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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorD'Souza, Francisen_US
dc.contributor.authorChitta, Raghuen_US
dc.contributor.authorOhkubo, Keien_US
dc.contributor.authorTasior, Mariuszen_US
dc.contributor.authorSubbaiyan, Navaneetha K.en_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorRogacki, Maciek K.en_US
dc.contributor.authorGryko, Daniel T.en_US
dc.contributor.authorFukuzumi, Shunichien_US
dc.identifier.citationJournal of the American Chemical Society. 2008 Oct 29; 130(43): 14263-72.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractThe first example of covalently linked free-base corrole-fullerene dyads is reported. In the newly synthesized dyads, the free-energy calculations performed by employing the redox and singlet excited-state energy in both polar and nonpolar solvents suggested the possibility of electron transfer from the excited singlet state of corrole to the fullerene entity. Accordingly, steady-state and time-resolved emission studies revealed efficient fluorescence quenching of the corrole entity in the dyads. Further studies involving femtosecond laser flash photolysis and nanosecond transient absorption studies confirmed electron transfer to be the quenching mechanism, in which the electron-transfer product, the fullerene anion radical, was able to be spectrally characterized. The rate of charge separation, kCS, was found to be on the order of 10(10)-10(11) s(-1), suggesting an efficient photoinduced electron-transfer process. Interestingly, the rate of charge recombination, kCR, was slower by 5 orders of magnitude in nonpolar solvents, cyclohexane and toluene, resulting in a radical ion-pair lasting for several microseconds. Careful analysis of the kinetic and thermodynamic data using the Marcus approach revealed that this novel feature is due to appropriately positioning the energy level of the charge-separated state below the triplet states of either of the donor and acceptor entities in both polar and nonpolar solvents, a feature that was not evident in donor-acceptor dyads constructed using symmetric tetrapyrroles as electron donors.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesJournal of the American Chemical Societyen_US
dc.relation.ispartofseriesJ. Am. Chem. Soc.en_US
dc.titleCorrole-fullerene dyads: formation of long-lived charge-separated states in nonpolar solventsen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2008 American Chemical Societyen_US

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