Graphite carbonitride (g-C3N4) has been developed and investigated as a heterogeneous photocatalyst for iodine-mediated photo-induced reversible complexation mediated radical polymerization (RCMP). The precise control of molecular weight and narrow molecular weight distribution (approximately 1.2) was achieved through careful examination of the polymerization conditions. Spatiotemporal control experiments and chain-extension reactions conducted on g-C3N4 catalyzed by iodine-mediated RCMP confirm the high fidelity of chain-ends in iodine-capped polymers. Furthermore, g-C3N4 can be easily separated and retains its catalytic capacity even after five cycles of polymerization, demonstrating the exceptional recyclability of this polymerization system.

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