TY - JOUR

T1 - Complexes of Ferrocenyl- Containing Polysiloxanes and Iron Triad Metals as Multiredox Active Materials

AU - Дерябин, Константин Валерьевич

AU - Городняя, Елена Витальевна

AU - Кочева, Анастасия Никитична

AU - Исламова, Регина Маратовна

PY - 2025/10/14

Y1 - 2025/10/14

N2 - Novel heterobimetallic polymer-metal complexes (PMCs) based on ferrocenyl-containing polysiloxanes with pyridine-2,6-dicarboxamide moieties coordinated with CoII, NiII, and FeII metallocenters (M-PyPMFSs), as well as ferrocenyl-containing polysiloxanes with 2,2′-bipyridine-4,4′-dicarboxamide fragments coordinated with CoII and NiII metallocenters (M-BipyP(MFS-co-DMS)s) were obtained by polymerization, polycondensation, and complexation reactions. The structure of the ferrocenyl-containing polymer ligands and their PMCs was confirmed by NMR, FTIR, UV–Vis, and EDX spectroscopies. The electrochemical behavior of the PMCs was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Both M-PyPMFSs and M-BipyP(MFS-co-DMS)s exhibit multiredox activity due to the presence of two redox active metallocenters (ferrocenyl group and NiII, CoII, or FeII coordination cross-links). A comprehensive analysis of the redox properties is conducted to establish the influence of both metallocenter and polymer ligand in the M-PyPMFSs—M-BipyP(MFS-co-DMS)s series. Thus, M-PyPMFSs demonstrate enhanced multiredox performance over M-BipyP(MFS-co-DMS)s, as evidenced by their two intensive well-resolved redox processes in CVs at E1/2 ≈ 0.1 V (Fc/Fc+ couple) and at E1/2 ≈ 0.8–1.1 V (CoII/CoIII and NiII/NiIII couples). However, M-BipyP(MFS-co-DMS)s exhibit up to three redox transitions (Fc/Fc+, MII/MIII, and Bipy•−/Bipy mixed with MI/MII). These polymer-metal complexes enable new applications as multiredox silicone materials in polymer engineering, especially for (opto)electronic, adaptive electrochromic, and stimuli-responsive devices.

AB - Novel heterobimetallic polymer-metal complexes (PMCs) based on ferrocenyl-containing polysiloxanes with pyridine-2,6-dicarboxamide moieties coordinated with CoII, NiII, and FeII metallocenters (M-PyPMFSs), as well as ferrocenyl-containing polysiloxanes with 2,2′-bipyridine-4,4′-dicarboxamide fragments coordinated with CoII and NiII metallocenters (M-BipyP(MFS-co-DMS)s) were obtained by polymerization, polycondensation, and complexation reactions. The structure of the ferrocenyl-containing polymer ligands and their PMCs was confirmed by NMR, FTIR, UV–Vis, and EDX spectroscopies. The electrochemical behavior of the PMCs was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Both M-PyPMFSs and M-BipyP(MFS-co-DMS)s exhibit multiredox activity due to the presence of two redox active metallocenters (ferrocenyl group and NiII, CoII, or FeII coordination cross-links). A comprehensive analysis of the redox properties is conducted to establish the influence of both metallocenter and polymer ligand in the M-PyPMFSs—M-BipyP(MFS-co-DMS)s series. Thus, M-PyPMFSs demonstrate enhanced multiredox performance over M-BipyP(MFS-co-DMS)s, as evidenced by their two intensive well-resolved redox processes in CVs at E1/2 ≈ 0.1 V (Fc/Fc+ couple) and at E1/2 ≈ 0.8–1.1 V (CoII/CoIII and NiII/NiIII couples). However, M-BipyP(MFS-co-DMS)s exhibit up to three redox transitions (Fc/Fc+, MII/MIII, and Bipy•−/Bipy mixed with MI/MII). These polymer-metal complexes enable new applications as multiredox silicone materials in polymer engineering, especially for (opto)electronic, adaptive electrochromic, and stimuli-responsive devices.

KW - complexes of cobalt(II) and nickel(II)

KW - ferrocenyl-containing polysiloxanes

KW - multiredox properties

KW - polymer-metal complexes

KW - synthesis of polymers

UR - https://www.mendeley.com/catalogue/7ee734e5-b626-3f05-9f65-f9408726899f/

U2 - 10.1002/pol.20250879

DO - 10.1002/pol.20250879

M3 - Article

JO - Journal of Polymer Science

JF - Journal of Polymer Science

SN - 2642-4150

ER -