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Synthesis, structural characterization, and theoretical studies of gold(I) and gold(I)−gold(III) thiolate complexes: Quenching of gold(I) thiolate luminescence

AuthorsBardají, Manuel; Calhorda, Maria José; Costa, Paulo J.; Jones, Peter G.; Laguna, Antonio ; Reyes Pérez, M.; Villacampa, M. Dolores
Issue DateJan-2006
PublisherAmerican Chemical Society
CitationInorganic Chemistry 45(3): 1059-1068 (2006)
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.
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.
Publisher version (URL)http://dx.doi.org/10.1021/ic051168u
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