Redox-Active Scandium Oxide Cluster inside a Fullerene Cage: Spectroscopic, Voltammetric, Electron Spin Resonance Spectroelectrochemical, and Extended Density Functional Theory Study of ScO@C and Its Ion Radicals.
The clusterfullerene ScO@C with a mixed redox state of scandium was found to be an exciting molecule for endohedral electrochemistry as demonstrated by means of an in situ electron spin resonance (ESR) spectroelectrochemical study of the spin density distribution in its electrochemically generated c...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 48; pp. 19607 - 19619 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
12/5/2012
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=84231964&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 84231964 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/5/2012 vid: 134 iid: 48 pid: 997 pub: American Chemical Society artinfo: ui: 84231964 10.1021/ja306728p ppf: 19607 ppct: 12 formats: tig: atl: Redox-Active Scandium Oxide Cluster inside a Fullerene Cage: Spectroscopic, Voltammetric, Electron Spin Resonance Spectroelectrochemical, and Extended Density Functional Theory Study of ScO@C and Its Ion Radicals. aug: au: Popov, Alexey A. Ning Chen Pinzón, Julio R. Stevenson, Steven Echegoyen, Luis A. Dunsch, Lothar affil: Leibniz-Institute for Solid State and Materials Research, Department of Electrochemistry and Conducting Polymers, 01069 Dresden, Germany Chemistry Department, Moscow State University, 119992 Moscow, Russian Federation Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968-0519, United States Department of Chemistry, Clemson University, Clemson, South Carolina 29634-0973, United States College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China Department of Chemistry, Indiana-Purdue University at Fort Wayne, Fort Wayne, Indiana 46895-1499, United States su: Scandium oxides Oxidation-reduction reaction Fullerenes Electron paramagnetic resonance spectroscopy Density functionals Radicals (Chemistry) Ions Electrochemistry sug: subj: Scandium oxides Oxidation-reduction reaction Fullerenes Electron paramagnetic resonance spectroscopy Density functionals Radicals (Chemistry) Ions Electrochemistry ab: The clusterfullerene ScO@C with a mixed redox state of scandium was found to be an exciting molecule for endohedral electrochemistry as demonstrated by means of an in situ electron spin resonance (ESR) spectroelectrochemical study of the spin density distribution in its electrochemically generated cation and anion radicals. The compound exhibits two reversible reduction and oxidation steps with a relatively small electrochemical gap of 1.10 V. The ESR spectra of the ion radicals have a rich hyperfine structure caused by two pairs of equivalent Sc atoms. The Sc-based hyperfine structure with large hyperfine coupling constants shows that both oxidation and reduction of ScO@C are in cavea redox processes, which is the subject of endohedral electrochemistry. The assignment of the experimentally determined a(Sc) values to the two types of Sc atoms in the ScO cluster was accomplished by extended density functional theory and molecular dynamics simulations. Sc atoms adopting a divalent state in the neutral ScO@C exhibited an especially large coupling constant of 150.4 G in the cation radical, which is the record high a(45Sc) value for Sc-based endohedral metallofullerenes. Such a high value is explained by the nature of the highest occupied molecular orbital (HOMO) localized on the six-atom ScO cluster. This HOMO is a Sc-Sc bonding MO and hence has large contributions from the 4s atomic orbitals of ScII. We claim that ESR spectroelectrochemistry is an invaluable experimental tool in the studies of metal-metal bonding in endohedral metallofullerenes and in endohedral electrochemistry. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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