“Push-Pull” Supramolecular Chromophores Supported on Cyclopolymers

Well-defined macromolecules have been obtained through free-radical cyclopolymerization and cyclocopolymerization of difunctional and acrylic-like monomers, which contained "push-pull" supramolecular chromophores, able to form 1:1 complexes with Eu3+ ions in solution. The monomeric molecular modules are built around bismalonate crown ethers in a convergent fashion, in which one of the malonate moiety is derivatized as the ylidene malonate push-pull fragment, and the other malonate moiety is elaborated to introduce two polymerizable and acrylic-like substituents. The free-radical induced cyclopolymerization of these monomers, or their cyclocopolymerization with UV/Vis "silent" but structurally related monomers, afforded macromolecular architectures characterized by GPC, NMR and DSC techniques. UV/Vis titration studies, performed with Eu(OTf)(3) as the supramolecular probe, revealed how adjacent chromophores within the polymeric backbone are virtually independent from each other, and how the binding ability towards the probe of these multivalent, highly packed cyclopolymeric architectures, although reduced, is still clearly detectable