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http://hdl.handle.net/10261/19680
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dc.contributor.author | Bardají, Manuel | - |
dc.contributor.author | Calhorda, Maria José | - |
dc.contributor.author | Costa, Paulo J. | - |
dc.contributor.author | Jones, Peter G. | - |
dc.contributor.author | Laguna, Antonio | - |
dc.contributor.author | Reyes Pérez, M. | - |
dc.contributor.author | Villacampa, M. Dolores | - |
dc.date.accessioned | 2009-12-18T09:27:00Z | - |
dc.date.available | 2009-12-18T09:27:00Z | - |
dc.date.issued | 2006-01 | - |
dc.identifier.citation | Inorganic Chemistry 45(3): 1059-1068 (2006) | en_US |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/10261/19680 | - |
dc.description | 10 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.abstract | The 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.sponsorship | We 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.extent | 259768 bytes | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | en_US |
dc.publisher | American Chemical Society | en_US |
dc.rights | closedAccess | en_US |
dc.title | Synthesis, structural characterization, and theoretical studies of gold(I) and gold(I)−gold(III) thiolate complexes: Quenching of gold(I) thiolate luminescence | en_US |
dc.type | artículo | en_US |
dc.identifier.doi | 10.1021/ic051168u | - |
dc.description.peerreviewed | Peer reviewed | en_US |
dc.relation.publisherversion | http://dx.doi.org/10.1021/ic051168u | en_US |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.cerifentitytype | Publications | - |
item.languageiso639-1 | en | - |
item.grantfulltext | none | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | No Fulltext | - |
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