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Thermal behavior of manganese(II) complexes with pyridine-2,3-dicarboxylic acid

Spectroscopic, X-ray, and magnetic studies

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Abstract

In this study, we analyzed influence of the type of the syntheses used: hydrothermal and non-hydrothermal on pyridine-2,3-dicarboxylic acid (2,3pydcH2) coordination fashion. Two manganese(II) complexes: [Mn(H2O)3(2,3pydc)] n (1) and [Mn(H2O)6][Mn(2,3pydcH)3]2 (2) were successfully synthesized from the non-hydrothermal reaction system containing organic ligand and different Mn(II) salts. The received complexes have been prepared and characterized by spectroscopic (IR, Raman), structural (X-ray single crystal), and thermogravimetric methods. The results of the crystal study give some evidence that ligand exhibits various topological structures and interesting properties. Pyridine-2,3-dicarboxylic acid acts as monodicarboxylate N,O-chelating anion (complex 2) or a doubly deprotonated three-dentate-N,O,O′ dicarboxylate ion (complex 1). In the [Mn(H2O)6][Mn(2,3pydcH)3]2 the coordination geometry around Mn(1) ion can be considered as being distorted octahedron {MnN3O3}. The Mn(2) cation possesses the same coordination polyhedron (octahedral). We have also analyzed influence of furnace atmosphere on the thermal behavior and the kind of final product. The sample of (1) decomposes in four stages in N2 (368–1073 K) and the final residue is MnO2. The thermogram of (2) exhibits three main distinct decomposition steps (383–973 K). A residue of MnO is remained. In both air and nitrogen atmosphere, Mn(II) complexes (1) and (2) keep unchanged over all steps of decomposition. Only the final residues are different (Mn2O3 are formed). The course of pyrolysis and molecular structure of the complexes lead to the same conclusion about the strength of metal–ligand bonds. On the basis of the above results, it is concluded that the thermal stability of the manganese(II) compounds is slightly different.

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Acknowledgements

The authors are grateful to Dr. Wiesław Surga and MSc Joanna Masternak for help during the thermal work and XRD investigations. European Union Project 8.2.1/POKL/2009 supported this work (M. Zienkiewicz) partly. The opportunity of making the Raman spectra in the Structural Laboratory of the Jan Kochanowski University is also gratefully acknowledged.

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Authors and Affiliations

  1. Institute of Chemistry, The Jan Kochanowski in Kielce, 15G Świętokrzyska Str., 25-406, Kielce, Poland

    Agnieszka Jabłońska–Wawrzycka, Małgorzata Zienkiewicz, Patrycja Rogala & Barbara Barszcz

  2. Faculty of Chemistry, Jagiellonian University, 3 Ingardena Str., 30-060, Kraków, Poland

    Maciej Hodorowicz

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  1. Agnieszka Jabłońska–Wawrzycka
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Correspondence to Agnieszka Jabłońska–Wawrzycka.

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Jabłońska–Wawrzycka, A., Zienkiewicz, M., Hodorowicz, M. et al. Thermal behavior of manganese(II) complexes with pyridine-2,3-dicarboxylic acid. J Therm Anal Calorim 110, 1367–1376 (2012). https://doi.org/10.1007/s10973-011-1971-1

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