Choosing sides: unusual ultrafast charge transfer pathways in an asymmetric electron-accepting cyclophane that binds an electron donor

Abstract

Constructing functional molecular systems for solar energy conversion and quantum information science requires a fundamental understanding of electron transfer in donor–bridge–acceptor (D–B–A) systems as well as competitive reaction pathways in acceptor–donor–acceptor (A–D–A) and acceptor–donor–acceptor′ (A–D–A′) systems. Herein we present a supramolecular complex comprising a tetracationic cyclophane having both phenyl-extended viologen (ExV²⁺) and dipyridylthiazolothiazole (TTz²⁺) electron acceptors doubly-linked by means of two p-xylylene linkers (TTzExVBox⁴⁺), which readily incorporates a perylene (Per) guest in its cavity (Per ⊂ TTzExVBox⁴⁺) to establish an A–D–A′ system, in which the ExV²⁺ and TTz²⁺ units serve as competing electron acceptors with different reduction potentials. Photoexcitation of the Per guest yields both TTz⁺˙–Per⁺˙–ExV²⁺ and TTz²⁺–Per⁺˙–ExV⁺˙ in <1 ps, while back electron transfer in TTz²⁺–Per⁺˙–ExV⁺˙ proceeds via the unusual sequence TTz²⁺–Per⁺˙–ExV⁺˙ → TTz⁺˙–Per⁺˙–ExV²⁺ → TTz²⁺–Per–ExV²⁺. In addition, selective chemical reduction of TTz²⁺ gives Per ⊂ TTzExVBox³⁺˙, turning the complex into a D–B–A system in which photoexcitation of TTz⁺˙ results in the reaction sequence ²*TTz⁺˙–Per–ExV²⁺ → TTz²⁺–Per–ExV⁺˙ → TTz⁺˙–Per–ExV²⁺. Both reactions TTz²⁺–Per⁺˙–ExV⁺˙ → TTz⁺˙–Per⁺˙–ExV²⁺ and TTz²⁺–Per–ExV⁺˙ → TTz⁺˙–Per–ExV²⁺ occur with a (16 ± 1 ps)⁻¹ rate constant irrespective of whether the bridge molecule is Per⁺˙ or Per. These results are explained using the superexchange mechanism in which the ionic states of the perylene guest serve as virtual states in each case and demonstrate a novel supramolecular platform for studying the effects of bridge energetics within D–B–A systems.