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

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^+·)(I₃)·I₂、(2^+·)(I₅)·I₂和(3²⁺)(I₃)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^+·)(I₃)·I₂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^+·)(I₅)·I₂为P1空间群，2^+·呈椅式构型。复合物(3²⁺)(I₃)₂为Pbca空间群，3²⁺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I₃^-或I₅^-/I₂组成的一维链状和I₃^-/I₂组成的二维网格状。

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

Three charge-transfer (CT) complexes (1^+·)(I₃)·I₂, (2^+·)(I₅)·I₂, and (3²⁺)(I₃)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^+·)(I₃)·I₂ crystallizes in the C2/c space group. 1^+· takes the chair configuration. The asymmetric unit contains half of 1^+· ions, half of I₃^- ions, and half of I₂ molecules. The charge transfer between compound 1 with iodine is consistent in the complex in solution. Complex (2^+·)(I₅)·I₂ crystallizes in the P1 space group, and 2^+· takes the chair conformation. The asymmetric unit contains one 2^+· ion, one I₅^- ion, and one I₂ molecule. Complex (3²⁺)(I₃)₂ crystallizes in the Pbca space group, and 3²⁺ takes the unique planar configuration. The asymmetric unit contains one 3²⁺ ion and two I₃^- 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 I₃^- or I₅^-/I₂, and 2D iodine networks comprised of I₂ and I₃^-. CCDC: 2258351, (1^+·)(I₃)·I₂; 2258352, (2^+·)(I₅)·I₂; 2258353, (3²⁺)(I₃)₂.