Tunable Photocatalytic Selectivity by Altering the Active Center Microenvironment of an Organic Polymer Photocatalyst

[Image: see text] The favored production of one product over another is a major challenge in synthetic chemistry, reducing the formation of byproducts and enhancing atom efficacy. The formation of catalytic species that have differing reactivities based on the substrate being converted, has been targeted to selectively control reactions. Here, we report the production of photocatalytic self-assembled amphiphilic polymers, with either hydrophilic or hydrophobic microenvironments at the reactive center. Benzothiadiazole-based photocatalysts were polymerized into either the hydrophilic or the hydrophobic compartment of a diblock copolymer by RAFT polymerization. The difference in the reactivity of each microenvironment was dictated by the physical properties of the substrate. Stark differences in reactivity were observed for polar substrates, where a hydrophilic microenvironment was favored. Conversely, both microenvironments performed similarly for very hydrophobic substrates, showing that reagent partitioning is not the only factor that drives photocatalytic conversion. Furthermore, the use of secondary swelling solvents allowed an additional reagent exchange between the continuous phase and the heterogeneous photocatalyst, resulting in a significant 5-fold increase in conversion for a radical carbon–carbon coupling.