Scholarlink

<p>In contrast to the rich chemistry of porphyrin and its analogs, the structural variety of phthalocyanine derivatives, which are widely utilized in material and life sciences, has been limited by the lack of versatile synthetic methods. Herein we present a synthetic strategy/methodology for the <i>meso</i>-position editing of phthalocyanine derivatives via deprotonative macrocyclization of open-form acyclic phthalonitrile Ni tetramer <b>1</b>, prepared by thiolate-mediated reductive tetramerization of phthalonitrile and metalation. To illustrate the utility of this protocol, we synthesize several <i>meso</i>-<i>N</i>-edited phthalocyanine derivatives, including 16<i>π</i>-electron antiaromatic tetrabenzodiazanorcorrole <b>2</b>, and 17<i>π</i>-electron paramagnetic tetrabenzotriazacorrole <b>3</b> and tetrabenzodiazacorrole <b>4</b>. The products are obtained as the nickel(II) complexes. Their unique electronic properties, such as paratropicity and radical character, are characterized both experimentally and computationally. Moreover, antiaromatic compound <b>2</b> undergoes further <i>meso</i>-position and skeletal transformations upon reaction with nucleophiles to give nonaromatic and aromatic <i>π</i>-conjugates.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Synthesis of nickel(II)-containing meso-edited phthalocyanine derivatives

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年3月29日

查看全文
  • Yuta Takiya,
  • Taiga Saito,
  • Naoyuki Toriumi,
  • Masanobu Uchiyama

摘要

In contrast to the rich chemistry of porphyrin and its analogs, the structural variety of phthalocyanine derivatives, which are widely utilized in material and life sciences, has been limited by the lack of versatile synthetic methods. Herein we present a synthetic strategy/methodology for the meso-position editing of phthalocyanine derivatives via deprotonative macrocyclization of open-form acyclic phthalonitrile Ni tetramer 1, prepared by thiolate-mediated reductive tetramerization of phthalonitrile and metalation. To illustrate the utility of this protocol, we synthesize several meso-N-edited phthalocyanine derivatives, including 16π-electron antiaromatic tetrabenzodiazanorcorrole 2, and 17π-electron paramagnetic tetrabenzotriazacorrole 3 and tetrabenzodiazacorrole 4. The products are obtained as the nickel(II) complexes. Their unique electronic properties, such as paratropicity and radical character, are characterized both experimentally and computationally. Moreover, antiaromatic compound 2 undergoes further meso-position and skeletal transformations upon reaction with nucleophiles to give nonaromatic and aromatic π-conjugates.