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International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
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TD-DFT investigations of electronic absorption spectra of niflumic acid
Małgorzata Kosińska
1
, Lidia Zapała
1
, Jan Kalembkiewicz
1
, Tadeusz Pietryga
2
,
Urszula Maciołek
1
, and Anna Kuźniar
1
1
Department of Inorganic and Analytical Chemistry, Faculty of Chemistry, Rzeszow University of
Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland, e-mail: mkosinska@prz.edu.pl
2
Department of Physical Chemistry, Faculty of Chemistry, Rzeszow University of Technology, Al.
Powstańców Warszawy 6, 35-959 Rzeszów, Poland
Niflumic acid (Fig. 1) is a non-steroidal anti-inflammatory analgesic and belongs to the
derivatives of N phenylanthranilic acid (fenamates). It demonstrates considerable anti-
inflammatory and analgesic activity as well as a slight antipyretic effect [1]. Niflumic acid is
used to treat inflammatory rheumatoid diseases and relieve acute pain. Moreover, it is effective
against period pains, pain after surgery, and fever [2, 3].
Fig. 1. The molecular structure of niflumic acid.
Niflumic acid and other fenamic acids are an important group of ligands in coordination
chemistry. The interest in the field of fenamates complexes is due the fact, that they have several
important potential applications, i.e. pharmaceutical application in therapy as antioxidant, anti-
inflammatory, antibacterial, antiproliferative, anti-tuberculosis or antifungal agents [4].
Consequently, knowledge about the spectral properties, including electronic spectra of
niflumic acid, may be helpful in determining the structure of its metal complexes.
In order to facilitate spectra interpretation the computational methods can be applied. In this
work the calculations of energies and intensities of spectral bands were reproduced by the time-
dependent density functional theory (TD-DFT), while the solvents were approximated by the
conductor-like polarizable continuum model (CPCM). The following procedure has been
applied:
1. Conformational studies of the ground-state geometry of niflumic acid.
2. Determination of the vertical electronic excitation energies using the TD-DFT framework.
Furthermore, in order to obtain the best compatibility with the experimental results, the
calculations have been conducted with use TD-DFT method and various functionals and basis
set, taking into account the polarization and diffusion functions. The results of calculations have
been used in detailed interpretation of the experimental electronic absorption spectra of the
investigated compound.
Keywords: nflumic acid; electronic spectra; TD-DFT
References
[1] A.C. Kennedy, C. Watkins, P. Brooks, D. Grennan, Current Medical Research and Opinion 2 (1974)
32.
[2] P. Tsiliki, F. Perdih, I. Turel, G. Psomas, Polyhedron 53 (2013) 215.
[3] S. Tsiliou, L.-A. Kefala, A.G. Hatzidimitriou, D.P. Kessissoglou, F. Perdih, A.N. Papadopoulos, I.
Turel, G. Psomas, Journal of Inorganic Biochemistry 160 (2016) 125.
[4] G. Psomas, D.P. Kessissoglou, Dalton Transactions 42 (2013) 6252.
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International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
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1,3-phenylenediacetates based on lanthanide(III) ions: synthesis,
structural, spectroscopic and thermal stability studies
Justyna Sienkiewicz-Gromiuk
1
, Iwona Rusinek
1
, and Renata Łyszczek
1
1
Department of General and Coordination Chemistry, Maria Curie-Sklodowska University,
M. Curie- Sklodowska Sq. 2, 20-031 Lublin, Poland,
e-mail: j.sienkiewicz-gromiuk@poczta.umcs.lublin.pl
The rational synthesis and design of polymeric metal-organic complexes have been greatly
developed in the latest decades, due to their intriguing architectures as well as potential
applications as functional materials. Flexible organic ligands, especially aromatic multi-
carboxylates are of immerse interest in the construction of polymeric coordination assemblies,
not only because of their strong coordination ability, but also because they provide the hydrogen
bond acceptors/donors and π-conjucted system [1, 2]. 1,3-Phenylenediacetic acid is a valuable
organic ligand which is composed of aromatic core and two flexible aliphatic acetic units
(−CH2COOH). 1,3-Phenylenediacetate ligand may take versatile coordination fashions and act
as effective bridging linker for constructing diverse coordination networks based on various
metal ions [3, 4].
Solid lanthanide(III) 1,3-phenylenediacetate complexes were prepared under conventional
mild and hydrothermal conditions. The synthesized products were investigated by single-crystal
X-ray and powder diffraction techniques and were also characterized by other analytical
methods, like elemental analysis, various spectroscopic techniques including IR, Raman, XPS as
well as thermogravimetric and TG−FT-IR coupled measurements. The analyzed complexes are
crystalline and they contain several molecules of water which are completely removed up to
about 200°C. The deprotonation of all carboxylic groups of the 1,3-phenylenediacetate ligand in
the complexes is confirmed by the lack of stretching carbonyl ν(C=O) vibrations at 1696 cm
–1
[5]. On the other hand, the participation of carboxylate groups in the coordination of the
lanthanide(III) ions is reflected in the infrared spectra through the presence of the stretching
carboxylate vibrations. The XPS electronic spectra (Fig. 1) also confirmed the full
transformation of acidic carboxylic groups into carboxylate systems during complexes
formation.
Fig. 1. XPS spectra of the acid (A) and its Sm(III) complex (B).
Keywords: Lanthanide(III) 1,3-phenylenediacetate complexes; infrared spectroscopy; XPS spectra
References
[1] X. Wang, J. Zhang, G. Liu, H. Lin, J. Solid State Chem. 184 (2011) 280.
[2] J.-Z. Liu, Z. Zhang, X.H. Yin, P. Gao, L. Wang, J. Chem. Crystallogr. 42 (2012) 1001.
[3] J-Z. Gu, D.-Y. Lv, Z.-Q. Gao, J-Z. Liu, W. Dou, Y. Tang, J. Solid State Chem. 184 (2011) 675.
[4] Y.X. Ren, M.L. Zhang, D.S. Li, F. Fu, J.J. Wang, M. Du, X.Y. Hou, Y.P. Wu, Inorg. Chem. Commun.
14 (2011) 231.
[5] H. Göcke, S. Bahceli, Spectrochim. Acta A 78 (2011) 803.
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