Solvent‐Dependent Iodoargentate Hybrids: Syntheses, Structural Diversity, Thermochromism, and Photocatalysis

Charge‐balanced by protonated pyridine, four iodoargentate hybrids, [(Hpy)(Ag 2 I 3 )] n ( 1 , 2D), {[(Hpy) 2 · dmf][Ag 6 I 8 ]} n ( 2 , 2D), {[(Hpy) 2 · H 2 O][Ag 3 I 5 ]} n ( 3 , 1D) and [(Hpy)(Ag 5 I 6 )] n ( 4 , reported 3D) (Hpy + = protonated pyridine, dmf = N , N ‐dimethylformamide), were synthesized in the system comprising pyridine/AgI/HI/solvent (solvent: acetone for 1 , DMF for 2 , acetone/H 2 O for 3 , and acetonitrile for 4 ). Structural analysis revealed the significant influence of the solvent on the assembly and crystallization of the iodoargentate hybrids. Noteworthy, compounds 2 – 4 reveal a good structural match between the structure‐directing agents and the inorganic frameworks. The band gaps of 1 – 4 (2.93, 3.05, 2.99, and 2.71 eV for 1 , 2 , 3 , and 4 , respectively) also exhibit an intense correlation between the structural features of the hybrids and their photocatalytic properties in the degradation of rhodamine B under UV‐light irradiation. Moreover, compound 4 shows interesting thermochromism owing to its temperature‐dependent intermolecular charge transfer.