芳基四硫富瓦烯与碘电荷转移复合物的合成及其晶体结构  

Synthesis and crystal structure of the charge transfer complexes of arylthiotetrathiafulvalenes and iodine

作　　者：左琦[1] 马龙飞 ZUO Qi;MA Long‑Fei(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》2023年第10期1869-1876,共8页Chinese Journal of Inorganic Chemistry

基　　金：河南省科技厅项目(No.222102310354)资助。

摘　　要：采用缓慢挥发溶剂的方法合成了硫原子桥联芳基取代四硫富瓦烯(Ar‑S‑TTF)与碘的3种电荷转移复合物(1+·)(I_(3))·I_(2)、(2^(+·))(I_(5))·I_(2)和(3^(2+))(I_(3))_(2),采用单晶X射线衍射、紫外可见光谱、循环伏安对其进行了表征。复合物(1+·)(I_(3))·I_(2)为C2/c空间群,1+·呈椅式构型。化合物1与碘之间在溶液中和复合物中电荷转移一致。复合物(2^(+·))(I_(5))·I_(2)为P1空间群,2^(+·)呈椅式构型。复合物(3^(2+))(I_(3))_(2)为Pbca空间群,3^(2+)呈独特的平面构型。化合物2和3与碘之间在溶液中和复合物中呈现不同的电荷转移。复合物中聚碘阴离子呈现不同的堆积结构:由I_(3)^(-)或I_(5)^(-)/I_(2)组成的一维链状和I_(3)^(-)/I_(2)组成的二维网格状。Three charge‑transfer(CT)complexes(1+·)(I_(3))·I_(2),(2^(+·))(I_(5))·I_(2),and(3^(2+))(I_(3))_(2)have been prepared via solvent evaporation method comprising arylthio‑substituted tetrathiafulvalene derivatives(Ar‑S‑TTF)and iodine.Single crystal X‑ray diffraction,UV‑Vis spectrum,and cyclic voltammetry were used to characterize the complexes.Complex(1+·)(I_(3))·I_(2)crystallizes in the C2/c space group.1+·takes the chair configuration.The asymmetric unit contains half of 1+·ions,half of I_(3)^(-)ions,and half of I_(2)molecules.The charge transfer between compound 1 with iodine is consistent in the complex in solution.Complex(2^(+·))(I_(5))·I_(2)crystallizes in the P1 space group,and 2^(+·)takes the chair conformation.The asymmetric unit contains one 2^(+·)ion,one I_(5)^(-)ion,and one I_(2)molecule.Complex(3^(2+))(I_(3))_(2)crystallizes in the Pbca space group,and 3^(2+)takes the unique planar configuration.The asymmetric unit contains one 3^(2+)ion and two I_(3)^(-)ions.Compounds 2 and 3 exhibit different charge transfers with iodine in solution and the complex.The iodine components in the complexes show various structures including the 1D chain of I_(3)^(-)or I_(5)^(-)/I_(2),and 2D iodine networks comprised of I_(2)and I_(3)^(-).CCDC:2258351,(1+·)(I_(3))·I_(2);2258352,(2^(+·))(I_(5))·I_(2);2258353,(3^(2+))(I_(3))_(2).

关 键 词：四硫富瓦烯 碘 晶体结构 电荷转移复合物 

分 类 号：O613.44[理学—无机化学]