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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.authorGadde, Sureshen_US
dc.contributor.authorIslam, D-M Shafiqulen_US
dc.contributor.authorSchumacher, Amy Leaen_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorAraki, Yasuyakien_US
dc.contributor.authorIto, Osamuen_US
dc.identifier.citationThe journal of physical chemistry. B. 2006 Dec 21; 110(50): 25240-50.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractSupramolecular ferrocene-porphyrin-fullerene constructs, in which covalently linked ferrocene-porphyrin-crown ether compounds were self-assembled with alkylammonium cation functionalized fullerenes, have been designed to achieve stepwise electron transfer and hole shift to generate long-lived charge separated states. The adopted crown ether-alkylammonium cation binding strategy resulted in stable conjugates as revealed by computational studies performed by the DFT B3LYP/3-21G(*) method in addition to the binding constants obtained from fluorescence quenching studies. The free-energy changes for charge-separation and charge-recombination were varied by the choice of different metal ions in the porphyrin cavity. Free-energy calculations suggested that the light-induced electron-transfer processes from the singlet excited state of porphyrins to be exothermic in all of the investigated supramolecular dyads and triads. Photoinduced charge-separation and charge-recombination processes have been confirmed by the combination of the time-resolved fluorescence and nanosecond transient absorption spectral measurements. In case of the triads, the charge-recombination processes of the radical anion of the fullerene moiety take place in two steps, viz., a direct charge recombination from the porphyrin cation radical and a slower step involving distant charge recombination from the ferrocene cation moiety. The rates of charge recombination for the second route were found to be an order of magnitude slower than the former route, thus fulfilling the condition for charge migration to generate long-lived charge-separated states in supramolecular systems.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe journal of physical chemistry. Ben_US
dc.relation.ispartofseriesJ Phys Chem Ben_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subject.meshCrown Ethers/chemistryen_US
dc.subject.meshFerrous Compounds/chemistryen_US
dc.subject.meshMacromolecular Substances/chemical synthesisen_US
dc.subject.meshModels, Chemicalen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshOrganometallic Compounds/chemical synthesisen_US
dc.subject.meshQuaternary Ammonium Compounds/chemistryen_US
dc.subject.meshMacromolecular Substances/chemistryen_US
dc.subject.meshOrganometallic Compounds/chemistryen_US
dc.titleDesign and studies on supramolecular ferrocene-porphyrin-fullerene constructs for generating long-lived charge separated statesen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2006, American Chemical Societyen_US

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