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 Eu3+ and Pd2+ 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.

Проанализировано поведение сополимеров на основе поли(метакрилата), которые содержат звенья ферроцена и/или терпиридина в боковых цепях, при их самоорганизации за счет координационных взаимодействиях с ионами Eu3+ и Pd2+ в разбавленных растворах. Установлено, что внутримолекулярное комплексообразование начинается при крайне небольшом соотношении молярных концентраций металла (M) к терпиридиновым лигандам (L) M:L ≈ 0,1, в то время как при M:L > 0,5 раствор/суспензия выпадает в осадок.