File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Mechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle

TitleMechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle
Authors
Issue Date2012
Citation
Proceedings of the National Academy of Sciences of the United States of America, 2012, v. 109, n. 29, p. 11546-11551 How to Cite?
AbstractThe kinetics and thermodynamics of intramolecular electron transfer (IET) can be subjected to redox control in a bistable [2]rotaxane comprised of a dumbbell component containing an electron-rich 1,5-dioxynaphthalene (DNP) unit and an electron-poor phenylenebridged bipyridinium (P-BIPY2+) unit and a cyclobis (paraquatp-phenylene) (CBPQT4+) ring component. The [2]rotaxane exists in the ground-state co-conformation (GSCC) wherein the CBPQT4+ring encircles the DNP unit. Reduction of the CBPQT 4+ leads to the CBPQT2(•+) diradical dication while the P-BIPY2+ unit is reduced to its P-BIPY•+ radical cation. A radical-state co-conformation (RSCC) results from movement of the CBPQT2(•+) ring along the dumbbell to surround the P-BIPY •+ unit. This shuttling event induces IET to occur between the pyridinium redox centers of the P-BIPY•+ unit, a property which is absent between these redox centers in the free dumbbell and in the 1:1 complex formed between the CBPQT2(•+)ring and the radical cation of methyl-phenylene-viologen (MPV•+). Using electron paramagnetic resonance (EPR) spectroscopy, the process of IET was investigated by monitoring the line broadening at varying temperatures and determining the rate constant (kET =1.33 × 107 s-1) and activation energy (ΔG‡ = 1.01 kcal mol-1) for electron transfer. These values were compared to the corresponding values predicted, using the optical absorption spectra and Marcus-Hush theory.
Persistent Identifierhttp://hdl.handle.net/10722/332994
ISSN
2023 Impact Factor: 9.4
2023 SCImago Journal Rankings: 3.737
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorBarnes, Jonathan C.-
dc.contributor.authorFahrenbach, Albert C.-
dc.contributor.authorDyar, Scott M.-
dc.contributor.authorFrasconi, Marco-
dc.contributor.authorGiesener, Marc A.-
dc.contributor.authorZhu, Zhixue-
dc.contributor.authorLiu, Zhichang-
dc.contributor.authorHartlieb, Karel J.-
dc.contributor.authorCarmieli, Ranaan-
dc.contributor.authorWasielewski, Michael R.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:15:57Z-
dc.date.available2023-10-06T05:15:57Z-
dc.date.issued2012-
dc.identifier.citationProceedings of the National Academy of Sciences of the United States of America, 2012, v. 109, n. 29, p. 11546-11551-
dc.identifier.issn0027-8424-
dc.identifier.urihttp://hdl.handle.net/10722/332994-
dc.description.abstractThe kinetics and thermodynamics of intramolecular electron transfer (IET) can be subjected to redox control in a bistable [2]rotaxane comprised of a dumbbell component containing an electron-rich 1,5-dioxynaphthalene (DNP) unit and an electron-poor phenylenebridged bipyridinium (P-BIPY2+) unit and a cyclobis (paraquatp-phenylene) (CBPQT4+) ring component. The [2]rotaxane exists in the ground-state co-conformation (GSCC) wherein the CBPQT4+ring encircles the DNP unit. Reduction of the CBPQT 4+ leads to the CBPQT2(•+) diradical dication while the P-BIPY2+ unit is reduced to its P-BIPY•+ radical cation. A radical-state co-conformation (RSCC) results from movement of the CBPQT2(•+) ring along the dumbbell to surround the P-BIPY •+ unit. This shuttling event induces IET to occur between the pyridinium redox centers of the P-BIPY•+ unit, a property which is absent between these redox centers in the free dumbbell and in the 1:1 complex formed between the CBPQT2(•+)ring and the radical cation of methyl-phenylene-viologen (MPV•+). Using electron paramagnetic resonance (EPR) spectroscopy, the process of IET was investigated by monitoring the line broadening at varying temperatures and determining the rate constant (kET =1.33 × 107 s-1) and activation energy (ΔG‡ = 1.01 kcal mol-1) for electron transfer. These values were compared to the corresponding values predicted, using the optical absorption spectra and Marcus-Hush theory.-
dc.languageeng-
dc.relation.ispartofProceedings of the National Academy of Sciences of the United States of America-
dc.titleMechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1073/pnas.1201561109-
dc.identifier.pmid22685213-
dc.identifier.scopuseid_2-s2.0-84863915625-
dc.identifier.volume109-
dc.identifier.issue29-
dc.identifier.spage11546-
dc.identifier.epage11551-
dc.identifier.eissn1091-6490-
dc.identifier.isiWOS:000306837100020-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats