Encapsulating an iron complex in a heme and anthraquinone codecorated capsule for multiphoton C(sp3)−H bond oxygenation

The allosteric effect in proteins controls biological function omnipotently, but simulating both the regulatory functions and catalytic processes of analogues faces marked challenges. By encapsulating a non-heme Fe ^III -complex into the cavity of an anthraquinone and heme co-decorated coordination capsule, herein we report a light-responsive allosteric catalysis for activating O ₂ and metabolizing C( sp ³ ) − H bonds. Light irradiation initially triggers the fast conformational switch from the bridged Fe ^III -porphyrins into unbridged Fe ^II /O = Fe ^IV -porphyrin pair for substrate oxygenation. Parallelly exciting the anthraquinone groups sensitizes O ₂ to ¹ O ₂ via energy transfer, meanwhile exciting the non-heme Fe ^III -complexes generates the chlorine radicals via ligand-to-metal charge transfer. The enforced proximities between the in-situ formed non-heme and heme Fe ^II fragments promise the formation of Fe − O−O − Fe intermediate with the reactive ¹ O ₂ species for O − O bond cleavage. The chlorine radical and O = Fe ^IV -porphyrin each abstracts a hydrogen atom from encapsulated substrate C( sp ³ ) − H bond to form the carbonyl product, combining the energy of more than one photon per catalytic turnover by synergizing the heme/non-heme modules. The unique allosteric capsule allows all reaction intermediates and active sites within one pocket for selectively oxygenating thioxanthene into thioxanthen-9-one in an extremely short period, reshaping oxygenase for selective metabolism in a supramolecular approach.