Homopolynuclear TlI and heteropolynuclear AuI-Tl I complexes with organodiselone ligands: Activation of luminescence by intermetallic interactions
- Arca, M. 3
- Aroz, T. 2
- Concepción Gimeno, M. 2
- Kulcsar, M. 2
- Laguna, A. 2
- Lasanta, T. 1
- Lippolis, V. 3
- López-De-Luzuriaga, J.M. 1
- Monge, M. 1
- Olmos, M.E. 1
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1
Universidad de La Rioja
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2
Instituto de Nanociencia y Materiales de Aragón
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3
University of Cagliari
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ISSN: 1434-1948
Année de publication: 2011
Volumen: 14
Número: 14
Pages: 2288-2297
Type: Article
D'autres publications dans: European Journal of Inorganic Chemistry
Résumé
The organodiselone ligands 1,1-bis(3-methyl-4-imidazolin-2-selone)methane (L1) and 1,2-bis(3-methyl-4-imidazolin-2-selone)ethane (L2) have been used for the synthesis of homopolynuclear Tl I [{Tl(L)}PF 6] n·(mMeCN) n [L = L1, m = 1 (1); L = L2, m = 0 (2)] and discrete heteropolynuclear [Tl{Au(C 6Cl 5) 2}(L)] [L = L1 (3), L2 (4)] complexes. The crystal structures of complexes 1 and 3 have been determined through X-ray diffraction studies. Complex 1 consists of alternating thallium(I) centres and bidentate Se-donor ligands that result in polymeric chains. The crystal structure of 3 is formed by [Tl(L1)] + cations and [Au(C 6Cl 5) 2] - anions joined together by an unsupported Au⋯Tl interaction. Compounds 3 and 4 are luminescent in the solid state at room temperature and at 77 K with lifetimes in the nanosecond range. DFT and time-dependent (TD)-DFT calculations have been carried out on different model systems including the free ligand L1, a representative model of complex 1 and a model system of complex 3. The character of the frontier molecular orbitals and the TD-DFT prediction of the absorption spectra are used to explain the origin of the luminescence of complexes 3 and 4 as an admixture of metal-metal (Au-Tl)-to-ligand charge transfer (MMLCT) and intraligand (IL) transitions as observed experimentally. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.