Coils, Rods and Rings in Hydrogen‐Bonded Supramolecular Polymers

Abstract

AbstractThe article discusses the development and properties of supramolecular polymers based on quadruple hydrogen bonds between self‐complementary ureidotriazine (UTr) and ureidopyrimidinone (UPy) functional groups. The high association constant with which these groups dimerize leads to polymers with a high degree of polymerization in isotropic solution. Application of these units for the functionalization of telechelic polymers results in new materials with mechanical properties approaching those of covalent polymers, but with a much stronger temperature‐dependent behavior. Solvophobic interactions between the hydrogen bonding moieties may be used to obtain supramolecular polymers with a well defined helical columnar architecture. Another consequence of the high dimerization constant of the UPy group is the phenomenon of a critical concentration in solutions of many bifunctional monomers. Below this concentration, only cycles are present, while above the critical concentration, the amount of cycles remains constant, and a polymer is formed. Conformational properties of the linker units are used to control the equilibrium between polymers and cycles, and are proposed to form a promising strategy toward tunable materials.Supramolecular polymer material with elastomeric properties resulting from functionalization with UPy groups. (Reproduced with permission. © John Wiley & Sons, Inc.)magnified imageSupramolecular polymer material with elastomeric properties resulting from functionalization with UPy groups. (Reproduced with permission. © John Wiley & Sons, Inc.)