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)Å, c=63.725(2)Å, V=9976.5(4)Å3, 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 3.3eV. Compound 1 exhibits a strong photoluminescent emission band at 567nm upon excitation at 489nm. A new 3-D iodoargentate was synthesized by transformation of dense AgI in I−-deficient system using thiophenol as mineralizer. [Display omitted] •We have developed a new method to synthesize iodide using thiophenol as mineralizer.•A new 3D iodide, (DabcoH)2[(Dabco)2Ag14I16], was synthesized by transformation of dense AgI under solvothermal condition.•The compound features a 3D Ag–I framework with highest Ag/I ratio.•Compound 1 is a semiconductor with the band gap of 3.3eV.•Compound 1 exhibits a strong photoluminescent emission band at 567nm upon excitation at 489nm.