1070-4272/03/7610-1631 $25.00 C 2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 10, 2003, pp. 1631!1636. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 10, 2003,
Original Russian Text Copyright C 2003 by Shagisultanova, Ardasheva, Orlova.
AND POLYMERIC MATERIALS
Electro- and Photoelectroactivity of Thin-Layer Polymers
Based on [NiSalen] and [NiSalphen] Complexes
G. A. Shagisultanova, L. P. Ardasheva, and I. A. Orlova
Herzen Russian State Educational University, St. Petersburg, Russia
Received April 8, 2003
Abstract-New experimental data on physicochemical properties of polymeric nickel(II) complexes with
N,N`-bis(salicylidene)ethylenediamine and N,N`-bis(salicylidene)-o-phenylenediamine (including redox con-
ductivity, photoactivity in a solution of a supporting electrolyte, and electrochemical stability) were obtained.
The rate of charge transport in the polymeric matrix was studied as a function of the polymer film thickness.
Electrochemical synthesis and study of thin-layer
metal-containing polymers attracts much researchers’
attention . The electrochemical synthesis allows
preparation of conducting polymers on solid supports
as solid and uniform films with controllable thickness.
Transition metal complexes with macrocyclic ligands
of various compositions and structures, which are
structural units in the synthesis of these polymers,
determine the variety of their properties , e.g.,
redox conductivity, photosensitivity, sensor and cat-
It has been found previously [6, 11] that, when
immersed in a solution of a supporting electrolyte,
polymers based on transition metal complexes with
ligands of the N,N`-bis(salicylidene)ethylenediamine
(Salen) type in the reduced and (or) partially oxidized
state are photoelectroactive and can exhibit a positive
photovoltaic effect [6, 11]. The maximum positive
change in the potential of the electrode with the poly-
mer layer applied by electrochemical synthesis was
first found for poly[PdSalen] and amounted to 450 mV
. The photoelectroactivity is the major property
required of polymers to be used in accumulation and
conversion of the energy of light.
Thus, these polymers are promising materials in
production of sensors, electro- and photocatalysts,
and solid-phase galvanic cells.
In the preceding publication , we considered
the optimal conditions of the synthesis and the kinet-
ic aspects of formation of polymers based on Ni(II)
complexes with N,N`-bis(salicylidene)ethylenediamine
(Salen) and N,N`-bis(salicylidene)-o-phenylenediamine
(Salphen). In this study, we analyzed the electro- and
photoinduced charge transfer in poly[NiSalen] and
poly[NiSalphen] and the electrochemical stability of
The method of the electrochemical measurements
was described in .
The photoelectric measurements were performed on
a device including an irradiation source (DRSh-1000
lamp), a potentiometric recorder, and a photoelectro-
chemical cell. A cell with parallel-plate windows was
the working part of a two-electrode Pyrex glass cell.
The samples were irradiated with focused polychro-
matic light; the IR light was cut off by two water
filters. A silver chloride electrode filled with a satu-
rated NaCl solution was used as reference. A platinum
(99.99% Pt) wire with surface area of 0.25 cm
in the glass served as indicator electrode. The elec-
trode was coated with a layer of the polymer studied,
which was deposited in the course of the electrochem-
ical synthesis. A 0.1 M solution of tetraethylammo-
nium perchlorate Et
in acetonitrile CH
was used as a supporting electrolyte.
The capability for reversible electroinduced charge
transfer is one of the major properties of Ni(II) poly-
mers studied and the related polymeric compounds.
Among conducting polymers, two main groups are
distinguished. To the first group belong polymers
with electrons delocalized over very extended poly-
conjugated systems. These are mainly organic poly-
mers containing no metal [9, 15317]. The second