Photochemical coupling of iron redox reactions and transformation of low-molecular-weight organic matter

The photoreactions between Fe(III)/Fe(II) and low-molecular-weight organic matter (LMWOM) under solar irradiation have significant implications for many biogeochemical cycles on the Earth and for the fates of environmental pollutants. In this Perspective, we focus on several fundamental aspects of the photochemical processes that couple the redox cycling of iron species and transformation of organic substrates. The primary photoprocesses (e.g., intramolecular electron transfer or photodissociation) are first highlighted by introducing the recently disputed observations on the photolysis of ferrioxalate complexes. The effects of LMWOM and its daughter radicals on the photochemical redox cycling of iron species are discussed with special attention given to the example of Fe–malonate complexes. These processes and mechanisms would provide us some refreshed understanding of environmental photochemistry of LMWOM and the iron species and would be helpful for our assessment of photochemical decontamination of organic pollutants.