Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions.
Luminescent Ce(III) complexes, Ce[N(SiMe)] (1) and [(MeSi)NC(RN)]Ce[N(SiMe)] (R = Pr, Pr; R = Cy, 1-Cy), with C and C solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, Pr, and 1-Cy with lifetimes of...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 29; pp. 9234 - 9238 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
7/29/2015
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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=108955510&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 108955510 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: 7/29/2015 vid: 137 iid: 29 pid: 997 pub: American Chemical Society artinfo: ui: 108955510 10.1021/jacs.5b05411 ppf: 9234 ppct: 4 formats: tig: atl: Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions. aug: au: Haolin Yin Carroll, Patrick J. Anna, Jessica M. Schelter, Eric J. affil: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States su: Halogens Abstraction reactions Photosensitizers Metathesis reactions Density functional theory Abstraction process (Catalysis) sug: subj: Halogens Abstraction reactions Photosensitizers Metathesis reactions Density functional theory Abstraction process (Catalysis) ab: Luminescent Ce(III) complexes, Ce[N(SiMe)] (1) and [(MeSi)NC(RN)]Ce[N(SiMe)] (R = Pr, Pr; R = Cy, 1-Cy), with C and C solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and Pr revealed the ²A excited states corresponded to singly occupied 5dz2 orbitals. The strongly reducing metalloradical character of 1, Pr, and 1-Cy in their ²A excited states afforded photochemical halogen atom abstraction reactions from sp³ and sp² C-X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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