Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1890−1893.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
M.A. Besedina, S.A. Krasikova, A.M. Timonov, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1738−1741.
AND POLYMERIC MATERIALS
Ionic Charge Transfer in Films of Polymeric Complexes
of Transition Metals with Schiff
M. A. Besedina, S. A. Krasikova, and A. M. Timonov
Herzen Russian State Pedagogical University, St. Petersburg, Russia
Received April 1, 2009
Abstract—Transport of charge-compensating ions in redox transformations in films of polymeric complexes
of nickel, copper, and palladium with tetradentate Schiff bases was studied by electrochemical quartz crystal
Polymer ﬁ lms exhibiting conjugate electronic–ionic
conductivity are promising materials for energy
storage systems, membrane electrochemistry, polymer
microelectronics, bioelectrochemistry, and selective
electrocatalysis. The basic problem whose solution will
determine further progress in the development and use of
such polymeric materials is elucidation of relationships
between their composition, structure, and properties.
Polymer films based on complexes of transition
metals (M) with tetradentate Schiff bases (examples
of the compounds are shown in Fig. 1a) are capable of
functioning in both nonaqueous and aqueous solutions.
They exhibit high mechanical strength and thermal
In our previous studies we determined the structure
of these materials (Fig. 1b) and found methods for
controlling it on the nano- and molecular levels [1, 2]. An
important characteristic of the polymers is also the rate
of charge transfer in the polymer matrix .
In the general case, the most important interrelated
steps of this process are as follows:
(i) electron transfer between the redox centers, which
can occur by the mechanism of electron hopping;
(ii) introduction into the polymer, diffusion–migration
transfer in the polymer, and exit from the polymer
of charge-compensating ions, due to the need for
compensating the volume charge arising in the polymer
in the course of redox processes (concept of conjugate
electron–ion ﬂ ows);
(iii) introduction into the polymer, diffusion transfer
in the polymer, and exit from the polymer of solvent
molecules in the course of redox processes.
Fig. 1. (a) Scheme of the structure of the starting complexes [M(Schiff)] and (b) structure of the polymers poly-[M(Schiff)]. (a) М = Ni,
Pd, Cu; R=H: [M(SalEn)] = N,N'-ethylenebis(salicylideniminato)metal(II); R=OCH
O–SalEn)] = N,N'-ethylenebis(3-meth-
oxysalicylideniminato)metal(II). (b) Polymers consist of stacks in which separate fragments are bonded by donor–acceptor interaction
between the metallic center of one fragment and the ligand of another fragment.