Luminescent characterization of solution oligomerization process mediated gold-gold interactions. DTF calculations on [Au2Ag2R4L2]n moieties.

  1. Fernández, E.J. 1
  2. Gimeno, M.C. 3
  3. Laguna, A. 3
  4. López-De-Luzuriaga, J.M. 1
  5. Monge, M. 1
  6. Pyykkö, P. 2
  7. Sundholm, D. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of Helsinki
    info

    University of Helsinki

    Helsinki, Finlandia

    ROR https://ror.org/040af2s02

  3. 3 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

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Journal:
Journal of the American Chemical Society

ISSN: 0002-7863

Year of publication: 2000

Volume: 122

Issue: 30

Pages: 7287-7293

Type: Article

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DOI: 10.1021/JA9942540 SCOPUS: 2-s2.0-0040488570 WoS: WOS:000088658400016 GOOGLE SCHOLAR

More publications in: Journal of the American Chemical Society

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Abstract

The optical properties of [Au2Ag2(C6F5)4(OCMe2)2](n) (1) have been studied in the solid state at room temperature and at 77 K and in acetone solution (5 x 10-4 M). The crystal structure of 1, analyzed by X-ray diffraction, consists of polymeric chains formed by repetition of Au2Ag2 moieties linked through short gold - gold interactions. The emission profile observed for 1 in dilute acetone solution (5 x 10-4 M) is assignable to pentafluorophenyl localized ππ* excited states or from π-MMCT transitions, and in the solid-state arises from metal-centered (dσ*)1(pσ)1 or (dδ*)1(pσ)1 excited states. When the absorption and emission spectra of compound 1 in acetone are registered at different concentrations, they display a band that does not obey the Lambert - Beer law. This deviation is consistent with molecular aggregation in solution through gold - gold interactions, and a clear correlation between the emission wavelength and the structure of 1 in the solid state and in solution is shown. DFT calculations accord with the observed experimental behavior and show the nature of the orbitals involved in each transition.