Twisting the Propotypic Molecules of Ph–C≡C–Ph, Ph–CH═CH–Ph, and Ph–N═N–Ph through Cocrystallization

Trans-stilbene, trans-azobenzene, and diphenylacetylene are the prototypic models for photochemical and photophysical studies. This work focuses on the structural investigation of their twisting behavior, which may significantly impact their electronic and photophysical properties. Here, we demonstrate the use of supramolecular derivatization to induce twists in these molecules without chemical modification using π···π-hole interactions with decafluorobiphenyl (FBPh). Cocrystallization with FBPh resulted in twisted conformations, which are further relaxed to the plane conformation in the melt.