Syntheses, Crystal Structures, and Photocatalytic Properties of Polymeric Iodoargentates [TM(2,2‐bipy)₃]Ag₃I₅ (TM = Mn, Fe, Co, Ni, Zn)

Abstract

Abstract Five isostructural polymeric iodoargentates incorporating similar transition metal complex cations as structure‐directing agents, – namely, [TM(2,2‐bipy) 3 ]Ag 3 I 5 [TM = Mn ( 1 ), Fe ( 2 ), Co ( 3 ), Ni ( 4 ), Zn ( 5 )] – have been solvothermally synthesized and structurally characterized. The title compounds contain saturated [TM(2,2‐bipy) 3 ] 2+ cations and one‐dimensional (1D) [Ag 3 I 5 ] 2– anionic chains formed by trans‐interconnection of [Ag 3 I 5 ] semicubes through Ag–I bonds. The optical absorption spectra indicate that compounds 1 – 5 are semiconductors with estimated band gaps of 2.28, 1.87, 1.95, 2.01, and 2.61 eV, respectively, which are mainly ascribed, on the basis of density functional theory (DFT) calculations, to charge transitions between the [Ag 3 I 5 ] 2– anionic chains and organic cationic units. We evaluated the photocatalytic efficiencies of compounds 1 , 2 , 4 , and 5 with regard to the decomposition of crystal violet (CV) under visible irradiation, and the four compounds showed excellent photodegradation abilities in comparison with N‐doped P25, with an order of 1 > 2 > 4 > 5 > P25. The luminescent properties and thermal stabilities of the title compounds were also studied.