LAUSR

Abstract The metal-free atom transfer radical polymerization (ATRP) process mediated by visible light and catalyzed by new organic photocatalysts (PCs) is investigated. The new PCs, designed by diversifying N-trifluoromethylphenyl phenoxazine, are analyzed and evaluated for organocatalyzed ATRP (O-ATRP) experimentally and theoretically. Especially, 3,7-di(4-biphenyl) 4-trifluoromethylphenyl-10-phenoxazine (4) enables successful O-ATRP with good catalytic performance, to produce well-defined polymers with low dispersity (Đ) under irradiation with a CFL bulb, white LEDs, or sunlight. The structure–property–performance relationships of PCs are investigated to determine the key parameters required for a good PC for use in O-ATRP. The scope of this process is explored in terms of monomer substrates and initiators using our new PC 4. Finally, a well-defined amphiphilic block copolymer is prepared using this method to form micelles, providing a basis for future biomedical applications.