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<p>Hexaphyrins are one of the most studied expanded porphyrins that show intriguing electronic structure and coordination abilities in the past decades. However, core-modified hexaphyrins especially for benzene-replaced hexaphyrins are much less explored. Herein, we revisit the dibenzihexaphyrin system and demonstrate how to achieve the hexaphyrin-like organometallic nature of a benzene-replaced expanded porphyrin. For the “true” di-<i>m</i>-benzihexaphyrin <b>2</b>, metal complex with anticipated CCNN coordination is not realized probably due to the steric hindrance. Further, we synthesized an internally linked dibenzihexaphyrin (<b>3</b>) with a direct carbon–carbon bond between two phenylenes. As prepared, <b>3</b> has a strained biphenyl unit and can effectively coordinate two Cu(III) ions with CCNN coordination. This sharp contrast underscores the critical importance of the formed pre-organized corrole-like <i>adj</i>-CCNN cavities after linking two flanking phenylenes. <b>3</b> can also act as a bidentate ligand like traditional hexaphyrin, enabling the formation of an even more strained bis-Rh(I) complex. The electronic structures and photophysical properties of the free base and metal complexes are systematically studied by steady state absorption and fs-transient absorptions (fs-TA) spectroscopies, as well as DFT calculations. Notably, <b>3</b> can be regarded as a hexaphyrin-sized back-to-back fused bis-dicarbacorrole, which stands as the smallest fused carbaporphyrinoid array prepared to date.</p>

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An internally linked dibenzihexaphyrin

  • 期刊论文

  • 发表日期：

    2025年1月3日

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  • Zhaohui Zong,
  • Xiaotong Zhang,
  • Zhe Liu,
  • Guangliu Ran,
  • Wenkai Zhang,
  • Xian-Sheng Ke

摘要

Hexaphyrins are one of the most studied expanded porphyrins that show intriguing electronic structure and coordination abilities in the past decades. However, core-modified hexaphyrins especially for benzene-replaced hexaphyrins are much less explored. Herein, we revisit the dibenzihexaphyrin system and demonstrate how to achieve the hexaphyrin-like organometallic nature of a benzene-replaced expanded porphyrin. For the “true” di-m-benzihexaphyrin 2, metal complex with anticipated CCNN coordination is not realized probably due to the steric hindrance. Further, we synthesized an internally linked dibenzihexaphyrin (3) with a direct carbon–carbon bond between two phenylenes. As prepared, 3 has a strained biphenyl unit and can effectively coordinate two Cu(III) ions with CCNN coordination. This sharp contrast underscores the critical importance of the formed pre-organized corrole-like adj-CCNN cavities after linking two flanking phenylenes. 3 can also act as a bidentate ligand like traditional hexaphyrin, enabling the formation of an even more strained bis-Rh(I) complex. The electronic structures and photophysical properties of the free base and metal complexes are systematically studied by steady state absorption and fs-transient absorptions (fs-TA) spectroscopies, as well as DFT calculations. Notably, 3 can be regarded as a hexaphyrin-sized back-to-back fused bis-dicarbacorrole, which stands as the smallest fused carbaporphyrinoid array prepared to date.