Two Iodoargentate Hybrid Coordination Polymers Induced by Transition-Metal Complexes: Structures and Properties

Two iodoargentate hybrid solids {[Ni(2,2′-bipy)(THF)2(H2O)2](Ag10I12)·2DMF}n (1) and {[Cu(2,2′-bipy)3](Ag5I7)}n (2) (THF=tetrahydrofuran, DMF=N,N′-dimethyl formamide, 2,2′-bipy =2,2′-bipyridine) have been synthesized in a polar organic solvent, whose one-dimensional iodoargentate polymers are induced by second entrapped metal−organic complexes. In 1, the [Ag5I6]nn− chain exhibits a columnar structure based on an Ag5I6 quasi-pentagram building block. In 2, the zigzag chain [Ag5I7]n2n− is constructed from an Ag6I11 building block. Two compounds exhibit intriguing semiconducting properties with Eg = 2.74 and 2.80 eV. As indicated by density functional theory calculations, the observed strong photoluminescence in 1 arises from band-edge transitions.