Hybrid silver haloplumbates containing metal complexes: Syntheses, structures and photoelectric properties

By using in situ-generated [M(phen)3]2+ (M ​= ​Fe and Ni; phen ​= ​1,10-phenanthroline) complexes as structural modifying agents, three new heterometallic silver-based haloplumbate hybrids, namely [M(phen)3]Ag2PbBr6 (M ​= ​Fe (1) and Ni (2)) and [Ni(phen)3]Ag2PbI6 (3), have been solvothermally obtained and structurally characterized. Compounds 1–3 are isomorphic phases, featuring the curve-like [Ag2PbX6]2− (X ​= ​Br, I) anions that are separated by [M(phen)3]2+ metal complexes. UV–Vis diffuse-reflectance analyses reveal that the title compounds possess the optical band gaps of 1.99–2.74 ​eV. Attractively, they showed evident and rapid photoelectrical switching properties when exposed to the alternate light irradiation, with the photocurrent densities comparable to many metal halide hybrids. In addition, the Hirshfeld surface analyses, X-ray photoelectron spectroscopy (XPS), theoretical band structure, as well as the density of states (DOS) have also been explored.