• Citer

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

par Li, Gen;Du, Zelin;Wu, Chao;Liu, Yawei;Xu, Yan;Lavendomme, Roy ;Liang, Shihang;Gao, En-Qing;Zhang, Dawei
Référence Nature communications, 16, 546
Publication Publié, 2025-01-09

Article révisé par les pairs

• Accès en ligne
• Détails
• Contenu
• Statistiques

Résumé :

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 CT for boosting PET-based functions and applications.