Transformation of dense AgI into a silver-rich framework iodide using thiophenol as mineralizer

A new three-dimensional framework iodide, (DabcoH)2[(Dabco)2Ag14I16] (1), was solvothermal synthesized by transformation of dense AgI using p-methylthiophenol as mineralizer, and characterized by elemental analysis, single-crystal and powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry analysis, UV–vis diffuse reflectance spectroscopy and fluorescence spectroscopy. Compound 1 crystallizes in the trigonal space group R-3c, a=13.4452(2) A, c=63.725(2) A, V=9976.5(4) A3, Z=6. It features a 3D silver-rich [(Dabco)2Ag14I16]2− anionic framework built up from corner-sharing of hybrid [(Dabco)2Ag14I19]5− clusters, with protonated DabcoH+ as counterions residing in the channels. UV–vis reflectance spectroscopy reveals the band gap of 1 is 3.3 eV. Compound 1 exhibits a strong photoluminescent emission band at 567 nm upon excitation at 489 nm.