1070-4272/04/7712-1962 C 2004 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 77, No. 12, 2004, pp. 1962!1966. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004,
Original Russian Text Copyright + 2004 by Ardasheva, Vovk, Pchelova, Shagisultanova.
AND CORROSION PROTECTION OF METALS
Anodic Electrochemical Polymerization
of Complexes [Ni(Salpn-1,3)] and [Cu(Salpn-1,3)]
L. P. Ardasheva, G. V. Vovk, L. G. Pchelova, and G. A. Shagisultanova
Hertzen Russian State Pedagogical University, St. Petersburg, Russia
Received July 9, 2004
Abstract-New experimental data characterizing the conditions of electrochemical synthesis of stable elec-
trically conducting electrochromic polymeric film systems based on the complexes [Ni(Salpn-1,3)] and
[Cu(Salpn-1,3)] [Salpn-1,3 is N, N`-propylenebis(salicylidenimine)] in a 0.1 M Bu
are presented. The redox conductivity of the new polymers is characterized by the charge diffusion coefficient.
The electrochemical stability of the polymeric films is analyzed in relation to the potential and time of
accumulation, and also to the range of potential sweeping.
Studies of thin electrically conducting electro-
chromic metal-containing polymeric films on solid
supports are of current interest because of the possibil-
ity of creating electro- and photocatalysts, sensors,
and solid-phase galvanic cells for conversion of the
energy of light on their basis [1, 2].
In the last fifteen years, polymeric film systems
based on complex compounds of transition metals
with macrocyclic ligands of varied composition and
structure have been synthesized and rather extensive-
ly studied, including N, N`-ethylenebis(salicylidenes)
, porphyrins , phthalocyanines , etc.
Complexes with ligands of this kind are of the utmost
interest to a researcher, because they are models and
(or) analogues of most important natural organometal-
However, despite that a considerably body of ex-
perimental data has been obtained, the optimization
of the synthesis conditions and analysis of the struc-
ture, stability, and functional features of organometal-
lic polymers, including the best-studied compounds of
copper(II) and nickel(II), remains a matter of current
The present communication reports original results
characterizing the synthesis conditions of polymeric
systems based on the complexes [Cu(Salpn-1,3)] and
[Ni(Salpn-1,3)], where Salpn-1,3 is N, N`-propylene-
bis(salicylidenimine)], in a solution of methylene chlo-
ride. It should be noted that the ability of the complex
[Cu(Salpn-1,3)] to form, as a result of oxidation at
the electrode, photosensitive electrically conducting
polymers has been revealed previously , whereas
the possibility, in principle, of polymerization of
[Ni(Salpn-1,3)] is established for the first time.
The complexes [Ni(Salpn-1,3)] and [Cu(Salpn-1,3)]
M = Ni(II), Cu(II)
were synthesized by the known methods .
The complexes were identified by electronic absorp-
tion spectroscopy in the visible and near-UV spectral
ranges and by X-ray photoelectron spectroscopy (XPS).
XPS spectra were obtained on an Axis Ultra electronic
spectrometer (Kratos Analytical, UK) under excitation
with monochromatic Al
radiation (1486.6 eV).
During the experiments, the initial vacuum in the spec-
trometer was 5 0 10
Pa. The spectra obtained were
processed with a Vision software package (Kratos
Analytical). The scale of binding energies was cali-
brated against the C1s line of aliphatic carbon (E
285.0 eV). The binding energies of photoelectrons and
the atomic concentrations of selected components of
the photoelectron spectra for the ligand H
The XPS spectra were measured by A.V. Shchukarev (St. Pe-
tersburg State University)