| Summary: | 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<sup>3+</sup> and Pd<sup>2+</sup> 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 (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>M</mi><mo>/</mo><mi>L</mi></mrow></semantics></math></inline-formula>) in extremely dilute polymer solutions <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mrow><mo>(</mo><mrow><mi>c</mi><mrow><mo>[</mo><mi>η</mi><mo>]</mo></mrow><mo>≈</mo><mn>0.006</mn></mrow><mo>)</mo></mrow></mrow></semantics></math></inline-formula> were determined. It was shown that intramolecular complexation is already detected at (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>L</mi><mo>≈</mo><mn>0.1</mn></mrow></semantics></math></inline-formula>), while at <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>M</mi><mo>/</mo><mi>L</mi><mo>></mo><mn>0.5</mn></mrow></semantics></math></inline-formula> 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.
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