Halogen‐ and Counterion‐Modulated Photochromic and Photoluminescence Properties of Haloargentate Hybrids

Five haloargentate hybrids with isostructural 1D [Ag2X3]nn– (X = Br/I) anionic chains have been designed and solvothermally synthesized with saturated tetraethylammonium (TEA+) and unsaturated methylated/ethylated 3‐cyanopyridinium (MCP+/ECP+) cations, which show reversible photochromic behavior and switchable photoluminescence based on photolysis of haloargentate anions. Existence of mixed halides and introduction of electron deficient organic cations can significantly enhance their photosensitivity. By selecting saturated tetraethylammonium (TEA+) and unsaturated methylated/ethylated 3‐cyanopyridinium (MCP+/ECP+) as cations, five haloargentate hybrids with isostructural 1D [Ag2X3]nn– (X = Br/I) anionic chains have been designed and solvothermally synthesized. These hybrids show reversible photochromic behavior based on photolysis of haloargentate anions.