Carbon-Bridged Phenylene-Vinylenes: On the Common Diradicaloid Origin of Their Photonic and Chemical Properties

  • Rafael C. González-Cano
    Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain
  • Simone Di Motta
    Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna, Via F. Selmi, 2, 40126 Bologna, Italy
  • Xiaozhang Zhu
    Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
  • Juan. T. López Navarrete
    Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain
  • Hayato Tsuji
    Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
  • Eiichi Nakamura
    Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
  • Fabrizia Negri
    Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna, Via F. Selmi, 2, 40126 Bologna, Italy
  • Juan Casado
    Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain

書誌事項

公開日
2017-10-09
資源種別
journal article
DOI
  • 10.1021/acs.jpcc.7b08011
公開者
American Chemical Society (ACS)

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説明

In this paper, experimental and computational investigations are combined to analyze the impact of the diradical character in the photonic and chemical properties of two tetracyano quinodimethane derivatives of phenylene-vinylenes. The photonic properties are evaluated with high-level quantum-chemical calculations and are rationalized in the context of the four-level model typical of diradical molecules, including one triplet and three singlet states, whereas the diradical extent in the ground electronic state is shown to be the driving force for the dimerization reactions. To this end DFT, CASSCF, and CASPT2//CASSCF calculations are carried out and complemented with experimental UV–vis–NIR absorption and emission measurements, as a function of the temperature along with resonance Raman spectroscopy investigations. The study of diradical molecules with enhanced chemical stability in the framework of organic electronics is an important field of research in organic π-conjugated molecules with direct applica...

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