Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations

作者：Yanke Hao, Yu‐Lin Lu, Zhiwei Jiao, Cheng‐Yong Su · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202317808 · 被引用次数：75 · 研究领域：Porphyrin and Phthalocyanine Chemistry、Supramolecular Chemistry and Complexes、Metal-Organic Frameworks: Synthesis and Applications

The self-assembled metal-organic cages (MOCs) have been evolved as a paradigm of enzyme-mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components and constitute microenvironments characteristic of enzymatic spatial confinement and versatile host-guest interactions, thus facilitating unconventional organic transformations via unique driving-forces such as weak noncovalent binding and electron/energy transfer. Recently, MOC-based photoreactors emerged as a burgeoning platform of supramolecular photocatalysis, displaying anomalous reactivities and selectivities distinct from bulk solution. This perspective recaps two decades journey of the photoinduced radical reactions by using photoactive metal-organic cages (PMOCs) as artificial reactors, outlining how the cage-confined photocatalysis was evolved from stoichiometric photoreactions to photocatalytic turnover, from high-energy UV-irradiation to sustainable visible-light photoactivation, and from simple radical reactions to multi-level chemo- and stereoselectivities. We will focus on PMOCs that merge structural and functional biomimicry into a single-cage to behave as multi-role photoreactors, emphasizing their potentials in tackling current challenges in organic transformations through single-electron transfer (SET) or energy transfer (EnT) pathways in a simple, green while feasible manner.