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dc.contributor.authorBardají, Manuel-
dc.contributor.authorCalhorda, Maria José-
dc.contributor.authorCosta, Paulo J.-
dc.contributor.authorJones, Peter G.-
dc.contributor.authorLaguna, Antonio-
dc.contributor.authorReyes Pérez, M.-
dc.contributor.authorVillacampa, M. Dolores-
dc.date.accessioned2009-12-18T09:27:00Z-
dc.date.available2009-12-18T09:27:00Z-
dc.date.issued2006-01-
dc.identifier.citationInorganic Chemistry 45(3): 1059-1068 (2006)en_US
dc.identifier.issn0020-1669-
dc.identifier.urihttp://hdl.handle.net/10261/19680-
dc.description10 pages, 8 figures, 6 tables, 1 scheme.-- This work is dedicated to Dr. José Antonio Abad on the occasion of his retirement.-- Supporting Information Available: http://pubs.acs.org.en_US
dc.description.abstractThe gold(I) thiolate complexes [Au(2-SC6H4NH2)(PPh3)] (1), [PPN][Au(2-SC6H4NH2)2] (2) (PPN = PPh3NPPh3), and [{Au(2-SC6H4NH2)}2(μ-dppm)] (3) (dppm = PPh2CH2PPh2) have been prepared by reaction of acetylacetonato gold(I) precursors with 2-aminobenzenethiol in the appropriate molar ratio. All products are intensely photoluminescent at 77 K. The molecular structure of the dinuclear derivative 3 displays a gold−gold intramolecular contact of 3.1346(4) Å. Further reaction with the organometallic gold(III) complex [Au(C6F5)3(tht)] affords dinuclear or tetranuclear mixed gold(I)−gold(III) derivatives with a thiolate bridge, namely, [(AuPPh3){Au(C6F5)3}(μ2-2-SC6H4NH2)] (4) and [(C6F5)3Au(μ2-2-SC6H4NH2)(AudppmAu)(μ2-2-SC6H4NH2)Au(C6F5)3] (5). X-ray diffraction studies of the latter show a shortening of the intramolecular gold(I)−gold(I) contact [2.9353(7) or 2.9332(7) Å for a second independent molecule], and short gold(I)−gold(III) distances of 3.2812(7) and 3.3822(7) Å [or 3.2923(7) and 3.4052(7) Å] are also displayed. Despite the gold−gold interactions, the mixed derivatives are nonemissive compounds. Therefore, the complexes were studied by DFT methods. The HOMOs and LUMOs for gold(I) derivatives 1 and 3 are mainly centered on the thiolate and phosphine (or the second thiolate for complex 2), respectively, with some gold contributions, whereas the LUMO for derivative 4 is more centered on the gold(III) fragment. TD-DFT results show a good agreement with the experimental UV−vis absorption and excitation spectra. The excitations can be assigned as a S → Au−P charge transfer with some mixture of LLCT for derivative 1, an LLCT mixed with ILCT for derivative 2, and a S → Au···Au−P charge transfer with LLCT and MC for derivative 3. An LMCT (thiolate → AuIII mixed with thiolate → Au−P) excitation was found for derivative 4. The differing nature of the excited states [participation of the gold(III) fragment and the small contribution of sulfur] is proposed to be responsible for quenching the luminescence.en_US
dc.description.sponsorshipWe thank the Dirección General de Investigación Científica y Técnica (Project BQU2001-2409-C02-01) and the Fonds der Chemischen Industrie for financial support. We thank Acçâo Integrada Luso-Espanhola E31/04. P.J.C. acknowledges FCT for a grant (SFRH/BD/10535/2002).en_US
dc.format.extent259768 bytes-
dc.format.mimetypeapplication/pdf-
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsclosedAccessen_US
dc.titleSynthesis, structural characterization, and theoretical studies of gold(I) and gold(I)−gold(III) thiolate complexes: Quenching of gold(I) thiolate luminescenceen_US
dc.typeartículoen_US
dc.identifier.doi10.1021/ic051168u-
dc.description.peerreviewedPeer revieweden_US
dc.relation.publisherversionhttp://dx.doi.org/10.1021/ic051168uen_US
dc.type.coarhttp://purl.org/coar/resource_type/c_6501es_ES
item.openairetypeartículo-
item.cerifentitytypePublications-
item.languageiso639-1en-
item.grantfulltextnone-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.fulltextNo Fulltext-
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