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We exploit the Thorpe–Ingold effect as a spontaneous end group transformation method during photo-induced polymerization of methacrylates using the functional (2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone) species as radical photoinitiator. Herein, the isopropyl hydroxyl function endows the polymer with geminal methyl groups inducing an angular compression, enabling through close proximity a ring-closing reaction between the hydroxyl group and the ester motif.

Graphical abstract: Installing lactone chain termini during photoinduced polymerization

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