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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorD'Souza, Francisen_US
dc.contributor.authorMaligaspe, Erandaen_US
dc.contributor.authorOhkubo, Keien_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorSubbaiyan, Navaneetha K.en_US
dc.contributor.authorFukuzumi, Shunichien_US
dc.date.accessioned2012-02-06T17:17:30Z
dc.date.available2012-02-06T17:17:30Z
dc.date.issued2009-07-01en_US
dc.identifier19505071en_US
dc.identifier7503056en_US
dc.identifier.citationJournal of the American Chemical Society. 2009 Jul 1; 131(25): 8787-97.en_US
dc.identifier.issn1520-5126en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://dx.doi.org/10.1021/ja903467wen_US
dc.identifier.urihttp://hdl.handle.net/10057/4430
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractBy employing well-defined self-assembly methods, a biomimetic bacterial photosynthetic reaction center complex has been constructed, and photoinduced electron transfer originating in this supramolecular donor-acceptor conjugate has been investigated. The biomimetic model of the bacterial "special pair" donor, a cofacial zinc phthalocyanine dimer, was formed via potassium ion induced dimerization of 4,5,4',5',4'', 5'',4''',5'''-zinc tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyanine. The dimer was subsequently self-assembled with functionalized fullerenes via "two-point" binding involving axial coordination and crown ether-alkyl ammonium cation complexation to form the donor-acceptor pair, mimicking the noncovalently bound entities of the bacterial photosynthetic reaction center. The adopted self-assembly methodology yielded a supramolecular complex of higher stability with defined geometry and orientation as revealed by the binding constant and computational optimized structure. Unlike the previously reported porphyrin analog, the present phthalocyanine macrocycle based model system exhibited superior electron-transfer properties including formation of a long-lived charge-separated state, a key step of the photosynthetic light energy conversion process. Detailed analysis of the kinetic data in light of the Marcus theory of electron transfer revealed that small reorganization energy of the relatively rigid phthalocyanine is primarily responsible for slower charge-recombination process. The importance of the cofacial dimer in stabilizing the charge-separated state is borne out in the present all-supramolecular "reaction center" donor-acceptor mimic.en_US
dc.format.extent8787-97en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesJournal of the American Chemical Societyen_US
dc.relation.ispartofseriesJ. Am. Chem. Soc.en_US
dc.sourceNLMen_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subjectResearch Support, U.S. Gov't, Non-P.H.S.en_US
dc.subject.meshBacteria/chemistryen_US
dc.subject.meshBiomimeticsen_US
dc.subject.meshComputer Simulationen_US
dc.subject.meshDimerizationen_US
dc.subject.meshElectrochemistryen_US
dc.subject.meshElectron Transporten_US
dc.subject.meshFullerenes/chemistryen_US
dc.subject.meshIndoles/chemistryen_US
dc.subject.meshMagnetic Resonance Spectroscopyen_US
dc.subject.meshModels, Biologicalen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshOrganometallic Compounds/chemistryen_US
dc.subject.meshPhotosynthetic Reaction Center Complex Proteins/chemistryen_US
dc.subject.meshQuantum Theoryen_US
dc.subject.meshSpectrometry, Fluorescenceen_US
dc.subject.meshSpectrophotometry, Ultravioleten_US
dc.subject.meshBacteria/metabolismen_US
dc.subject.meshPhotosynthetic Reaction Center Complex Proteins/metabolismen_US
dc.titlePhotosynthetic reaction center mimicry: low reorganization energy driven charge stabilization in self-assembled cofacial zinc phthalocyanine dimer-fullerene conjugateen_US
dc.typeArticleen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2009 American Chemical Societyen_US


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