Photophysical and Theoretical Studies on Luminescent Tetranuclear Coinage Metal Building Blocks

Organometallics (Impact Factor: 4.15). 06/2006; 25(15). DOI: 10.1021/om060181z

ABSTRACT The synthesis, structural characterization, and the study of the photophysical properties of complexes [Au2Ag2(C6F5)4(NCCH3)2]n (1) and [Au2Cu2(C6F5)4(NCCH3)2]n (2) have been carried out. The crystal structure of both complexes consists of polymeric chains formed by repetition of Au2Ag2 or Au2Cu2 units built up by metallophilic Au(I)···M(I) interactions that are linked through Au(I)···Au(I) interactions. Complexes 1 and 2 are brightly luminescent in the solid state at room temperature and at 77 K with lifetimes in the nanosecond range. Both compounds 1 and 2 undergo oligomerization in solution, as observed through UV−vis and excitation spectra in acetonitrile solutions at high concentrations. Thus, a correlation between the excitation spectra in solution at different concentrations and the absorption spectra in the solid state for complex 1 can be established. Time-dependent DFT calculations agree well with the experimental results and support the idea of that the origin of the luminescence of these complexes arises from orbitals located in the tetranuclear Au2M2 units.

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    ABSTRACT: Reaction of the polymeric alkynyl complexes (AuC(2)C(6)H(4)R)(n) (R = 4-NH(2) and 3-NH(2)) with the diphosphine PPh(2)C(6)H(4)PPh(2) in the presence of Cu(+) ions gave two novel heterometallic aggregates [{Au(3)Cu(2)(C(2)C(6)H(4)R)(6)}Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](PF(6))(2) (R = 4-NH(2) (2), 3-NH(2) (3)). The compounds obtained were characterized by NMR spectroscopy and ESI-MS measurements. The solid-state structure of their 4-NMe(2) congener 1 is reported. The complexes 1-3 reversibly react with strong (HSO(3)Me and HSO(3)CF(3)) acids to give the adducts [{Au(3)Cu(2)(C(2)C(6)H(4)-R)(6)*(R'SO(3)H)(6)}Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](PF(6))(2) (R = 4-NMe(2) (4), 4-NH(2) (5), 3-NH(2) (6)) with six acid molecules bound to the amine groups of the alkynyl ligands. Composition and structure of the adducts were established using ESI-MS and multinuclear ((31)P, (1)H and (1)H-(1)H COSY) NMR spectroscopy. It was found that formation of these adducts results in crucial changes of luminescence characteristics of the complexes 1-3 to give substantial (ca. 100 nm) blue shift of the emission maxima and a sharp increase (about an order of magnitude) in luminescence quantum yield for 4-NR(2) substituted derivatives. In the case of 3-substituted complex 3 the effect of adduct formation is much less pronounced and leads to blue-shift of emission maximum for 30 nm accompanied with a small drop in emission quantum yield. Computational studies have been performed to provide additional insight into the structural, electronic and photophysical properties of the starting complexes and their acid adducts. Interpretation of the photophysical effects induced by the adduct formation was suggested.
    Dalton Transactions 03/2010; 39(10):2676-83. · 3.81 Impact Factor
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    ABSTRACT: The synthesis, structural characterization and the study of the photophysical properties of complexes [AuCu(C6F5)2(N[triple bond]C-CH3)2] 1, [AuCu(C6F5)2(N[triple bond]C-Ph)2]2 2, and [AuCu(C6F5)2(N[triple bond]C-CH=CH-Ph)2] 3 have been carried out. The crystal structures of complexes 1-3 consist of dinuclear Au-Cu units built from mediated metallophilic Au(I)...Cu(I) interactions. In the case of complex 2 two dinuclear units interact via an aurophilic interaction leading to a tetranuclear Cu-Au-Au-Cu arrangement. Complex 2 is brightly luminescent in solid state at room temperature and at 77 K with a lifetime in the nanoseconds range, while complexes 1 and 3 do not display luminescence under the same conditions. The presence of the aurophilic interaction in complex 2 seems to be responsible for the blue luminescence observed. DFT and time-dependent DFT calculations agree with the experimental results and support the idea that the origin of the luminescence of these complexes arise from orbitals located in the interacting metals.
    Dalton Transactions 10/2009; · 3.81 Impact Factor
  • 01/2012; , ISBN: 9780471125471