ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 11, pp. 2332–2344. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.A. Minaeva, B.F. Minaev, G.V. Baryshnikov, T.N. Kopylova, R.M. Gadirov, N.S. Eremina, 2011, published in Zhurnal Obshchei
Khimii, 2011, Vol. 81, No. 11, pp. 1881–1893.
2332
Study of Structure and Spectral Characteristics
of the Binuclear Zinc Complex
with (E)-2-({2-[3-(pyridin-2-yl)-1H-1,2,4-triazol-
5-yl]phenylimino}methyl)phenol
V. A. Minaeva
a
, B. F. Minaev
a
, G. V. Baryshnikov
a
,
T. N. Kopylova
b
, R. M. Gadirov
b
, and N. S. Eremina
b
a
Khmelnitskii Cherkassy National University, ul. Shevchenko 81, Cherkassy, 18031 Ukraine
e-mail: minaeva@cdu.edu.ua
b
Tomsk State University, Tomsk, Russia
Received October 7, 2010
Abstract—A study of the structure and spectral properties of the compound (E)-2-({2-[3-(pyridin-2-yl)-1H-
1,2,4-triazol-5-yl]phenylimino}methyl)phenol and its binuclear complex with zinc was carried out by the
quantum-chemical calculations at a level of density functional theory. Within the framework of the time-
dependent density functional theory were calculated electron spectra of both compounds, which gave good
agreement with experiment, and was revealed the nature of the absorption bands in the visible and near UV
region taking into account the solvent effect. Complete interpretation of the absorption bands in the infrared
spectra of the complex and protonated ligand was given, and the frequency shift and changes in the intensities
of IR bands of the ligand at the complex formation were analyzed.
The organometallic structures capable of the
effective mutual transformation of electric and light
energy, have attracted much attention of researchers in
different fields of science and technology [1–4]. This
is due primarily to the development of technology of
organic light-emitting diodes used in microelectronics,
whose operating principle is based on the ability of an
organic or organometallic compound to electro-
luminescence. Such requirements are satisfied by the
synthesized earlier 1,2,4-triazole derivative, (E)-2-({2-
[3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl]phenylimino}-
methyl)phenol (H
2
L) [5]. Electroluminescence of a
sensor devices based on this compound and its
binuclear complex with zinc (Zn
2
L
2
) has been studied
[6], and the complex Zn
2
L
2
was shown to exhibit a
more stable electroluminescence and is more resistant
to oxidation (burning out) than the compound H
2
L.
This paper concerns the results of quantum-
chemical study of the structure and spectral properties
of the compound H
2
L and its binuclear complex with
zinc (Zn
2
L
2
). The data obtained explain the influence
of complexation on the structure and spectral
properties of these compounds. On the basis of the
calculations we revealed the nature of compound H
2
L
and its complex absorption in the visible and infrared
regions, which can be useful in designing new
electroluminescent devices. A detailed study of IR
spectra allowed us to determine the nature of all the
bands, as well as to trace the changes in the
frequencies and intensities of infrared absorption at the
complexation. This provides additional criteria for
establishing the relationship between the structure of
the compounds, the nature of complex formation, and
their electronic and photophysical properties.
Analysis of the Structure of Molecular Complex Zn
2
L
2
and Protonated Ligand H
2
L
Optimized structure of the complex Zn
2
L
2
is shown
in Fig. 1. All calculated frequencies in the vibration
spectrum of the complex are real, indicating that it
corresponds to the true global minimum on the
potential energy hypersurface of the molecule.
DOI: 10.1134/S1070363211110193