Long‐range Through‐space Charge Transfer in a pH‐responsive Mixed Cyclophane of Pyridine and Teropyrene

Abstract

AbstractA large, strained (SE=44.2 kcal/mol) and conformationally flexible mixed cyclophane of pyridine and teropyrene was synthesized using two intramolecular Wurtz coupling reactions and an unprecedented Scholl reaction between the unreactive 2 positions of the pyrene systems in a triply bridged pyrenophane. Protonation of the pyridine unit results in a greatly enhanced preference for nesting in the cavity of the highly bent teropyrene system (θcalc=162.6°) and emergence of a charge transfer absorption band (λmax=592 nm) due to a long range (5.0–5.5 Å), through‐space intramolecular transition between the teropyrene and pyridinium units, which does not exist in the neutral cyclophane.