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

ABSTRACT

A 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.