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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 (ExV 2+ ) and dipyridylthiazolothiazole (TTz 2+ ) electron acceptors doubly-linked by means of two p -xylylene linkers (TTzExVBox 4+ ), which readily incorporates a perylene (Per) guest in its cavity (Per ⊂ TTzExVBox 4+ ) to establish an A-D-A' system, in which the ExV 2+ and TTz 2+ units serve as competing electron acceptors with different reduction potentials. Photoexcitation of the Per guest yields both TTz + ˙-Per + ˙-ExV 2+ and TTz 2+ -Per + ˙-ExV + ˙ in &lt;1 ps, while back electron transfer in TTz 2+ -Per + ˙-ExV + ˙ proceeds via the unusual sequence TTz 2+ -Per + ˙-ExV + ˙ → TTz + ˙-Per + ˙-ExV 2+ → TTz 2+ -Per-ExV 2+ . In addition, selective chemical reduction of TTz 2+ gives Per ⊂ TTzExVBox 3+ ˙, turning the complex into a D-B-A system in which photoexcitation of TTz + ˙ results in the reaction sequence 2 *TTz + ˙-Per-ExV 2+ → TTz 2+ -Per-ExV + ˙ → TTz + ˙-Per-ExV 2+ . Both reactions TTz 2+ -Per + ˙-ExV + ˙ → TTz + ˙-Per + ˙-ExV 2+ and TTz 2+ -Per-ExV + ˙ → TTz + ˙-Per-ExV 2+ 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.

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