Polymeric Iodoplumbate Incorporating Copper Iodide Complex Cation Layer: Structure and Theoretical Study of a New Semi-conductive Hybrid:{Cu(Ⅱ)(bipy)2IPbI3(H2O)2}n

摘要

A new iodoplumbate polymer incorporating copper iodide complex cation {[Cu(Ⅱ)(bipy)2I][PbI3](H2O)2}n 1(bipy = 2,2'-bipyridine) has been synthesized and structurally determined.It crystallizes in the triclinic system,space group P1 with a = 7.979(4),b = 14.538(11),c = 15.853(8),α = 110.77(2),β = 97.955(18),γ = 104.88(2)°,V = 1607.3(17)3,Z = 2,C20H16CuI4N4O2Pb,Mr = 1122.72,Dc = 2.320 g/cm3,F(000) = 1006,μ(MoKα) = 9.753,the final R = 0.0627 and wR = 0.1741 for 4846 observed reflections with Ⅰ > 2σ(Ⅰ).Structural analysis indicates that 1 consists of 2-D {[Cu(Ⅱ)(bipy)2I]}nn+ cation layers(based on π-π interaction and hydrogen bonds) and [PbI3]nn-polyanions.The C-H···I hydrogen bonds between {[Cu(Ⅱ)(bipy)2I]}nn+ cation layers and [PbI3]nn-polyanions lead to the formation of an interesting 3-D network.Optical absorp-tion spectrum indicates that 1 is a semiconductor,which is further validated by DFT calculation.Its electronic structure is also discussed.