A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions.

Mechanoinduced phase transitions of emissive organic crystalline materials have received much attention. Although a variety of such luminescent mechanochromic compounds have been reported, it is challenging to develop mechanochromic compounds with crystal-to-crystal phase transitions in which precis...

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Publicado en:Journal of the American Chemical Society Vol. 138; no. 19; pp. 6252 - 6261
Autores principales: Tomohiro Seki, Yuki Takamatsu, Hajime Ito
Formato: Artículo
Publicado: American Chemical Society 5/18/2016
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 5/18/2016
      vid: 138
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      pub: American Chemical Society
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        10.1021/jacs.6b02409
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        atl: A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions.
      aug:
        au:
          Tomohiro Seki
          Yuki Takamatsu
          Hajime Ito
        affil: Division of Applied Chemistry and Frontier Chemistry Center (FCC), Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan
      su:
        Allotropic transition
        Chromic materials
        Ultraviolet radiation
        Emission spectroscopy
        Diffraction patterns
        Intermolecular interactions
      sug:
        subj:
          Allotropic transition
          Chromic materials
          Ultraviolet radiation
          Emission spectroscopy
          Diffraction patterns
          Intermolecular interactions
      ab: Mechanoinduced phase transitions of emissive organic crystalline materials have received much attention. Although a variety of such luminescent mechanochromic compounds have been reported, it is challenging to develop mechanochromic compounds with crystal-to-crystal phase transitions in which precise structural information about molecular arrangements can be obtained. Here, we report a screening approach to explore mechanochromic compounds exhibiting a crystal-to-crystal phase transition. We prepared 48 para-substituted (R) phenyl[para-substituted (R) phenyl isocyanide]gold(I) complexes designated R-R (six R and eight R substituents) and then performed three-step screening experiments. The first screening step was selection of emissive complexes under UV light, which gave 37 emissive R-R complexes. The second screening step involved evaluation of the mechanochromic properties by emission spectroscopy. Twenty-eight complexes were found to be mechanochromic. The third screening step involved preparation of single crystals, reprecipitated powders, and ground powders of the 28 mechanochromic R-R complexes. The changes in the powder diffraction patterns of these complexes induced by mechanical stimulation were investigated. Two compounds exhibited a crystal-to-crystal phase transition upon mechanical stimulation, including the previously reported H-H complex. Single crystals of the as-prepared and ground forms of the newly discovered CF-CN complex were obtained. Density functional theory calculations indicated that the mechanoinduced red-shifted emission of CF-CN is caused by formation of aurophilic interactions. Comparison of the crystal structures of CF-CN with those of the other complexes suggests that the weaker intermolecular interactions in the as-prepared form are an important structural factor for the observed mechanoinduced crystal-to-crystal phase transition.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2016
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