Aleksander M. Timonov

Conductive electrochemically active metallopolymers are outstanding materials for energy storage and conversion, electrocatalysis, electroanalysis, and other applications. The hybrid inorganic–organic nature of these materials ensures their rich chemistry and offers wide opportunities for fine-tuning their functional properties. The electrochemical modulation of the nanomechanical properties of metallopolymers is rarely investigated, and the correlations between the structure, stiffness, and capacitive properties of these materials have not yet been reported. We use electrochemical atomic force microscopy (EC-AFM) to perform in-situ quantitative nanomechanical measurements of two Schiff base metallopolymers, poly[NiSalphen] and its derivative that contains two methoxy substituents in the bridging phenylene diimine unit poly[NiSalphen(CH₃O)₂], during their polarization in the electrolyte solution to the undoped and fully doped states. We also get insight into the electrochemical p-doping of these polymers using electrochemical quartz crystal microgravimetry (EQCM) coupled with cyclic voltammetry (CV). Combined findings for the structurally similar polymers with different interchain interactions led us to propose a correlation between Young’s modulus of the material, its maximum doping level, and ion and solvent fluxes in the polymer films upon electrochemical oxidation.

The new complex [Co^III(3-CH₃Salen)(CH₂CN)]·CH₃CN was synthesized and its crystal structure was determined by the X-ray diffraction analysis. The cyanomethylene ligand is bound to the metallocenter by a Co‒C bond. In the crystalline state, an organometallic polymer structure is formed, in which metal atoms are interconnected by cyanomethylene bridges.

The crystal structure of the N,N′-(2,3-dimethylbutane-2,3-diylbis(3-methylsalicylideneiminate)nickel(II) complex was determined by means of single crystal X-ray analysis. The main characteristics of the complex obtained by ¹H NMR, UV-VIS, and IR spectroscopy and voltammetry are presented.

The copper(II) complex ethylene-N-(salicylideniminato)-N'-(3-methoxy-salicylideniminato)copper(II) [Cu(Sal-CH₃OSal)en] with the asymmetric N₂O₂ Schiff base was synthesized. The complex was identified by the NMR, IR, and UV-Vis spectroscopy and voltammetry methods. The crystal structure of the complex was determined by the X-ray structural analysis.

Crystal structures of N,N'-ethylenebis(3-nitrosalicylideneiminato)nickel(II) [Ni(3-NO₂SalEn)] and N,N'-(2,3-dimethylbutane-2,3-diyl)bis(3-nitrosalicylideneiminato)nickel(II) [Ni(3-NO₂SaltmEn)] were determined by single crystal X-ray diffraction analysis. The [Ni(3-NO₂SalEn)] complex forms supramolecular associates in the crystal phase, which affects its solubility, thermogravimetric, and spectral characteristics.

A new electroconductive polymer based on a nickel complex with N₄ Schiff base has been synthesized for the first time. Electrochemical properties of this material and the nature of charge carriers have been studied. The possibility of using this polymer as a functional component of cathodes in lithium-ion batteries is demonstrated.

Conductive polymer based on a Nickel complex with N4 Schiff base were prepared for the first time, its electrochemical properties and the nature of charge carriers were investigated, and the fundamental possibility of using the polymer as a functional cathode additive in lithium-ion batteries was shown.

The data on polymeric complexes of nickel with salen-type Schiff bases containing electron-withdrawing nitro groups in ligand’s aromatic fragments are acquired by an in situ technique based...