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A hypervalent (HV) iodine(III)‐containing crosslinker, (diacryloyloxyiodo)benzene, is synthesized and its crystal structure is reported. Highly branched polymers with hypervalent iodine(III) groups as the building blocks present at the branching points are synthesized by copolymerization of tert‐butyl acrylate and the diacrylate crosslinker (up to 12 mol% vs the monovinyl monomer), under reversible...