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Article: Photoinduced electron transfer within a zinc porphyrin-cyclobis(paraquat-p-phenylene) donor-acceptor dyad

TitlePhotoinduced electron transfer within a zinc porphyrin-cyclobis(paraquat-p-phenylene) donor-acceptor dyad
Authors
KeywordsDonor-acceptor systems
Electron transfer
Porphyrinoids
Transient absorption spectroscopy
Issue Date2014
Citation
Chemistry - A European Journal, 2014, v. 20, n. 45, p. 14690-14697 How to Cite?
AbstractUnderstanding the mechanism of efficient photoinduced electron-transfer processes is essential for developing molecular systems for artificial photosynthesis. Towards this goal, we describe the synthesis of a donor-acceptor dyad comprising a zinc porphyrin donor and a tetracationic cyclobis(paraquat-p-phenylene) (CBPQT4+ ) acceptor. The Xray crystal structure of the dyad reveals the formation of a dimeric motif through the intermolecular coordination between the triazole nitrogen and the central Zn metal of two adjacent units of the dyad. Photoinduced electron transfer within the dyad in MeCN was investigated by femtosecond and nanosecond transient absorption spectroscopy, as well as by transient EPR spectroscopy. Photoexcitation of the dyad produced a weakly coupled ZnP+ -C-CBPQT 3+ C spin-correlated radical-ion pair having a t = 146 ns lifetime and a spin-spin exchange interaction of only 0.23 mT. The long radical-ion-pair lifetime results from weak donor-acceptor electronic coupling as a consequence of having nine bonds between the donor and the acceptor, and the reduction in reorganization energy for electron transfer caused by charge dispersal over both paraquat units within CBPQT3+.
Persistent Identifierhttp://hdl.handle.net/10722/333098
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorFathalla, Maher-
dc.contributor.authorBarnes, Jonathan C.-
dc.contributor.authorYoung, Ryan M.-
dc.contributor.authorHartlieb, Karel J.-
dc.contributor.authorDyar, Scott M.-
dc.contributor.authorEaton, Samuel W.-
dc.contributor.authorSarjeant, Amy A.-
dc.contributor.authorCo, Dick T.-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:16:43Z-
dc.date.available2023-10-06T05:16:43Z-
dc.date.issued2014-
dc.identifier.citationChemistry - A European Journal, 2014, v. 20, n. 45, p. 14690-14697-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/333098-
dc.description.abstractUnderstanding the mechanism of efficient photoinduced electron-transfer processes is essential for developing molecular systems for artificial photosynthesis. Towards this goal, we describe the synthesis of a donor-acceptor dyad comprising a zinc porphyrin donor and a tetracationic cyclobis(paraquat-p-phenylene) (CBPQT4+ ) acceptor. The Xray crystal structure of the dyad reveals the formation of a dimeric motif through the intermolecular coordination between the triazole nitrogen and the central Zn metal of two adjacent units of the dyad. Photoinduced electron transfer within the dyad in MeCN was investigated by femtosecond and nanosecond transient absorption spectroscopy, as well as by transient EPR spectroscopy. Photoexcitation of the dyad produced a weakly coupled ZnP+ -C-CBPQT 3+ C spin-correlated radical-ion pair having a t = 146 ns lifetime and a spin-spin exchange interaction of only 0.23 mT. The long radical-ion-pair lifetime results from weak donor-acceptor electronic coupling as a consequence of having nine bonds between the donor and the acceptor, and the reduction in reorganization energy for electron transfer caused by charge dispersal over both paraquat units within CBPQT3+.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectDonor-acceptor systems-
dc.subjectElectron transfer-
dc.subjectPorphyrinoids-
dc.subjectTransient absorption spectroscopy-
dc.titlePhotoinduced electron transfer within a zinc porphyrin-cyclobis(paraquat-p-phenylene) donor-acceptor dyad-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.201403744-
dc.identifier.pmid25303639-
dc.identifier.scopuseid_2-s2.0-84919346731-
dc.identifier.volume20-
dc.identifier.issue45-
dc.identifier.spage14690-
dc.identifier.epage14697-
dc.identifier.eissn1521-3765-
dc.identifier.isiWOS:000344358900021-

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