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Engineering Cavity and Aperture Binding Sites Within a Metal–Organic Cage for Up- and Down-Regulation of Catalysis

par Xu, Yan;Li, Gen;Liang, Shihang;De Leener, Gaël ;Luhmer, Michel ;Lavendomme, Roy ;Gao, En-Qing;Zhang, Dawei
Référence Angewandte Chemie
Publication Publié, 2025-09-01

Article révisé par les pairs

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Résumé :

Engineering molecular recognition events into catalytic systems to precisely control the up- or down-regulation of catalysis in a biomimetic fashion is a challenging goal in supramolecular chemistry. In this work, we report on the construction of a new metal–organic cage, ZnII4L4 tetrahedron 1, using a protonated azacalix[3](2,6)pyridine-based ligand as the capping faces. The cage features a large cavity and wide gaps between its faces, enabling the simultaneous binding of anionic guests centrally and peripherally. Encapsulation of α-Mo8O264− within the T-symmetric tetrahedron 1 leads to a C3-symmetric inclusion complex Mo8O264−⊂1. The apertures of Mo8O264−⊂1 act as secondary binding sites for accommodating tetraarylborate guests or for providing access to the included Mo8O264− for catalyzing reactions. Catalytic experiments demonstrated that inclusion within 1 significantly enhances the catalytic activity of Mo8O264− for the oxidation of sulfides into sulfoxides. In contrast, peripheral binding of the bulky tetraarylborate anion to the inclusion complex Mo8O264−⊂1 effectively inhibits its catalytic activity by obstructing access to the catalytic active sites of Mo8O264−.