Source:http://linkedlifedata.com/resource/pubmed/id/12658657
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
7
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| pubmed:dateCreated |
2003-3-26
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| pubmed:abstractText |
Pulse-radiolytic studies were performed to determine the rate constants of intermolecular electron transfer (k(et)) from fullerenes (C(60), C(76), and C(78)) to a series of arene radical cations in dichloromethane. The one-electron oxidation potentials of the employed arenes-corresponding to the one-electron reduction potentials of arene pi-radical cations-were determined in dichloromethane to evaluate the driving forces of electron-transfer oxidation of fullerenes with arene pi-radical cations. The driving force dependence of log k(et) shows a pronounced decrease towards the highly exothermic region, representing the first definitive confirmation of the existence of the Marcus inverted region in a truly intermolecular electron transfer. Electron-transfer reduction of fullerenes with anthracene radical anion was also examined by laser flash photolysis in benzonitrile. The anthracene radical anion was produced by photoinduced electron transfer from 10,10'-dimethyl-9,9',10,10'-tetrahydro-9,9'-biacridine [(AcrH)(2)] to the singlet excited state of anthracene in benzonitrile. The rate constants of electron transfer (k(et)) from anthracene radical anion to C(60), C(70), and a C(60) derivative were determined from the decay of anthracene radical anion in the presence of various concentrations of the fullerene. Importantly, a significant decrease in the k(et) value was observed at large driving forces (1.50 eV) as compared to the diffusion-limited value seen at smaller driving forces (0.96 eV). In conclusion, our study presents clear evidence for the Marcus inverted region in both the electron-transfer reduction and oxidation of fullerenes.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Apr
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| pubmed:issn |
0947-6539
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
4
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| pubmed:volume |
9
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
1585-93
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| pubmed:dateRevised |
2009-8-4
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| pubmed:year |
2003
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| pubmed:articleTitle |
Driving force dependence of intermolecular electron-transfer reactions of fullerenes.
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| pubmed:affiliation |
Department of Material and Life Science Graduate School of Engineering, Osaka University, Japan. fukuzumi@ap.chem.eng.osaka-u.ac.jp
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| pubmed:publicationType |
Journal Article
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