Photoconversion Bonding Mechanism in Ruthenium Sulfur Dioxide Linkage Photoisomers Revealed by in Situ Diffraction.
Three new ruthenium-sulfur dioxide linkage photoisomeric complexes in the [Ru(NH)(SO)X]Cl∙HO family (X = pyridine (1); 3-chloropyridine (2); 4-chloropyridine (3)) have been developed in order to examine the effects of the trans-ligand on the nature of the photo-induced SO coordination to the rutheni...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 29; pp. 11860 - 11864 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
7/25/2012
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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=78336709&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 78336709 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: 7/25/2012 vid: 134 iid: 29 pid: 997 pub: American Chemical Society artinfo: ui: 78336709 10.1021/ja303943q ppf: 11860 ppct: 4 formats: tig: atl: Photoconversion Bonding Mechanism in Ruthenium Sulfur Dioxide Linkage Photoisomers Revealed by in Situ Diffraction. aug: au: Sylvester, Sven O. Cole, Jacqueline M. Waddell, Paul G. affil: Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 OHE, U.K. Department of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton E3B 5A3, Canada Department of Physics, University of New Brunswick, P.O. Box 4400, Fredericton E3B 5A3, Canada su: Isomers Chemical bonds Optical diffraction Ruthenium compounds Sulfur dioxide Crystallography sug: subj: Isomers Chemical bonds Optical diffraction Ruthenium compounds Sulfur dioxide Crystallography ab: Three new ruthenium-sulfur dioxide linkage photoisomeric complexes in the [Ru(NH)(SO)X]Cl∙HO family (X = pyridine (1); 3-chloropyridine (2); 4-chloropyridine (3)) have been developed in order to examine the effects of the trans-ligand on the nature of the photo-induced SO coordination to the ruthenium ion. Solid-state metastable η-O-bound (MS1) and η-side S,O-bound (MS2) photoisomers are crystallographically resolved by probing a light-induced crystal with in situ diffraction. This so-called photocrystallography reveals the highest known photoconversion fraction of 58(3)% (in 1) for any solid-state SO(2) linkage photoisomer. The decay of this MS1 into the MS2 state was modeled via first-order kinetics with a non-zero asymptote. Furthermore, the MS2 decay kinetics of the three compounds were examined according to their systematically varying trans-ligand X; this offers the first experimental evidence that the MS2 state is primarily stabilized by donation from the S∔O electrons into the Ru dσ-orbital rather than σ-backbonding as previously envisaged. This has important consequences for the optoelectronic application of these materials since this establishes, for the first time, a design protocol that will enable one to control their photoconversion levels. 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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