Metallo-Supramolecular Complexation Behavior of Terpyridine- and Ferrocene-Based Polymers in Solution—A Molecular Hydrodynamics Perspective

The contribution deals with the synthesis of the poly(methacrylate)-based copolymers, which contain ferrocene and/or terpyridine moieties in the side chains, and the subsequent analysis of their self-assembly behavior upon supramolecular/coordination interactions with Eu 3+ and Pd 2+ ions in dilute solutions. Both metal ions provoke intra and inter molecular complexation that results in the formation of large supra-macromolecular assembles of different conformation/shapes. By applying complementary analytical approaches (i.e., sedimentation-diffusion analysis in the analytical ultracentrifuge, dynamic light scattering, viscosity and density measurements, morphology studies by electron microscopy), a map of possible conformational states/shapes was drawn and the corresponding fundamental hydrodynamic and macromolecular characteristics of metallo-supramolecular assemblies at various ligand-to-ion molar concentration ratios ( M / L ) in extremely dilute polymer solutions ( c [ η ] ≈ 0.006 ) were determined. It was shown that intramolecular complexation is already detected at ( L ≈ 0.1 ), while at M / L > 0.5 solution/suspension precipitates. Extreme aggregation/agglomeration behavior of such dilute polymer solutions at relatively “high” metal ion content is explained from the perspective of polymer-solvent and charge interactions that will accompany the intramolecular complexation due to the coordination interactions.