1070-4272/03/7602-0217 $25.00 C 2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 2, 2003, pp. 217!222. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 2, 2003,
Original Russian Text Copyright + 2003 by Semenistaya, Shchukarev, Shagisultanova.
AND CORROSION PROTECTION OF METALS
Electrically Conducting and Photosensitive Polymers
Derived from CuSalbn-1,4
T. V. Semenistaya, A. V. Shchukarev, and G. A. Shagisultanova
Herzen State Educational University, St. Petersburg, Russia
Mekhanobr-Analit Regional Analytical Center, Private Company, St. Petersburg, Russia
Received October 21, 2002
Abstract-A new electrically conducting photosensitive polymer was prepared by electrochemical poly-
merization of [CuSalbn-1,4]. Poly-[CuSalbn-1,4] was studied by X-ray photoelectron spectroscopy, voltam-
metry, and the photoelectrochemical methods.
Previously , we have prepared and isolated crys-
talline platinum, palladium, nickel, and copper com-
plexes with tridentate bis(salicylidene)-1,4-butylenedi-
amine ligand (Salbn-1,4
). These complexes contain
four methylene groups in the aliphatic diamine moiety,
unlike complexes with Salen and Salpn-1,3  li-
gands containing two and three methylene groups,
Electrochemical synthesis of electrically conducting
photosensitive poly-[PdSalbn-1,4] and parameters of
reversible electro- and photoredox processes occurring
in the bulk of the polymer were reported in our previous
paper . In this study, we prepared poly-[CuSalbn-
1,4] by an electrochemical procedure and studied its
physicochmeical and electrochemical properties.
complex [CuSalbn-1,4] was prepared by the modi-
fied procedure from . To a methanolic solution
O (2.2 mM, 30 ml CH
was added a methanolic solution of [Salbn-1,4]
5 wt % excess. To prevent hydrolysis of copper(II)
acetate, the solution was acidified with acetic acid.
The resulting dark green solution was heated at 100oC,
evaporated by half, cooled, and kept at 0oC for 12 h.
Dark green crystals were filtered off, washed with
OH and C
O, and dried in air. Yield 60365%.
Found (%): C 60.34, H 5.25, N 7.83.
Calculated (%): C 60.47, H 5.07, N 7.84.
Gruber et al.  studied the paramagnetic proper-
ties of [CuSalbn-1,4] and determined its magnetic
moments at room temperature.
The C1s,O1s,N1s, and Cu2p binding energies
and the atomic concentrations of the elements in dif-
ferent chemical states in the initial ligand H
and complex [CuSalbn-1,4] are listed in Table 1.
The electronic absorption spectra of H
in acetonitrile and [CuSalbn-1,4] in various solvents
are shown in Fig. 1. The spectrum of the free ligand
contains strong p3p
intraligand charge-transfer band
= 315 nm (e = 8400 l mol
). In the spec-
trum of [CuSalbn-1,4], a shoulder with l
= 300 nm
(e = 7500 lmol
is observed in the range of
absorption of the uncoordinated ligand. The spectrum
of an acetonitrile solution of the complex contains an
additional band with l
= 375 nm and high molar
extinction coefficient of 9000 l mol
. The shape
of this band is similar to that of allowed p3p
electronic transitions. The peak position of this band
Table 1. C1s,O1s,N1s, and Cu2p binding energies and
atomic concentrations of C, O, N, and Cu in [H
and [CuSalbn-1,4] (XPS data)
Salbn-1,4 ³ CuSalbn-1,4
³ BE, eV ³ c,% ³ BE, eV ³ c,%
C1s ³ 285.0 ³ 57.74 ³ 285.0 ³ 55.70
³ 286.3 ³ 26.41 ³ 286.4 ³ 24.71
N1s ³ 398.9 ³ 5.64 ³ 399.4 ³ 6.33
³ 399.7 ³ 1.58 ³³
³³³401.7 ³ 0.50
³ 402.9 ³ 0.68 ³ 403.5 ³ 0.87
O1s ³³³531.4 ³ 6.90
³ 532.9 ³ 7.93 ³ 532.4 ³ 0.53
Cu2p3/2³³³934.7 ³ 4.45