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Ultrafast singlet-singlet energy transfer in self-assembled via metal-ligand axial coordination of free-base porphyrin-zinc phthalocyanine and free-base porphyrin-zinc naphthalocyanine dyads

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dc.contributor Wichita State University. Department of Chemistry en_US
dc.contributor.author Maligaspe, Eranda en_US
dc.contributor.author Kumpulainen, Tatu en_US
dc.contributor.author Lemmetyinen, Helge en_US
dc.contributor.author Tkachenko, Nikolai V. en_US
dc.contributor.author Subbaiyan, Navaneetha K. en_US
dc.contributor.author Zandler, Melvin E. en_US
dc.contributor.author D'Souza, Francis en_US
dc.date.accessioned 2012-02-06T17:17:04Z
dc.date.available 2012-02-06T17:17:04Z
dc.date.issued 2010-01-14 en_US
dc.identifier 19928821 en_US
dc.identifier 9890903 en_US
dc.identifier.citation The journal of physical chemistry. A. 2010 Jan 14; 114(1): 268-77. en_US
dc.identifier.issn 1520-5215 en_US
dc.identifier.issn 1089-5639 en_US
dc.identifier.uri http://dx.doi.org/10.1021/jp908115e en_US
dc.identifier.uri http://hdl.handle.net/10057/4389
dc.description Click on the DOI link below to access the article (may not be free). en_US
dc.description.abstract Singlet-singlet energy transfer in self-assembled via axial coordination of imidazole-appended (at different positions of one of the meso-phenyl entities) free-base tetraphenylporphyrin, H(2)PIm, to either zinc phthalocyanine, ZnPc, or zinc naphthalocyanine, ZnNc, dyads is investigated in noncoordinating solvents, o-dichlorobenzene and toluene, using both steady-state and time-resolved transient absorption techniques. The newly formed supramolecular dyads were fully characterized by spectroscopic, computational, and electrochemical methods. The binding constants measured from optical absorption spectral data were found to be in the range of 10(4)-10(5) M(-1) for the 1:1 dyads, suggesting fairly stable complex formation. Electrochemical and computational studies suggested that photoinduced electron transfer is a thermodynamically unfavorable process when free-base porphyrin is excited in these dyads. Selective excitation of the donor free-base porphyrin entity was possible in both types of dyads formed by either of the ZnPc or ZnNc energy acceptors. Efficient singlet-singlet energy transfer was observed in these dyads, and the position of imidazole linkage on the free-base porphyrin entity, although flexible, seems to have some control over the overall efficiency of excited energy transfer process. Kinetics of energy transfer was monitored by performing transient absorption measurements using both up-conversion and pump-probe techniques. Such studies revealed ultrafast singlet-singlet energy transfer in the studied dyads with time constants on the order of 2-25 ps depending upon the type of the dyad. en_US
dc.format.extent 268-77 en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries The journal of physical chemistry. A en_US
dc.relation.ispartofseries J Phys Chem A 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 Chlorobenzenes/chemistry en_US
dc.subject.mesh Energy Transfer en_US
dc.subject.mesh Fluorescent Dyes/chemistry en_US
dc.subject.mesh Indoles/chemistry en_US
dc.subject.mesh Kinetics en_US
dc.subject.mesh Ligands en_US
dc.subject.mesh Molecular Structure en_US
dc.subject.mesh Organometallic Compounds/chemistry en_US
dc.subject.mesh Porphyrins/chemistry en_US
dc.subject.mesh Toluene/chemistry en_US
dc.title Ultrafast singlet-singlet energy transfer in self-assembled via metal-ligand axial coordination of free-base porphyrin-zinc phthalocyanine and free-base porphyrin-zinc naphthalocyanine dyads 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 © 2010, American Chemical Society en_US

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