The ligands L in hypervalent iodine(III) and bismuth(V) compounds with the general structures ArIL2 and Ar3BiL2, respectively (Ar = aryl), can be displaced easily by carboxylates RCOO- to yield the corresponding ArI(OOCR)2 and Ar3Bi(OOCR)2 compounds. When dicarboxylates (or dicarboxylic acids) are employed in the ligand-exchange reactions, dynamic linear polymers are formed containing the structural motif O-E-O (E = iodine(III) or bismuth(V)) in their backbones. On the other hand, the ligand-exchange reactions with multicarboxylates afford network dynamic polymers. For example, the reaction of random copolymers of acrylic acid with vinyl monomers (butyl acrylate or styrene) with (diacetoxyiodo)benzene yields gels that are dynamic and also self-healing. The reaction of block copolymers of acrylic acid and styrene with the same hypervalent iodine(III) compound produces star-shaped structures, or, more precisely, nanoparticles with cores containing the hypervalent atoms and polystyrene coronas, even when the reaction is conducted in good solvents for both segments. Similar reactions were carried out using triphenylbismuth(V) diacetate or carbonate. All materials (linear and crosslinked) underwent degradation upon addition of monocarboxylates or other monofunctional nucleophiles. Further, the ability of hypervalent element-based polymers to exchange their building blocks with other similar materials (e.g., derived from a different di- or polycarboxylate) is demonstrated.

Dynamic and self-healing polymers containing hypervalent iodine(III) and bismuth(V) atoms as structural elements

254th National Meeting (2017)

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