Transition-Metal-Complex-Directed Synthesis of Hybrid Iodoargentates with Single-Crystal to Single-Crystal Structural Transformation and Photocatalytic Properties
Chunying Tang, Jie Yao, Yueying Li, Zhuoran Xia, Jian‐Biao Liu, Chun‐yang Zhang
Abstract
We synthesized and characterized three types of isostructural iodoargentates, [TM(phen)3]Ag2I4·3DMF (TM = Co (1), Ni (2), Zn (3)), [TM(phen)3]Ag3I5·DMF (TM = Co (4), Ni (5), Zn (6)), and [TM(phen)3]2Ag8I12·7DMF (TM = Co (7), Ni (8), Zn (9)) (phen = 1,10-phenanthroline, DMF = dimethylformamide) using transition-metal (TM) complexes as the structure-directing agents. Compounds 1–3 and compounds 4–6 feature zero-dimensional anionic [Ag4I8]4– and [Ag6I10]4– clusters, respectively. All of the [TM(phen)3]2+ cations in compounds 1–6 are arranged into a two-dimensional (2D) (6,3) net layer. Interestingly, compounds 1–3 are kinetically unstable in the mother solution, and they can be converted to compounds 4–6 via irreversible single-crystal to single-crystal transformation processes, respectively, with distinct changes in the crystal morphology and structure. Compounds 7–9 feature one-dimensional (1D) zigzag chains constructed from [Ag8I12]4– units. The UV–vis diffuse reflectance measurements demonstrate that compounds 1–9 possess the characteristics of semiconductors with band gaps of 2.58–2.71 eV and visible-light-irradiation-induced photocatalytic activities. Especially, compound 3 possesses higher photocatalytic degradation activity toward crystal violet (CV) and rhodamine B (RhB) in comparison to P25 under identical conditions. Moreover, the mechanism study reveals that the TM complex cations make a great contribution to the photocatalytic activity.