results indicate that there are TCNQ - and TCNQ 0 in the molecules of these charge transfer salts; TCNQ - interacts with TCNQ 0 to form a structural unit 2- n (n =2,3); these structural units stack along with one dimension direction to form molecular column; it leads the metals of these compounds to mixed valence state because partial charges transfer from 2- n to [M(Py) m ] 2+ ; three of these charge transfer salts show a good electrical conductivity.