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

作者：Gen Li, Zhihong Du, Chao Wu, Yawei Liu, Yan Xu, Roy Lavendomme, Shihang Liang, En‐Qing Gao, Dawei Zhang · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-55893-z · 被引用次数：41 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Supramolecular Chemistry and Complexes、Porphyrin and Phthalocyanine Chemistry

Abstract 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 F − ) 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 C...