TY - JOUR

T1 - Metallo-Supramolecular Complexation Behavior of Terpyridine-and Ferrocene-Based Polymers in Solution—A Molecular Hydrodynamics Perspective

AU - Perevyazko, Igor

AU - Mikusheva, Nina

AU - Lezov, Alexey

AU - Gubarev, Alexander

AU - Enke, Marcel

AU - Winter, Andreas

AU - Schubert, Ulrich S.

AU - Tsvetkov, Nikolay

N1 - Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2022/2/26

Y1 - 2022/2/26

N2 - 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 ap-plying 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 corre-sponding 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 aggrega-tion/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.

AB - 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 ap-plying 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 corre-sponding 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 aggrega-tion/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.

KW - Analytical ultracentrifugation

KW - Conformation

KW - Metal-ligand interactions

KW - Metallo-supramolecular complexes

KW - Molecular hydrodynamics

KW - Solution properties

UR - http://www.scopus.com/inward/record.url?scp=85125580264&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/f6794387-bd44-3db7-b33a-8b684cb4d557/

U2 - 10.3390/polym14050944

DO - 10.3390/polym14050944

M3 - Article

AN - SCOPUS:85125580264

VL - 14

JO - Polymers

JF - Polymers

SN - 2073-4360

IS - 5

M1 - 944

ER -