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Ion-mediated Electron Transfer in a Supramolecular Donor-Acceptor Ensemble

Ion-mediated Electron Transfer in a Supramolecular Donor-Acceptor Ensemble

Jung Su Park, Elizabeth Karnas, Kei Ohkubo, Ping Chen, Karl M Kadish, Shunichi Fukuzumi, Christopher W Bielawski, Todd W Hudnall, Vincent M Lynch, Jonathan L Sessler

Science. 2010 Sep 10;329(5997):1324-7.

PMID: 20829481

Abstract:

Ion binding often mediates electron transfer in biological systems as a cofactor strategy, either as a promoter or as an inhibitor. However, it has rarely, if ever, been exploited for that purpose in synthetic host-guest assemblies. We report here that strong binding of specific anions (chloride, bromide, and methylsulfate but not tetrafluoroborate or hexafluorophosphate) to a tetrathiafulvalene calix[4]pyrrole (TTF-C4P) donor enforces a host conformation that favors electron transfer to a bisimidazolium quinone (BIQ2+) guest acceptor. In contrast, the addition of a tetraethylammonium cation, which binds more effectively than the BIQ2+ guest in the TTF-C4P cavity, leads to back electron transfer, restoring the initial oxidation states of the donor and acceptor pair. The products of these processes were characterized via spectroscopy and x-ray crystallography.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP429072	Tetraethylammonium hexafluorophosphate		429-07-2	Price

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