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<p>Single, double, triple, and quadruple installations of directly-fused hemiporphycenes at the periphery of Ni<sup>II</sup> porphyrin were accomplished by a concise synthetic protocol consisting of (1) appending of 2-pyrryl group(s) at the <i>β</i>-position(s) of Ni<sup>II</sup> porphyrin, (2) Friedel-Crafts type electrophilic substitution reaction with <i>α,α</i>′-dibromotripyrrin, and (3) subsequent Pd or Ni-catalyzed intramolecular Heck cyclization. Importantly, this protocol provides a single product regioselectively. Demetallation of the Ni<sup>II</sup> complexes under acidic conditions furnished the corresponding free base compounds, which were efficiently converted to the corresponding Zn<sup>II</sup> complexes. Hemiporphycene-fused porphyrins show distorted structures and panchromatic absorption spectra with red-shifted and enhanced Q-bands, which become more manifest with an increasing number of the fused hemiporphycenes. These fused porphyrinoids are also promising as a multi-electron reservoir, as evinced by multiple reversible redox waves, typically as many as eleven for <b>3Ni</b> and <b>4Ni</b>.</p>

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Multiple installations of directly fused hemiporphycenes at the periphery of NiII porphyrin

  • 期刊论文

  • 发表日期：

    2026年7月30日

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  • Boyu Xiao,
  • Jiale Liu,
  • Yutao Rao,
  • Ling Xu,
  • Bangshao Yin,
  • Mingbo Zhou,
  • Atsuhiro Osuka,
  • Jianxin Song

摘要

Single, double, triple, and quadruple installations of directly-fused hemiporphycenes at the periphery of NiII porphyrin were accomplished by a concise synthetic protocol consisting of (1) appending of 2-pyrryl group(s) at the β-position(s) of NiII porphyrin, (2) Friedel-Crafts type electrophilic substitution reaction with α,α′-dibromotripyrrin, and (3) subsequent Pd or Ni-catalyzed intramolecular Heck cyclization. Importantly, this protocol provides a single product regioselectively. Demetallation of the NiII complexes under acidic conditions furnished the corresponding free base compounds, which were efficiently converted to the corresponding ZnII complexes. Hemiporphycene-fused porphyrins show distorted structures and panchromatic absorption spectra with red-shifted and enhanced Q-bands, which become more manifest with an increasing number of the fused hemiporphycenes. These fused porphyrinoids are also promising as a multi-electron reservoir, as evinced by multiple reversible redox waves, typically as many as eleven for 3Ni and 4Ni.