Transition-Metal-Complex-Directed Synthesis of Hybrid Iodoargentates with Single-Crystal to Single-Crystal Structural Transformation and Photocatalytic Properties.

We synthesized and characterized three types of isostructural iodoargentates, [TM(phen)]AgI·3DMF (TM = Co (), Ni (), Zn ()), [TM(phen)]AgI·DMF (TM = Co (), Ni (), Zn ()), and [TM(phen)]AgI·7DMF (TM = Co (), Ni (), Zn ()) (phen = 1,10-phenanthroline, DMF = dimethylformamide) using transition-metal (TM) complexes as the structure-directing agents. Compounds - and compounds - feature zero-dimensional anionic [AgI] and [AgI] clusters, respectively. All of the [TM(phen)] cations in compounds - are arranged into a two-dimensional (2D) (6,3) net layer. Interestingly, compounds - are kinetically unstable in the mother solution, and they can be converted to compounds - via irreversible single-crystal to single-crystal transformation processes, respectively, with distinct changes in the crystal morphology and structure. Compounds - feature one-dimensional (1D) zigzag chains constructed from [AgI] units. The UV-vis diffuse reflectance measurements demonstrate that compounds - possess the characteristics of semiconductors with band gaps of 2.58-2.71 eV and visible-light-irradiation-induced photocatalytic activities. Especially, compound 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.