The invention belongs to the technical field of organic photochemical synthesis and
catalysis, and discloses application of a spin catalyst based on a macrocyclic
gadolinium complex in photooxidation reduction reaction. According to the spin catalyst, the high-spin
ground state of
gadolinium ions is utilized,
intersystem crossing of a photoreaction intermediate singlet-state free
radical ion pair to a triplet-state free
radical ion pair is promoted through the paramagnetic effect, and the reverse
electron transfer process is effectively inhibited. Particularly, in a water-containing
system, the Gd-DOTP complex induces
solvent water molecules to form an ordered
hydrogen bond network through a phosphonic
acid group on a ligand, a
proton-mediated spin
transmission channel is constructed, and efficient
catalysis can be achieved under the millimole-level low concentration (0.53.0 mM). The
system obviously inhibits BET, improves the organic photooxidation reduction reaction efficiency, is suitable for reactions such as halogenated
aromatic hydrocarbon dehalogenation and
benzene oxidation
hydroxylation, and has the advantages of small catalyst dosage, good stability, wide application range and the like.