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A direct photochemical thiolation of C(sp 3 )–H bond-containing substrates with thiophenol was developed. A halogen bonding-type EDA complex was found to trigger the downstream single electron transfer and hydrogen atom transfer process.

A photoexcited halogen-bonded EDA complex of the thiophenolate anion with iodobenzene for C(sp3)–H activation and thiolation

A photoexcited halogen-bonded EDA complex of the thiophenolate anion with iodobenzene for C(sp³)–H activation and thiolation