Introducing Transition-Metal Complex Together with Conjugated Ligand into Polymeric Iodoplumbate: Structure Characterization, Properties and Theoretical Study of a New Semi-Conductive Hybrid: {[Cu(II)(2,2′-bipy)3][Pb2I6]}n

A new hybrid coordination polymer {[Cu(II)(2,2'-bipy)(3)][Pb2I6]}(n) (1) was synthesized by the reaction of Cu(NO3)(2), 2,2'-bipy, PbI2 and NaI in DMF/DMSO mixed solvent. As revealed by X-ray structural analysis, 1 consists of [Pb2I6](n)(2n-) polyanions and discrete [Cu(II)(2,2'-bipy)(3)](2+) structure-directing agent cations. The polymeric negative chain [Pb2I6](n)(2-) is built up by face-sharing of PbI6 octahedra. Structure-directing reagent cations and polymeric negative chains are in combination with each other by static attracting force to form so-called hybrid structure. Experimental and theoretical optical property investigations indicate that 1 possesses semiconductor property. DFT calculation was executed to probe the electronic structure of 1. To our interest, when using both second metal and pi system as electronic tuning species, conjugated system is more preferable.