Visible-light-induced copper-mediated reversible deactivation radical polymerisation without additional photocatalysts

Photochemistry mediated by visible light is attractive as it avoids the limitations of higher energy UV light. Photo-induced copper-mediated reversible deactivation radical polymerisation (photo Cu-RDRP) typically requires both a copper catalyst and a separate photocatalyst (PC) to exploit lower energy irradiation. However, by covalently anchoring a PC to another reagent, dual functionality can be established. Herein, a simiplified approach is demonstrated using a modified commerically available dye as an initiator and PC simultaneously. A visibly fluorescent and highly absorbing dye, Hostasol Yellow, is chemically incorporated into a polymer following irradiation under six different UV and visible light wavelengths, resulting in high monomer conversion (>90%) and polymers with low dispersity (≤1.13). The wavelength-dependent behaviour of the dye was probed, reaffirming a mismatch between reactivity and absorptivity. Kinetic studies show high monomer conversions within just a few minutes, with good end-group fidelity confirmed by <i>in situ</i> chain extension and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF). The versatility of this PC initiator was extended to give a wide variety of molecular weights (2700-420 000 g mol^-1) and different hydrophobic, hydrophilic and semi-fluorinated polyacrylates.