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Photosynthetic reaction center mimicry: low reorganization energy driven charge stabilization in self-assembled cofacial zinc phthalocyanine dimer-fullerene conjugate

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dc.contributor Wichita State University. Department of Chemistry en_US
dc.contributor.author D'Souza, Francis en_US
dc.contributor.author Maligaspe, Eranda en_US
dc.contributor.author Ohkubo, Kei en_US
dc.contributor.author Zandler, Melvin E. en_US
dc.contributor.author Subbaiyan, Navaneetha K. en_US
dc.contributor.author Fukuzumi, Shunichi en_US
dc.date.accessioned 2012-02-06T17:17:30Z
dc.date.available 2012-02-06T17:17:30Z
dc.date.issued 2009-07-01 en_US
dc.identifier 19505071 en_US
dc.identifier 7503056 en_US
dc.identifier.citation Journal of the American Chemical Society. 2009 Jul 1; 131(25): 8787-97. en_US
dc.identifier.issn 1520-5126 en_US
dc.identifier.issn 0002-7863 en_US
dc.identifier.uri http://dx.doi.org/10.1021/ja903467w en_US
dc.identifier.uri http://hdl.handle.net/10057/4430
dc.description Click on the DOI link below to access the article (may not be free). en_US
dc.description.abstract By 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.extent 8787-97 en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries Journal of the American Chemical Society en_US
dc.relation.ispartofseries J. Am. Chem. Soc. en_US
dc.source NLM en_US
dc.subject Research Support, Non-U.S. Gov't en_US
dc.subject Research Support, U.S. Gov't, Non-P.H.S. en_US
dc.subject.mesh Bacteria/chemistry en_US
dc.subject.mesh Biomimetics en_US
dc.subject.mesh Computer Simulation en_US
dc.subject.mesh Dimerization en_US
dc.subject.mesh Electrochemistry en_US
dc.subject.mesh Electron Transport en_US
dc.subject.mesh Fullerenes/chemistry en_US
dc.subject.mesh Indoles/chemistry en_US
dc.subject.mesh Magnetic Resonance Spectroscopy en_US
dc.subject.mesh Models, Biological en_US
dc.subject.mesh Models, Molecular en_US
dc.subject.mesh Organometallic Compounds/chemistry en_US
dc.subject.mesh Photosynthetic Reaction Center Complex Proteins/chemistry en_US
dc.subject.mesh Quantum Theory en_US
dc.subject.mesh Spectrometry, Fluorescence en_US
dc.subject.mesh Spectrophotometry, Ultraviolet en_US
dc.subject.mesh Bacteria/metabolism en_US
dc.subject.mesh Photosynthetic Reaction Center Complex Proteins/metabolism en_US
dc.title Photosynthetic reaction center mimicry: low reorganization energy driven charge stabilization in self-assembled cofacial zinc phthalocyanine dimer-fullerene conjugate en_US
dc.type Article en_US
dc.coverage.spacial United States en_US
dc.description.version peer reviewed en_US
dc.rights.holder Copyright © 2009 American Chemical Society en_US

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