Mechanism of Ligand Photodissociation in Photoactivable [Ru(bpy)L] Complexes: A Density Functional Theory Study.
A series of four photodissociable Ru polypyridyl complexes of general formula [Ru(bpy)L], where bpy = 2,2′-bipyridine and L = 4-aminopyridine (1), pyridine (2), butylamine (3), and γ-aminobutyric acid (4), was studied by density functional theory (DFT) and time-dependent density functional theory (T...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 29; pp. 9590 - 9598 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
7/23/2008
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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=33769163&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 33769163 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: 7/23/2008 vid: 130 iid: 29 pid: 997 pub: American Chemical Society artinfo: ui: 33769163 10.1021/ja8025906 ppf: 9590 ppct: 8 formats: tig: atl: Mechanism of Ligand Photodissociation in Photoactivable [Ru(bpy)L] Complexes: A Density Functional Theory Study. aug: au: Salassa, Luca Garino, Claudio Salassa, Giovanni Gobetto, Roberto Nervi, Carlo affil: Dipartimento di Clinica I.F.M., Università di Torino, Via P. Giuria 7, 1-10125 Torino, italy su: Ruthenium compounds Ligands (Chemistry) Dissociation (Chemistry) Photochemistry Density functionals sug: subj: Ruthenium compounds Ligands (Chemistry) Dissociation (Chemistry) Photochemistry Density functionals ab: A series of four photodissociable Ru polypyridyl complexes of general formula [Ru(bpy)L], where bpy = 2,2′-bipyridine and L = 4-aminopyridine (1), pyridine (2), butylamine (3), and γ-aminobutyric acid (4), was studied by density functional theory (DFT) and time-dependent density functional theory (TDDFT). DFT calculations (B3LYP/LanL2DZ) were able to predict and elucidate singlet and triplet excited-state properties of 1-4 and describe the photodissociation mechanism of one monodentate ligand. All derivatives display a Ru → bpy metal-to-ligand charge transfer (MLCT) absorption band in the visible spectrum and a corresponding emitting triplet ³MLCT state (Ru → bpy). 1-4 have three singlet metal-centered (MC) states 0.4 eV above the major ¹MLCT states. The energy gap between the MC states and lower-energy MLCT states is significantly diminished by intersystem crossing and consequent triplet formation. Relaxed potential energy surface scans along the Ru-L stretching coordinate were performed on singlet and triplet excited states for all derivatives employing DFT and TDDFT. Excited-state evolution along the reaction coordinate allowed identification and characterization of the triplet state responsible for the photodissociation process in 1-4; moreover, calculation showed that no singlet state is able to cause dissociation of monodentate ligands. Two antibonding MC orbitals contribute to the ³MC state responsible for the release of one of the two monodentate ligands in each complex. Comparison of theoretical triplet excited-state energy diagrams from TDDFT and unrestricted Kohn-Sham data reveals the experimental photodissociation yields as well as other structural and spectroscopic features. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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