Redox polymer poly-N,N′-2,3-dimethylbutane-2,3-diyl-bis(salicylideniminato)nickel: An impedance spectroscopy study

Abstract

Films of poly-N,N'-2,3-dimethylbutane-2,3-diyl-bis(salicylideniminato)nickel are studied by cyclic voltammetry and faradaic impedance methods in acetonitrile solutions containing 0.1 M tetraethylammonium tetrafluoroborate. The resistance to charge transfer and the double-layer capacitance, calculated from the semicircle in the high-frequency spectrum portion, are referred to the film/electrolyte interface. From the low-and mid-frequency impedance spectra portions, the low-frequency capacitance and the effective diffusion coefficient of charge carriers are determined. The assumption about a noticeable film porosity is shored up by direct scanning electron microscopy examination of film surfaces.

Electronic Spectra of Mono‐ and Dinuclear Complexes of Fully π‐Conjugated salphen Ligands Synthesized by Using 2,6‐Dihydroxynaphthalene Carbaldehydes

“…[8][9][10][11][12][13] In addition, electrolytic polymerization of Ni-salen complexes is interesting methodology for the fabrication of conductive films, although the mechanism of conduction (e.g., by an intrachain or interchain carrier path) is still controversial. [14][15][16] p π -conjugated metallopolysalen and polysalphen compounds requires the preparation and analysis of well-defined oligonuclear complexes. However, there have been few reports [17] highlighting the effects of intracomplex (metalmetal and ligand-metal) interactions on the spectroscopic features of fully π-conjugated oligonuclear salen and salphen complexes.…”

Synthesis and Properties of Polymeric Copper Complexes with Schiff Bases

“…In particular, for poly-[Ni,Þd(Schiff)] complexes, cD ct 1/2 substantially increases on passing from the polymers with the SalEn ligand to those with the SaltmEn ligand. As shown in [19], the introduction of four methyl groups into the structure of the diamine bridge between the phenyl moieties results in a noticeable increase in the repulsive interactions between the polymer stacks and in the formation of a less compact polymeric film. For [Cu(Schiff)] polymers, such a change in the ligand surrounding results in increasing efficiency of the motion of charge-compensating ions, but does not noticeably affect the charge-transfer rate.…”

Atomic and Electronic Structure of Metal–Salen Complexes [M(Salen)], Their Polymers and Composites Based on Them with Carbon Nanostructures: Review of X-ray Spectroscopy Studies

“…Despite a significant amount of research into the structure and properties of electrically conductive redox polymers poly-[M(Salen)], and in particular poly-[Ni(Salen)], there is no consensus on the mechanism of polymerization of monomer molecules [1,2,[11][12][13][14][15][16][19][20][21][23][24][25][26][27][28][29][30][31][32][33][34][35][40][41][42][43]. The first model assumes chemical linkage between the phenyl groups of the ligands of neighboring molecules (chainlike structure).…”

“…Until now, the most popular methods for experimentally characterizing the properties of these new materials remain scanning electron microscopy (SEM), in situ UV-visible and IR spectroscopy, in situ ellipsometry, and electrochemical methods (cyclic voltammetry, chronoamperometry, impedance spectroscopy, etc.) [3][4][5][6][7][8][9][10][11][12][13][14][15][16]. However, the methods used provide far from a complete understanding and description of the formation processes of these systems.…”