Synthesis, Structure and Photophysical Studies of Luminescent Two- and Three-Dimensional Gold-Thallium Supramolecular Arrays

  1. Fernández, E.J. 1
  2. Jones, P.G. 3
  3. Laguna, A. 2
  4. López-de-Luzuriaga, J.M. 1
  5. Monge, M. 1
  6. Pérez, J. 1
  7. Olmos, M.E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  3. 3 Braunschweig University of Technology
    info

    Braunschweig University of Technology

    Brunswick, Alemania

    ROR https://ror.org/010nsgg66

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Journal:
Inorganic Chemistry

ISSN: 0020-1669

Year of publication: 2002

Volume: 41

Issue: 5

Pages: 1056-1063

Type: Article

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DOI: 10.1021/IC010961U PMID: 11874338 SCOPUS: 2-s2.0-0037061044 WoS: WOS:000174259300008 GOOGLE SCHOLAR

More publications in: Inorganic Chemistry

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Abstract

The reactions of tetrahydrofuran solutions of NBu4[AuR2] (R = C6F5, C6Cl5) with TIPF6 and 4,4′-bipyridine lead to the synthesis of the luminescent materials [Tl(bipy)]2[Au(C6F5)2] 2 1 and [Tl(bipy)][Tl(bipy)0.5(thf)][Au(C6Cl5) 2]2 2 in high yield. The structures of these complexes, as analyzed by X-ray diffraction, consist of planar polymers formed by repetition of Tl-Au-Au-Tl (1) or Tl-Au-Tl′-Au (2) moieties linked through bidentate bridging bipy ligands. In complex 1 these layers are associated via Tl···F contacts between atoms of adjacent planes, whereas in complex 2 each two polymeric layers are linked through additional bridging bipy molecules. Both complexes are strongly luminescent at room temperature and at 77 K in the solid state, losing this characteristic in solution even at high concentrations. The luminescence is attributed to interactions between metal atoms which are strongly affected by their structural dispositions. DFT calculations are in accord with the observed experimental behavior, showing the nature of the orbitals involved in each transition. Detailed analyses reveal a substantial participation of the metals in the transition giving rise to the emission maxima, and also other more energetic bands in which the ligands are involved and which also give rise to these emissions. The obtained theoretical excitation spectra clearly match the experimental results.