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

The gold(I) thiolate complexes [Au(2-SC6H4NH2)(PPh3)] (1), [PPN][Au(2-SC6H4NH2)(2)] (2) (PPN = Pph(3)= N = Pph(3)), and [{Au(2-SC6H4NH2)}(2)(mu-dppm)] (3) (dppm = PPh2CH2PPh2) have been prepared by reaction of acetylacetonato gold(l) 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) angstrom. 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)}(mu(2)-2-SC6H4NH2)] (4) and [(C6F5)(3)Au(mu(2)-2-SC6H4NH2)(AudppmAu) (mu(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) angstrom for a second independent molecule], and short gold(l)-gold(III) distances of 3.2812(7) and 3.3822(7) angstrom [or 3.2923(7) and 3.4052(7) angstrom] 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(l) 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 center dot center dot center dot Au-P charge transfer with LLCT and MC for derivative 3. An LMCT (thiolate -> Au-III 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.