Three Iodoargentate-Based Hybrids Decorated by Metal Complexes: Structures, Optical/Photoelectric Properties and Theoretical Studies

So far, the development of new iodoargentate-based hybrids, especially those compounds with metal complex cations, and the understanding of their structure–activity relationships have been of vital importance but full of challenges. Herein, using the in-situ-generated metal complex cations as structural directing agents, three new iodoargentate-based hybrids, namely, [Co(phen)3]Ag2PbI6 (phen = 1,10-phenanthroline; 1), [Ni(5,5-dmpy)3]Ag7I9·CH3CN (5,5-dmpy = 5,5-dimethyl-2,2-bipyridine; 2) and [Co(5,5-dmpy)3]Ag5I8 (3), have been solvothermally prepared and then structurally characterized. Compound 1 represents one new heterometallic Ag–Pb–I compound characteristic of the chain-like [Ag2PbI6]n2n− anions. Compound 2 features the straight one-dimensional (1D) [Ag7I9]n2n− anionic moieties, while compound 3 contains infrequent two types of curved [Ag5I8]n3n− anions. Optical properties reveal that the title compounds exhibit interesting semiconductor behaviors with the band gaps of 1.59–2.78 eV, which endow them with good photoelectric switching performances under the alternate light irradiations. We also present their Hirshfeld surface analyses, and the theoretical studies (band structures, density of states (DOS) and partial density of states (PDOS)).