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

Gen Li, Zelin Du, Chao Wu, Yawei Liu, Yan Xu, Roy Lavendomme, Shihang Liang, En-Qing Gao (eqgao@chem.ecnu.edu.cn) and Dawei Zhang (dwzhang@chem.ecnu.edu.cn)
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Gen Li: East China Normal University
Zelin Du: East China Normal University
Chao Wu: Durham University
Yawei Liu: East China Normal University
Yan Xu: East China Normal University
Roy Lavendomme: Université libre de Bruxelles (ULB)
Shihang Liang: SINOPEC Research Institute of Petroleum Processing
En-Qing Gao: East China Normal University
Dawei Zhang: East China Normal University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: 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 (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.

Date: 2025
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DOI: 10.1038/s41467-025-55893-z

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