Two [Co(bipy)3]3+-Templated Silver Halobismuthate Hybrids: Syntheses, Structures, Photocurrent Responses, and Theoretical Studies

Employing in situ-generated metal complexes as structural decorating agents, we, for the first time, isolated two [Co(bipy)3]3+-templated silver halobismuthate hybrids, namely [Co(bipy)3]2Ag4Bi2X16 (X = Br (1), I (2); bipy = 2,2'-bipyridine). Compounds 1 and 2 belong to the isomorphic phrases and exhibit the nonperovskite structures characteristic of the discrete [Ag4Bi2X16]6- anions. UV-vis absorption spectra analyses showed that the optical band gaps of compounds 1 and 2 are 2.40 and 1.95 eV, respectively, implying the visible light responding semiconductor properties. Moreover, under the alternate light illumination, the title compounds exhibited "on/off" photocurrent behaviors, with high photocurrent densities comparable to many metal halide hybrids. Presented in this work also involved the Hirshfeld surface analyses and X-ray photoelectron spectroscopy studies together with the theoretical band structures, density of states, and electron wave functions.