芳基四硫富瓦烯与溴化铜电荷转移复合物的合成及晶体结构  

Synthesis and Crystal Structure of Arylthiotetrathiafulvalenes and Cupric Bromide Charge Transfer Complexes

作　　者：马龙飞 祝招辉 黄小波 MA Long-Fei;ZHU Zhao-Hui;HUANG Xiao-Bo(Department of Criminal Science and Technology,Henan Police College,Zhengzhou 450046,China)

机构地区：[1]河南警察学院刑事科学技术系,郑州450046

出　　处：《无机化学学报》2022年第5期821-828,共8页Chinese Journal of Inorganic Chemistry

基　　金：河南省重点研发与推广专项(科技攻关)项目(No.212102210476);河南警察学院青年项目(No.HNJY-2020-QN-28)资助。

摘　　要：采用溶液扩散的方法合成了硫原子桥联芳基取代四硫富瓦烯1~4与CuBr_(2)的4种电荷转移复合物(1^(+)·)(Cu_(2)Br_(6))_(0.5)、(2^(+)·)(Cu_(2)Br_(6))_(0.5)、(3^(+)·)(Cu_(2)Br_(6))_(0.5)和(4^(+)·)(CuBr_(2))。晶体结构研究表明,复合物中阴离子呈现2种构型:八面体型(CuⅡ_(2)Br_(6))2-和直线型(CuⅠBr_(2))-,并且4种复合物呈现不同的堆积结构。通过调控芳基上卤素原子取代位置和大小,实现了对电荷转移复合物堆积结构和阴离子构型的有效调控。Four charge-transfer complexes,(1^(+)·)(Cu_(2)Br_(6))_(0.5),(2^(+)·)(Cu_(2)Br_(6))_(0.5),(3^(+)·)(Cu_(2)Br_(6))_(0.5)and(4^(+)·)(CuBr_(2)),have been prepared via diffusion methods comprising arylthio-substituted tetrathiafulvalene derivatives 1-4 and CuBr_(2).Crystallographic studies indicate that the anions in the complexes,which are derived from CuBr_(2),show diverse configurations including octahedral(CuⅡ_(2)Br_(6))^(2-)and linear(CuⅠBr_(2))^(-).The plane of the outer four Br atoms and the plane of the central quadrilateral on(CuⅡ_(2)Br_(6))^(2-)have a different dihedral angle.Compounds 1-4 show radical cation and the central framework of compounds 1-4 are nearly planar in the complexes.The stacking structure and anionic configuration of the charge transfer complexes can be effectively regulated by regulating the substitution positions and sizes of halogen atoms on the aryl groups.CCDC:2119456,(1^(+)·)(Cu_(2)Br_(6))_(0.5);2119457,(2^(+)·)(Cu_(2)Br_(6))_(0.5);2119458,(3^(+)·)(Cu_(2)Br_(6))_(0.5);2119459,(4^(+)·)(CuBr_(2)).

关 键 词：四硫富瓦烯 溴化铜 晶体结构 电荷转移复合物 

分 类 号：O614.121[理学—无机化学]