Dye-Binding Metal–Organic Cage for Highly Efficient Multiphoton Activation of C(sp3)–H Bonds AITranslate

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DOI：https://doi.org/10.1021/acsmaterialslett.3c00491

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Enzymes facilitate chemical conversions through the integrated activity of multicomponents, but the aggregation of multiactive sites with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new CeIII-based octahedral cage with chloride ligands that boosts C(sp3)−H photoactivation by marrying a CeIV–Cl photocatalyst and photoredox catalyst to integrate photoinduced electron transfer (PET), ligand-to-metal charge transfer (LMCT), and hydrogen-atom transfer (HAT) events through multiphoton excitation. This molecular cage binds 2-chloro-9H-thioxanthen-9-one (TXO) for boosting PET via a pseudointramolecular pathway to oxidize CeIII–Cl to CeIV–Cl and form TXO•–. The LMCT excitation of CeIV–Cl is triggered to form Cl• that activates C(sp3)−H via HAT, resulting in the regeneration of CeIII–Cl and the formation of an alkyl radical. TXO•– reduces the reaction intermediate, which transforms C(sp3)−H and facilitates recovery of TXO for subsequent recycling. This approach offers a feasible strategy for creating highly electrophilic radicals resembling enzymes and demonstrates their potential for C(sp3)−H functionalization.