ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 2, pp. 226−231. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.S. Tverjanovich, A.O. Aver’yanov, M.A. Ilyshin, Yu.S. Tverjanovich, A.V. Smirnova, 2015, published in Zhurnal Prikladnoi Khimii,
2015, Vol. 88, No. 2, pp. 221−226.
INORGANIC SYNTHESIS AND INDUSTRIAL
Decomposition of Cobalt(III) Nitrotetrazolato Amminates
under the Action of Laser Light
A. S. Tverjanovich
, A. O. Aver’yanov
, M. A. Ilyshin
, Yu. S. Tverjanovich
and A. V. Smirnov
St. Petersburg State University, Universitetskaya nab. 7–9, St. Petersburg, 199034 Russia
St. Petersburg State Technological Institute (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
Received October 28, 2014
Abstract—IR spectroscopy was used to study (5-nitrotetrazolato–N
)pentaaminecobalt(III) perchlorate (1) and
)]}tetraaminecobalt(III) perchlorate (2) and products of their decomposition under
the action of laser light resonant in energy with d–d transitions observed in these complexes. The electronic spectra
of complexes 1 and 2 are governed by d–d transitions of cobalt ions (
at 328–330 nm and
at 455–466 nm) and ligand–metal charge transfer in a shorter wavelength range. Comparison of the vibration
spectra of the decomposition products and starting complexes suggests that cobalt amminates decompose to give
] groups in unknown compounds.
Strong attention is being given to the development
of methods for finding energy-saturated substances
and products of their actuation . The importance
of solving this problem is due to the necessity for
counter-terrorism measures. These measures include
investigative activities aimed to determine products
formed in actuation of energetic substances (ESs) the
purpose of their identification. The composition of
these products may vary with actuation conditions and,
possibly, initiation method and, consequently, furnishes
information about these factors. Therefore, it is necessary
to have information about products formed with various
mechanisms of ES decomposition.
In addition, information about ES decomposition
products is also of interest for studying the occurring
chemical processes. When products are not obtained under
extreme conditions (high pressure and temperature), they
provide information about the chemical mechanism of
the ES initiation. It is particular important in this case to
determine their formation conditions.
Recently, researchers’ interest has been attracted by
ESs initiated by laser light. This initiation technique has
a number of advantages. In the ﬁ rst place, there is no
need for engineering efforts to lay out electric circuits
or use disposable wireless devices. Otherwise, not only
additional technical efforts are required, but, what is more
important, there is danger of unsanctioned actuation.
A study of products formed in decomposition of
ESs under the action of laser light is also of interest for
ﬁ nding their trace amounts because just these methods of
ES detection have been successfully developed recently.
These include the laser-induced breakdown spectroscopy
(LIBS)  and the photofragmentation–laser-induced
ﬂ uorescence (PF-LIF) of ESs .
Taking into account the aforesaid, we studied optical
spectra of products formed in laser decomposition of ESs.
In the process, particular attention was give to choosing
the wavelength of the decomposing laser light because the
composition of the products may depend on the primarily
excited particular structural elements.
As objects of study were chosen two complexes be-
longing to cobalt(III) amminates, which contain one or
two 5-nitrotetrazole anions as heterocyclic ligands (L) and
outer-sphere perchlorate anions. These are (5-nitrotetrazo-