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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorMaligaspe, Erandaen_US
dc.contributor.authorKumpulainen, Tatuen_US
dc.contributor.authorLemmetyinen, Helgeen_US
dc.contributor.authorTkachenko, Nikolai V.en_US
dc.contributor.authorSubbaiyan, Navaneetha K.en_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorD'Souza, Francisen_US
dc.identifier.citationThe journal of physical chemistry. A. 2010 Jan 14; 114(1): 268-77.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractSinglet-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.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe journal of physical chemistry. Aen_US
dc.relation.ispartofseriesJ Phys Chem Aen_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.meshEnergy Transferen_US
dc.subject.meshFluorescent Dyes/chemistryen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshOrganometallic Compounds/chemistryen_US
dc.titleUltrafast singlet-singlet energy transfer in self-assembled via metal-ligand axial coordination of free-base porphyrin-zinc phthalocyanine and free-base porphyrin-zinc naphthalocyanine dyadsen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2010, American Chemical Societyen_US

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