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Syntheses and excitation transfer studies of near-orthogonal freebase porphyrin-ruthenium phthalocyanine dyads and pentad

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dc.contributor.author Jacobs, Rachel
dc.contributor.author Stranius, Kati
dc.contributor.author Maligaspe, Eranda
dc.contributor.author Lemmetyinen, Helge
dc.contributor.author Tkachenko, Nikolai V.
dc.contributor.author Zandler, Melvin E.
dc.contributor.author D'Souza, Francis
dc.date.accessioned 2012-06-15T21:04:14Z
dc.date.available 2012-06-15T21:04:14Z
dc.date.issued 2012-03-19
dc.identifier.citation Jacobs, Rachel; Stranius, Kati; Maligaspe, Eranda; Lemmetyinen, Helge; Tkachenko, Nikolai V.; Zandler, Melvin E. & Francis, D'Souza. 2012. Syntheses and excitation transfer studies of near-orthogonal freebase porphyrin-ruthenium phthalocyanine dyads and pentad. INORGANIC CHEMISTRY, 51 (6):3656-3665; 10.1021/ic202574q MAR 19 2012 en_US
dc.identifier.issn 0020-1669
dc.identifier.issn 1520-510X
dc.identifier.uri http://hdl.handle.net/10057/5135
dc.identifier.uri http://dx.doi.org/10.1021/ic202574q
dc.description Click on the DOI link below to access the article (may not be free). en_US
dc.description.abstract A new series of molecular dyads and pentad featuring free-base porphyrin and ruthenium phthalocyanine have been synthesized and characterized. The synthetic strategy involved reacting free-base porphyrin functionalized with one or four entities of phenylirnidazole at the meso position of the porphyrin ring with ruthenium carbonyl phthalocyanine followed by chromatographic separation and purification of the products. Excitation transfer in these donor acceptor polyads (dyad and pentad) is investigated in nonpolar toluene and polar benzonitrile solvents using both steady-state and time-resolved emission techniques. Electrochemical and computational studies suggested that the photoinduced electron transfer is a thermodynamically unfavorable process in nonpolar media but may take place in a polar environment. Selective excitation of the donor, free-base porphyrin entity, resulted in efficient excitation transfer to the acceptor, ruthenium phthalocyanine, and the position of imid! azole linkage on the free-base porphyrin could be used to tune the rates of excitation transfer. The singlet excited Ru phthalocyanine thus formed instantly relaxed to the triplet state via intersystem crossing prior to returning to the ground state. Kinetics of energy transfer (kENT) was monitored by performing transient absorption and emission measurements using pump probe and upconversion techniques in toluene, respectively, and modeled using a Forster-type energy transfer mechanism. Such studies revealed the experimental lcEi,rr values on the order of 10(10)-10(11) s(-1), which readily agreed with the theoretically estimated values. Interestingly, in polar benzonitrile solvent, additional charge transfer interactions in the case of dyads but not in the case of pentad, presumably due to the geometry/orientation consideration, were observed. en_US
dc.language.iso en_US en_US
dc.publisher American Chemical Society en_US
dc.relation.ispartofseries INORGANIC CHEMISTRY;2012, v.51, no.6
dc.title Syntheses and excitation transfer studies of near-orthogonal freebase porphyrin-ruthenium phthalocyanine dyads and pentad en_US
dc.type Article en_US
dc.description.version Peer reviewed
dc.rights.holder © 2012 American Chemical Society

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