TY - JOUR

T1 - Ferrocenyl-Containing Fe(II)-Bipyridinedicarboxamide Polysiloxane Complexes With Multiredox Activity

AU - Дерябин, Константин Валерьевич

AU - Городняя, Елена Витальевна

AU - Кочева, Анастасия Никитична

AU - Волков, Алексей Игоревич

AU - Левин, Олег Владиславович

AU - Исламова, Регина Маратовна

PY - 2024/11/28

Y1 - 2024/11/28

N2 - Ferrocenyl-containing Fe(II)-bipyridinedicarboxamide polysiloxane complexes with two redox metal centers were obtained by anionic ring-opening polymerization, polycondensation, and complexation reactions utilizing various FeII:Bipy molar ratios of 1:(3–12). The polymer ligand was characterized by liquid-state NMR, FTIR, and gel permeation chromatography (Mn = 8800). The structure of the polymer-metal complexes (PMCs), that is, the presence of ferrocenyl groups and [FeII(Bipy)3] coordination cross-links with FeII–NBipy bond formation, was confirmed by solid-state NMR, FTIR, UV–vis, and EDX. The PMCs exhibit multiredox activity showing three redox waves at E1/2 ≈ −1.3, 0.2, and 1.0 V related to Fc/Fc+ couple, [Fe(Bipy)2]+/[FeII(Bipy)3]2+, and [Fe(Bipy)3]2+/[Fe(Bipy)3]3+ transformations. The PMCs possess electrochromic properties resulting from the reduction–oxidation of ferrocenyl (Fc/Fc+) and [FeII(Bipy)3] fragments and leading to changes in intensity of bands at 628, 542, and 380 nm in the UV–vis spectra (coloring efficiency reaches 13.4 cm2·C−1). The PMCs are flexible, stretchable, and mechanically strong silicone materials with elongation at break, tensile strength, and Young's modulus reaching 110%, 3.5 MPa, and 21.8 MPa, respectively, with self-healing ability at 100°C. The described properties expand applications of PMCs as multiredox materials in polymer engineering for fabrication of (opto)electronic devices and protective coatings with a long service life compared to previously reported multiredox polymers.

AB - Ferrocenyl-containing Fe(II)-bipyridinedicarboxamide polysiloxane complexes with two redox metal centers were obtained by anionic ring-opening polymerization, polycondensation, and complexation reactions utilizing various FeII:Bipy molar ratios of 1:(3–12). The polymer ligand was characterized by liquid-state NMR, FTIR, and gel permeation chromatography (Mn = 8800). The structure of the polymer-metal complexes (PMCs), that is, the presence of ferrocenyl groups and [FeII(Bipy)3] coordination cross-links with FeII–NBipy bond formation, was confirmed by solid-state NMR, FTIR, UV–vis, and EDX. The PMCs exhibit multiredox activity showing three redox waves at E1/2 ≈ −1.3, 0.2, and 1.0 V related to Fc/Fc+ couple, [Fe(Bipy)2]+/[FeII(Bipy)3]2+, and [Fe(Bipy)3]2+/[Fe(Bipy)3]3+ transformations. The PMCs possess electrochromic properties resulting from the reduction–oxidation of ferrocenyl (Fc/Fc+) and [FeII(Bipy)3] fragments and leading to changes in intensity of bands at 628, 542, and 380 nm in the UV–vis spectra (coloring efficiency reaches 13.4 cm2·C−1). The PMCs are flexible, stretchable, and mechanically strong silicone materials with elongation at break, tensile strength, and Young's modulus reaching 110%, 3.5 MPa, and 21.8 MPa, respectively, with self-healing ability at 100°C. The described properties expand applications of PMCs as multiredox materials in polymer engineering for fabrication of (opto)electronic devices and protective coatings with a long service life compared to previously reported multiredox polymers.

KW - ferrocenyl-containing polysiloxanes

KW - polymer-metal complexes

KW - redox-activity

KW - synthesis of polymers

UR - https://onlinelibrary.wiley.com/doi/10.1002/pol.20240859

UR - https://www.mendeley.com/catalogue/ebb3a176-1993-370a-8349-8350c6850f2f/

U2 - 10.1002/pol.20240859

DO - 10.1002/pol.20240859

M3 - Article

JO - Journal of Polymer Science

JF - Journal of Polymer Science

SN - 2642-4150

ER -