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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorD'Souza, Francisen_US
dc.contributor.authorSmith, Phillip M.en_US
dc.contributor.authorRogers, Lisa M.en_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorIslam, D-M Shafiqulen_US
dc.contributor.authorAraki, Yasuyakien_US
dc.contributor.authorIto, Osamuen_US
dc.identifier.citationInorganic chemistry. 2006 Jun 26; 45(13): 5057-65.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractDonor-acceptor dyads were constructed using zinc N-confused porphyrin (ZnNCP), a structural isomer of zinc tetraphenylporphyrin, as a donor, and fullerene as an electron acceptor. Two derivatives, pyridine-coordinated zinc N-confused porphyrin (Py:ZnNCP) and the zinc N-confused porphyrin dimer (ZnNCP-dimer) were utilized to form the dyads with an imidazole-appended fulleropyrrolidine (C60Im). These porphyrin isomers formed well-defined 1:1 supramolecular dyads (C60Im:ZnNCP) via axial coordination. The dyads were characterized by optical absorption and emission, ESI-mass, 1H NMR, and electrochemical methods. The binding constant, K, was found to be 2.8 x 10(4) M(-1) for C60Im:ZnNCP. The geometric and electronic structure of C60Im:ZnNCP were probed by using DFT B3LYP/3-21G methods. The HOMO was found to be on the ZnNCP entity, while the LUMO was primarily on the fullerene entity. The electrochemical properties of C60Im:ZnNCP was probed using cyclic voltammetry in o-dichlorobenzene, 0.1 n-Bu4NClO4. The Py:ZnNCP was found to be easier to oxidize by over 340 mV compared to Py:ZnTPP. Upon dyad formation via axial coordination, the first oxidation revealed an anodic shift of nearly 90 mV. Evidence of photoinduced charge separation from the singlet excited ZnNCP to the appended fullerene was established from time-resolved emission and nanosecond transient absorption studies.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic chemistryen_US
dc.relation.ispartofseriesInorg Chemen_US
dc.titleFormation, spectral, electrochemical, and photochemical behavior of zinc N-confused porphyrin coordinated to imidazole functionalized fullerene dyadsen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2006 American Chemical Societyen_US

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