A Detailed Study of the Vapochromic Behavior of {Tl[Au(C6Cl5)2]}n

  1. Fernández, E.J. 4
  2. López-De-Luzuriaga, J.M. 4
  3. Monge, M. 4
  4. Montiel, M. 4
  5. Olmos, M.E. 4
  6. Pérez, J. 4
  7. Laguna, A. 3
  8. Mendizabal, F. 1
  9. Mohamed, A.A. 2
  10. Fackler Jr. 2
  1. 1 Universidad de Chile
    info

    Universidad de Chile

    Santiago de Chile, Chile

    ROR https://ror.org/047gc3g35

  2. 2 Texas A&M University
    info

    Texas A&M University

    College Station, Estados Unidos

    ROR https://ror.org/01f5ytq51

  3. 3 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  4. 4 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Revue:
Inorganic Chemistry

ISSN: 0020-1669

Année de publication: 2004

Volumen: 43

Número: 12

Pages: 3573-3581

Type: Article

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DOI: 10.1021/IC0499446 SCOPUS: 2-s2.0-18544410676 WoS: WOS:000221989000005 GOOGLE SCHOLAR

D'autres publications dans: Inorganic Chemistry

Dépôt institutionnel: lock_openAccès ouvert Editor

Résumé

The linear-chain polymer {TI[Au(C6Cl5) 2]}n, 1, reacts in the solid state and in solution with different volatile organic compounds such as tetrahydrofuran, acetone, tetrahydrothiophene, 2-fluoropyridine, acetonitrile, acetylacetone, and pyridine. Solid-state exposure of 1 to vapors of the above VOCs produces a selective and reversible change in its color that is perceptible to the human eye and even deeper under UV irradiation, allowing 1 to function as a sensor for these VOCs. Heating the samples exposed to the VOCs for a few minutes at 100° C regenerates the original material without degradation, even after several exposure/heating cycles. The reversibility is further confirmed by X-ray powder diffraction measurements of complex 1 before and after exposure to vapors and again after heating the samples. The products obtained by reactions of complex 1 with the above VOCs as ligands in solution contain extended linear chains of alternating gold and thallium centers with two molecules of the organic ligands attached to each thallium atom. The stoichiometry of these materials has been confirmed by single-crystal X-ray diffraction as {TI(THF)2[Au(C6Cl5)2]}, 3, and {TI(acacH)2[Au(C6Cl5)2]}, 5. Comparison of FT-IR, UV-vis, and luminescence spectra at room temperature and at 77 K of the solid samples of complexes 2-9 with the spectra of complex 1 after its exposure to VOCs suggests interaction occurs between the organic VOCs and thallium in each case. Thermogravimetric analyses data indicate that all the thallium centers in these derivatives of complex 1 are neither fully nor equally coordinatively saturated. The materials formed appear to be intermediates between complex 1 with no VOCs attached and complexes 3-9 which contain two organic ligands coordinated to each thallium. A crystal structure analyses of one of these intermediates, {TI(THF)0.5[Au(C 6Cl5)2]}, 1·0.5THF, confirms this. Density functional calculations are in accord with the observed experimental results. Analysis reveals a substantial participation of the metal atoms in transitions that give rise to the observed emissions. Crystallographic data are as follows. For 1·0.5THF: triclinic, P1, a = 8.9296(1) Å, b = 11.2457(1) Å, c = 21.2465(3) Å, α = 96.7187(7)°, β = 92.5886(6)°, γ = 98.5911(8)°, V = 2090.87(4) Å3, and Z = 2. For 3: monoclinic, P21/c1 a = 26.4163(6) Å, b = 12.1619(2) Å, c = 28.0813(6) Å, α = 90°, β = 161.9823(6)°, γ = 90°, V = 2790.51(10) A3, and Z = 4. For 5: monoclinic, P21/c1, a = 9.8654(2) Å, b = 29.8570(5) Å, c = 11.6067(2) Å, α = 90°, β = 114.5931(6)°, 7 = 90°, V = 3108.64(10) Å3, and Z = 4.