Capturing and Analyzing the Excited-State Structure of a Cu(l) Phenanthroline Complex by Time-Resolved Diffraction and Theoretical Calculations.
Time-resolved crystallography and density functional theory calculations are used to analyze the geometric and electronic changes that occur upon photoexcitation of [Cu(l)(dmp)(dppe)][sup+] in crystalline [Cu(l)(dmp)(dppe)][PF[sub6]] [dmp = 2,9-dimethyl-1 , 1 0-phenanthroline; dppe = 1 ,2-bis(diphen...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 18; pp. 6566 - 6574 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
5/13/2009
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| Materias: | |
| 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=40309060&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 40309060 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: 5/13/2009 vid: 131 iid: 18 pid: 997 pub: American Chemical Society artinfo: ui: 40309060 10.1021/ja900921p ppf: 6566 ppct: 8 formats: tig: atl: Capturing and Analyzing the Excited-State Structure of a Cu(l) Phenanthroline Complex by Time-Resolved Diffraction and Theoretical Calculations. aug: au: Vorontsov, Ivan I. Graber, Tim Kovalevsky, Andrey Yu. Novozhilova, Irma V. Gembicky, Milan Yu-Sheng Chen Coppens, Philip affil: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260 Department of Biochemistry and Molecular Biophysics, University of Arizona, Tucson, AZ 85721 University of Chicago, Chicago, Illinois 60637 Bioscience Division, Group B-8, Los Alamos National Laboratory, Los Alamos, NM 87545 Department of Chemistry, Box 68, Middle Tennessee State University, Murfreesboro, TN 37132 University of Toledo, Toledo, Ohio 43606 ChemMatCARS, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 su: Excited state chemistry Density functionals Crystals Phenyl compounds Electron distribution Charge exchange Copper sug: subj: Excited state chemistry Density functionals Crystals Phenyl compounds Electron distribution Charge exchange Copper ab: Time-resolved crystallography and density functional theory calculations are used to analyze the geometric and electronic changes that occur upon photoexcitation of [Cu(l)(dmp)(dppe)][sup+] in crystalline [Cu(l)(dmp)(dppe)][PF[sub6]] [dmp = 2,9-dimethyl-1 , 1 0-phenanthroline; dppe = 1 ,2-bis(diphenylphosphino)- ethane]. In the pump-probe experiment, laser and X-ray pulses are synchronized to capture an image of the instantaneous molecular distortions in the transient triplet state. Parallel theoretical calculations, with the phenyl groups replaced by methyl groups, yield information on the distortion of the isolated cation and the change in electron density upon excitation. The experimental distortions are significantly less than the calculated values and are different for the two independent molecules in the asymmetric unit; these findings are attributed to the constraining influence of the crystal matrix. The calculations indicate that the electron transfer upon excitation is mostly from the dmpe ligand to the dmp ligand, while the Cu atomic charge changes by only ∼+0.1 e, although the charge distribution on Cu is significantly affected. As found for homoleptic [Cu(l)(dmp)[sub2]][sup+], the change in the population of the Cu atom is close to the calculated difference between the corresponding Cu(ll) and Cu(l) complexes. Charge density difference maps confirm these conclusions and show a large rearrangement of the electron density on the Cu atom upon excitation. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
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