The new super bulky 2-benzhydryl-4,6-dimethyl azide (2) was synthesized and used in click reaction for the synthesis of super-bulky 1-(2-benzhydryl-4,6-dimethylphenyl)-4-phenyl-1H-1,2,3-traizole (3). Further, the 1-(2-benzhydral-4,6-dimethylphenyl)-3-methyl-4-phenyl-1H-1,2,3-traizol-3-ium iodide (4) was isolated from the reaction between 3 and methyl iodide. These molecules were examined by FT-IR, TGA, CHN analysis, (1H and 13C) multinuclear NMR, UV–Vis, fluorescence, and SCXRD techniques. Molecules 2 and 3 depict the C-H····π intermolecular interactions, while 4 exhibits a rare intermolecular I····H-C(sp2) interactions (2.821 Å). The thermal stability of new super bulky triazole (3) and triazolium salt (4) was further exhibited by thermogravimetric analysis. The photophysical properties were investigated. © 2022 Wiley Periodicals LLC.