1070-4272/01/7411-1854$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 11, 2001, pp. 1854!1857. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 11,
2001, pp. 1799!1802.
Original Russian Text Copyright + 2001 by Borisov, Shagisultanova.
PRODUCTION AND USE
OF NEW MATERIALS
Factors Determining the Charge Transfer Rate in Polymers
Based on Fe(II), Ru(II), and Os(II) Complexes
A. N. Borisov and G. A. Shagisultanova
St. Petersburg State University of Low-Temperature and Food Technologies, St. Petersburg, Russia
Herzen Russian State Educational University, St. Petersburg, Russia
Received June 29, 2001
Abstract-The effect of ionic diffusion on parameters of redox electrical conductivity in poly-
(M = Fe, Ru, Os) was studied.
Supramolecular chemistry studying ordered asso-
ciations of coordination-saturated species is an urgent
branch of the modern basic science showing promise
for high technologies . Electroconducting supra-
molecular structures that are formed from polymers
based on organometallic and coordination compounds
of transition metals are of special interest. As a rule,
these are intensely colored substances with a series of
practically important properties such as redox elec-
trical conductivity of polymeric complexes, photosen-
sitivity, photo- and electroactivity, electrocatalytic and
From the viewpont of the practical use, polymeric
structures with a high rate of charge transfer in the
bulk of the solid phase, stable to action of chemical
and physical factors, are of the most interest. Such
complexes can be promising materials for production
of sensors, chemotronic, photo- and electrocatalytic
devices, and solid converters of the light energy .
In this work, we studied the electrochemical prop-
erties of polymers based on Fe(II), Ru(II), and Os(II)
complexes with 5-chloro-1,10-phenanthroline with the
aim to reveal factors determining the rate of charge
transfer in the polymer bulk.
(M = Fe, Ru,
Os; 5-Cl-phen = 5-chloro-1,10-phenanthroline) were
synthesized by methods described in  and indenti-
fied by elemental analysis and electronic absorption
spectra [5, 6].
1,10-phenanthroline)iron(II) perchlorate [Fe(4,7-ph
was prepared by suc-
cessively mixing the initial reagents 5-Cl-phen
(0.466 mmol), FeSO
O (0.233 mmol), and
-phen (0.233 mmol) in 50 ml of hot ethanol.
The resulting dark red solution was vigorously agi-
tated at moderate heating for 2 h. The claret-colored
complex (perchlorate form) was filtered off, washed
with water, hot benzene, and diethyl ether, and dried
in a vacuum over phosphorus(V) oxide. Yield 85%.
Found (%): C 61.89, H 2.74, N 7.45.
Calculated (%): C 62.06, H 2.58, N 7.24.
The electrochemical synthesis of polymeric
was performed in the potentiostatic
mode. The optimal conditions of growth of polymeric
layers were as follows : polarization potential of
the working electrode in 2 0 10
M acetonitrile solu-
tions of monomeric complexes E
= 31.6 V, polariza-
tion time 7 min.
The electrochemical properties of the polymeric
complexes were studied by cyclic voltammetry.
A PI-50-1 pulse potentiostat with incorporated IR-
compensation system set the potential of the working
electrode. The potential of the working electrode was
scanned in the cyclic mode at a rate of 10, 20, 50,
100, 200, and 500 mV s
. Voltammograms were
recorded on a 307 two-coordinate potentiometric
Voltammetric measurements were performed in
a hermetically sealed three-electrode Pyrex cell with
separated compartments of the working, auxiliary, and