Macrocyclic Donor-Acceptor Dyads Composed of a Perylene Bisimide Dye Surrounded by Oligothiophene Bridges

Angew Chem Int Ed Engl. 2022 Jan 3;61(1):e202113598. doi: 10.1002/anie.202113598. Epub 2021 Nov 23.

Abstract

Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide (PBI) dye have been synthesized via a platinum-mediated cross-coupling strategy. The crystal structure of the double bridged PBI reveals all syn-arranged thiophene units that completely enclose the planar PBI chromophore via a 12-membered macrocycle. The target structures were characterized by steady-state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Both donor-acceptor dyads show ultrafast Förster Resonance Energy Transfer and photoinduced electron transfer, thereby leading to extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent.

Keywords: donor-acceptor dyads; macrocycles; oligothiophenes; perylene bisimide; photoinduced electron transfer.