Ion-Mediated Electron Transfer in a Supramolecular Donor-Acceptor Ensemble
- Authors
- Park, Jung Su; Karnas, Elizabeth; Ohkubo, Kei; Chen, Ping; Kadish, Karl; Fukuzumi, Shunichi; Bielawski, Christopher W.; Hudnall, Todd W.; Lynch, Vincent M.; Sessler, Jonathan L.
- Issue Date
- Sep-2010
- Publisher
- AMER ASSOC ADVANCEMENT SCIENCE
- Citation
- SCIENCE, v.329, no.5997, pp 1324 - 1327
- Pages
- 4
- Journal Title
- SCIENCE
- Volume
- 329
- Number
- 5997
- Start Page
- 1324
- End Page
- 1327
- URI
- https://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/147975
- DOI
- 10.1126/science.1192044
- ISSN
- 0036-8075
1095-9203
- 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 (BIQ(2+)) guest acceptor. In contrast, the addition of a tetraethylammonium cation, which binds more effectively than the BIQ(2+) 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.
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