Two Silver Halobismuthate Hybrids Decorated by Photosensitive Metal Complexes: Syntheses, Structures, Photoelectric Properties, and Theoretical Studies

Guided by photosensitive metal complexes, two new organic–inorganic hybrid silver halobismuthates, namely, [Co(bipy)3]2[AgBiBr7][Bi2Br9]·H2O (bipy = 2,2′-bipyridine, 1) and [Zn(phen)3]2[Ag2Bi2I12] (phen = 1,10-phenanthroline, 2) have been solvothermally fabricated and structurally characterized. Compound 1 is a rare [Co(bipy)3]3+-templated Ag–Bi–X compound, featuring [AgBiBr7]3– and [Bi2Br9]3– as the two types of binuclear clusters. Compound 2 exhibits discrete [Ag2Bi2I12]4– anions formed by two centrosymmetric [AgBiI8] dimers via edge-sharing. UV–vis diffuse reflection analyses showed that compounds 1 and 2 have semiconductor behaviors, with the optical absorption edges of 2.40 and 2.15 eV, respectively. Moreover, they also display excellent photoelectric switching properties, which greatly outperform or are well comparable to many halide-based counterparts, especially compound 1. The Hirshfeld surface analyses, X-ray photoelectron spectroscopy characterizations, thermal stabilities, and theoretical studies (band gaps, density of states, and wave functions) are also discussed.