A New 3D Iodoargentate Hybrid: Structure, Optical/Photoelectric Performance and Theoretical Research

The explorations of new three-dimensional (3D) microporous metal halides, especially the iodoargentate-based hybrids, and understanding of their structure-activity relationships are still quite essential but full of great challenges. Herein, with the aromatic 4,4'-dpa (4,4'-dpa = 4,4'-dipyridylamine) ligands as the structural directing agents, we solvothermal synthesized and structurally characterized a novel member of microporous iodoargentate family, namely [H -4,4'-dpa]Ag I ( ). Compound possesses a unique and complicated 3D [Ag I ] anionic architecture that was built up from the unusual hexameric [Ag I ] secondary building units (SBUs). Research on optical properties indicated that compound exhibited semiconductor behavior, with an optical band gap of 2.50 eV. Under the alternate irradiation of light, prominent photoelectric switching abilities could be achieved by compound [H -4,4'-dpa]Ag I , whose photocurrent densities (0.37 μA·cm for visible light and 1.23 μA·cm for full-spectrum) compared well with or exceeded those of some high-performance halide counterparts. Further theoretical calculations revealed that the relatively dispersed conduction bands (CBs) structures in compound induced higher electron mobilities, which may be responsible for its good photoelectricity. Presented in this work also comprised the analyses of Hirshfeld surface, powder X-ray diffractometer (PXRD), thermogravimetric measurement, energy-dispersive X-ray spectrum (EDX) along with X-ray photoelectron spectroscopy (XPS).