Modifying Parallel Excitations into One Framework for C( sp ³ )─H Bond Activation with Energy Combined More Than Two Photons

Abstract Natural photosynthesis enzymes utilize energies of several photons for challenging oxidation of water, whereas artificial photo‐catalysis typically involves only single‐photon excitation. Herein, a multiphoton excitation strategy is reported that combines parallel photo‐excitations with a photoinduced electron transfer process for the activation of C( sp ³ )─H bonds, including methane. The metal–organic framework Fe ₃ ‐MOF is designed to consolidate 4,4′,4″‐nitrilotrisbenzoic units for the photoactivation of dioxygen and trinuclear iron clusters as the HAT precursor for photoactivating alkanes. Under visible light irradiation, the dyes and iron clusters absorbed parallel photons simultaneously to reach their excited states, respectively, generating ¹ O ₂ via energy transfer and chlorine radical via ligand‐to‐metal charge transfer. The further excitation of organic dyes leads to the reduction of ¹ O ₂ into O ₂ ^•− through a photoinduced electron transfer, guaranteeing an extra multiphoton oxygen activation manner. The chlorine radical abstracts a hydrogen atom from alkanes, generating the carbon radical for further oxidation transformation. Accordingly, the total oxidation conversion of alkane utilizing three photoexcitation processes combines the energies of more than two photons. This new platform synergistically combines a consecutive excited photoredox organic dye and a HAT catalyst to combine the energies of more than two photons, providing a promising multiphoton catalysis strategy under energy saving, and high efficiency.