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<p>Intensified host-guest electronic interplay within stable metal-organic cages (MOCs) presents great opportunities for applications in stimuli response and photocatalysis. Zr-MOCs represent a type of robust discrete hosts for such a design, but their host-guest chemistry in solution is hampered by the limited solubility. Here, by using pyridinium-derived cationic ligands with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BAr<sub>F</sub><sup>−</sup>) as solubilizing counteranions, we report the preparation of soluble Zr-MOCs of different shapes (<b>1</b>-<b>4</b>) that are otherwise inaccessible through a conventional method. Enforced arrangement of the multiple electron-deficient pyridinium groups into one cage (<b>1</b>) leads to magnified positive electrostatic field and electron-accepting strength in favor of hosting electron-donating anions, including halides and tetraarylborates. The strong charge-transfer (CT) interactions activate guest-to-host photoinduced electron transfer (PET), leading to pronounced and regulable photochromisms. Both ground-state and radical structures of host and host-guest complexes have been unambiguously characterized by X-ray crystallography. The CT-enhanced PET also enables the use of <b>1</b> as an efficient photocatalyst for aerobic oxidation of tetraarylborates into biaryls and phenols. This work presents the solution assembly of soluble Zr-MOCs from cationic ligands with the assistance of solubilizing anions and highlights the great potential of harnessing host-guest CT for boosting PET-based functions and applications.</p>

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Charge-transfer complexation of coordination cages for enhanced photochromism and photocatalysis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月9日

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  • Gen Li,
  • Zelin Du,
  • Chao Wu,
  • Yawei Liu,
  • Yan Xu,
  • Roy Lavendomme,
  • Shihang Liang,
  • En-Qing Gao,
  • Dawei Zhang

摘要

Intensified host-guest electronic interplay within stable metal-organic cages (MOCs) presents great opportunities for applications in stimuli response and photocatalysis. Zr-MOCs represent a type of robust discrete hosts for such a design, but their host-guest chemistry in solution is hampered by the limited solubility. Here, by using pyridinium-derived cationic ligands with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BArF−) as solubilizing counteranions, we report the preparation of soluble Zr-MOCs of different shapes (1-4) that are otherwise inaccessible through a conventional method. Enforced arrangement of the multiple electron-deficient pyridinium groups into one cage (1) leads to magnified positive electrostatic field and electron-accepting strength in favor of hosting electron-donating anions, including halides and tetraarylborates. The strong charge-transfer (CT) interactions activate guest-to-host photoinduced electron transfer (PET), leading to pronounced and regulable photochromisms. Both ground-state and radical structures of host and host-guest complexes have been unambiguously characterized by X-ray crystallography. The CT-enhanced PET also enables the use of 1 as an efficient photocatalyst for aerobic oxidation of tetraarylborates into biaryls and phenols. This work presents the solution assembly of soluble Zr-MOCs from cationic ligands with the assistance of solubilizing anions and highlights the great potential of harnessing host-guest CT for boosting PET-based functions and applications.