Stable 3,6-Linked Fluorenyl Radical Oligomers with Intramolecular Antiferromagnetic Coupling and Polyradical Characters.

Organic radicals display unique physical structures and could become next generation functional materials. However, design and synthesis of stable neutral radicals with a significant polyradical character has been an enormous challenge for chemists. In this work, we synthesized a series of stable 3,...

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Publicado en:Journal of the American Chemical Society Vol. 138; no. 39; pp. 13048 - 13059
Autores principales: Xuefeng Lu, Sangsu Lee, Jun Oh Kim, Gopalakrishna, Tullimilli Y., Hoa Phan, Tun Seng Herng, Zhenglong Lim, Zebing Zeng, Jun Ding, Dongho Kim, Jishan Wu
Formato: Artículo
Publicado: American Chemical Society 10/5/2016
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 10/5/2016
      vid: 138
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      pub: American Chemical Society
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        10.1021/jacs.6b08138
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        atl: Stable 3,6-Linked Fluorenyl Radical Oligomers with Intramolecular Antiferromagnetic Coupling and Polyradical Characters.
      aug:
        au:
          Xuefeng Lu
          Sangsu Lee
          Jun Oh Kim
          Gopalakrishna, Tullimilli Y.
          Hoa Phan
          Tun Seng Herng
          Zhenglong Lim
          Zebing Zeng
          Jun Ding
          Dongho Kim
          Jishan Wu
        affil:
          Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore
          Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749, Korea
          Department of Materials Science & Engineering, National University of Singapore, 119260, Singapore
          College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, People's Republic of China
      su:
        Radicals
        Chemists
        Density functional theory
        Molecular theory
        Electrochemical analysis
      sug:
        subj:
          Radicals
          Chemists
          Density functional theory
          Molecular theory
          Electrochemical analysis
      ab: Organic radicals display unique physical structures and could become next generation functional materials. However, design and synthesis of stable neutral radicals with a significant polyradical character has been an enormous challenge for chemists. In this work, we synthesized a series of stable 3,6-linked, kinetically blocked fluorenyl radical oligomers up to hexamer (FR-n, n = 1-6). Their ground-state geometric and electronic structures were systematically studied by various experimental methods including X-ray crystallographic analysis, variable temperature nuclear magnetic resonance, electron spin resonance, and superconducting quantum interference device measurements, supported by density functional theory and ab initio calculations. Moderate antiferromagnetic coupling between the fluorenyl radicals was observed, and moderate to large diradical and polyradical characters were calculated from dimer onward. Furthermore, their photophysical properties were estimated by steady-state, transient absorption, and two-photon absorption measurements, and their electrochemical properties were investigated by cyclic voltammetry/differential pulse voltammetry and spectro-electrochemical measurements. A clear chain length dependence of their optical, electrochemical, and magnetic properties was found for the oligomers with an odd or even number of spin centers, respectively.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2016
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