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The features of iodine loss at high temperatures

The case study of crystalline thiazoloquinolinium polyiodides

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Abstract

A series of crystalline thiazoloquinolinium iodides has been studied using a combination of thermal analysis, mass and Raman spectroscopy techniques. The influence of composition and polyiodide anion stoichiometry on the features of iodine loss has been revealed. It has been shown that the existence of a bound diiodine molecule in a polyiodide chain leads to significant decrease in melting point and decomposition temperatures in comparison with corresponding mono- and triiodide salts. The loss of the diiodine molecule from the complex polyiodide proceeds independently, without decomposition of the organic cation, while the release of diiodine from the triiodide anion goes simultaneously with thermal decomposition of the cation. In addition, the decomposition processes on the surface of the thiazoloquinolinium polyiodide crystal have been investigated during sample storage. Iodine loss and formation of more stable triiodide have been proved using Raman spectroscopy data.

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References

  1. Svensson PH, Kloo L. Synthesis, structure, and bonding in polyiodide and metal iodide-iodine systems. Chem Rev. 2003;103:1649–84.

    Article  CAS  Google Scholar 

  2. Yamanaka N, Kawano R, Kubo W. Dye-sensitized TiO2 solar cells using imidazolium-type ionic liquid crystal systems as effective electrolytes. J Phys Chem B. 2007;111:4763–9.

    Article  CAS  Google Scholar 

  3. Fei Z, Kuang D, Zhao D, Klein C, Ang WH, Zakeeruddin SM, Grätzel M, Dyson PJ. A supercooled imidazolium iodide ionic liquid as a low-viscosity electrolyte for dye-sensitized solar cells. Inorg Chem. 2006;45:10407–9.

    Article  CAS  Google Scholar 

  4. Waentig L, Jakubowski N, Hayen H, Roos PH. Iodination of proteins, proteomes and antibodies with potassium triodide for LA-ICP-MS based proteomic analyses. J Anal At Spectrom. 2011;26:1610–8.

    Article  CAS  Google Scholar 

  5. Moulay S. Molecular iodine/polymer complexes. J Polym Eng. 2013;33:389–443.

    Article  CAS  Google Scholar 

  6. Kaiho T. Iodine chemistry and applications. New York: Wiley; 2014.

    Book  Google Scholar 

  7. Miyao K, Funabiki A, Takahashi K, Mochida T, Uruichi M. Reversible iodine absorption of nonporous coordination polymer Cu(TCNQ). New J Chem. 2014;38:739–43.

    Article  CAS  Google Scholar 

  8. Mukherjee A, Tothadi S, Desiraju GR. Halogen bonds in crystal engineering: like hydrogen bonds yet different. Acc Chem Res. 2014;47:2514–24.

    Article  CAS  Google Scholar 

  9. Reiss GJ, Engel JS. Crystal engineering of a new layered polyiodide using 1,9-diammoniononane as a flexible template cation. Z Naturforsch. 2004;59b:1114–7.

    Article  Google Scholar 

  10. Subashini A, Rajarajan K, Sagadevan S, et al. Preparation and characterization of a bis thiourea sodium iodide (BTSI). J Therm Anal Calorim. 2018;131:2179.

    Article  CAS  Google Scholar 

  11. Tebbe KF, Farida T, Stegemann H, Fullbier H. Untersuchungen an Polyhalogeniden. XXIII. Kristallstrukturen der N‐Alkylurotropiniumtriiodide UrRI3 mit R = Methyl, Ethyl, n‐Propyl und n‐Butyl. Z Anorg Allg Chem. 1996;622:525.

    Article  CAS  Google Scholar 

  12. Tebbe KF, Loukili R. Über das Dimethyl(n‐propyl)phenylammoniumtriiodid n‐PrMe2PhNI3 und die Reihe der Dimethyl(isopropyl)phenylammoniumpolyiodide i‐PrMe2PhNIx mit x = 3, 5, 7, 8, 9. Z Anorg Allg Chem. 1998;624:1175.

    Article  CAS  Google Scholar 

  13. Tebbe KF, Nagel K. Untersuchungen an Polyhalogeniden. XXVI [1]. Über NPropylurotropiniumpolyiodide UrPrIx mit x = 5 und 7: Strukturelle Charakterisierung eines Pentaiodids und eines Heptaiodids. Z Anorg Allg Chem. 1996;622:1323.

    Article  CAS  Google Scholar 

  14. Bartashevich EV, Yushina ID, Vershinina EA, Slepukhin PA, Kim DG. Complex structure tri- and polyiodides of iodocyclization products of 2-allylthioquinoline. J Struct Chem. 2014;55:112–9.

    Article  CAS  Google Scholar 

  15. Iwata R, Kitagawa K, Zhang NY, Wu B, Inagaki C. Non-steroidal anti-inflammatory drugs protect amyloid beta protein-induced increase in the intracellular Cl-concentration in cultured rat hippocampal neurons. Neurosci Lett. 2004;367:156–9.

    Article  CAS  Google Scholar 

  16. Metrangolo P, Resnati G. Halogen donding II: impact on materials chemistry and life sciences. Berlin: Springer; 2015.

    Book  Google Scholar 

  17. Desiraju GR, Ho PS, Kloo L. Definition of the halogen bond (IUPAC Recommendations 2013). Pure Appl Chem. 2013;85:1711–3.

    Article  CAS  Google Scholar 

  18. Politzer P, Murray JS, Clark T. Halogen bonding: an electrostatically-driven highly directional noncovalent interaction. Phys Chem Chem Phys. 2010;12:127748–57.

    Article  Google Scholar 

  19. Gordon ER, Walsh RB, Pennington WT, Hanks TW. Syntheses and structures of two acridine orange polyiodide salts. J Chem Crystallogr. 2003;33:385–90.

    Article  CAS  Google Scholar 

  20. Bartashevich EV, Nasibullina SE, Bol’shakov OI, Tsirelson VG. Exploring heterocyclic cations ability to form the iodide–iodine halogen bond: case study of chalco-genazolo(ino)quinolinium crystals. Struct Chem. 2016;27:305–13.

    Article  CAS  Google Scholar 

  21. Das GC, Das B, Sarma NS, Medhi OK. Synthesis, structure and properties of cetyltrimethylammonium polyiodides. Polyhedron. 2012;37:14–20.

    Article  CAS  Google Scholar 

  22. Wang Y, Xue Y, Wang X, Cui Z, Wang L. The stable polyiodides: experimental and theoretical studies of formation mechanism. J Mol Struct. 2014;1074:231–9.

    Article  CAS  Google Scholar 

  23. Yushina ID, Rudakov BV, Krivtsov IV, Bartashevich EV. Thermal decomposition of tetraalkylammonium iodides. J Therm Anal Calorim. 2014;118:425–9.

    Article  CAS  Google Scholar 

  24. Aliev ZS, Musayeva SS, Imamaliyeva SZ, et al. Thermodynamic study of antimony chalcoiodides by EMF method with an ionic liquid. J Therm Anal Calorim. 2018;133:1115.

    Article  CAS  Google Scholar 

  25. Sawicka M, Storoniak P, Skurski P, Błazejowski J, Rak J. TG-FTIR, DSC and quantum chemical studies of the thermal decomposition of quaternary methylammonium halides. Chem Phys. 2006;324:425–37.

    Article  CAS  Google Scholar 

  26. Keshavarz MH, Mousaviazar A, Hayaty M. A novel approach for assessment of thermal stability of organic azides through prediction of their temperature of maximum mass loss. J Therm Anal Calorim. 2017;129:1659.

    Article  CAS  Google Scholar 

  27. Deplano P, Ferraro JR, Mercuri ML, Trogu EF. Structural and Raman spectroscopic studies as complementary tools in elucidating the nature of the bonding in polyiodides and in donor-I2 adducts. Coord Chem Rev. 1999;188:71–95.

    Article  CAS  Google Scholar 

  28. Kim DG. Synthesis and halocyclization of 2-alkenylthioquinolines. Chem Heterocycl Compd. 2008;11:1664–8.

    Google Scholar 

  29. Bartashevich EV, Yushina ID, Stash AI, Tsirelson VG. Halogen bonding and other iodine interactions in crystals of dihydrothiazolo(oxazino)quinolinium oligoiodides from the electron-density viewpoint. Cryst Growth Des. 2014;14:5674–84.

    Article  CAS  Google Scholar 

  30. Grafe-Kavoosian A, Nafepour S, Nagel K, Tebbe KF. Studies on polyhalides, XXXVI on the octaiodide ion I82−: preparation and crystal structure of [(Crypt-2.2.2)H2]I8, of [Ni(phen)3]I8·2CHCl3 and of the (N-alkylurotropinium)octaiodides (UrR)2I8 with R = methyl and ethyl. Z Naturforsch B Chem Sci. 1998;53:641.

    Article  Google Scholar 

  31. Bertolotti F, Shishkina AV, Forni A, Gervasio G, Stash AI, Tsirelson VG. Intermolecular bonding features in solid iodine. Cryst Growth Des. 2014;14:3587–95.

    Article  CAS  Google Scholar 

  32. Topol LE. Thermodynamic studies in the tetramethylammonium iodide-polyiodide and tetraethylammonium iodide-polyiodide system. Inorg Chem. 1971;10:736.

    Article  CAS  Google Scholar 

  33. Do K, Klein TI, Pommerening CA, Sunderlin LS. A new flowing afterglow-guided ion beam tandem mass spectrometer. Applications to the thermochemistry of polyiodide ions. J Am Soc Mass Spectrom. 1997;8:688–96.

    Article  CAS  Google Scholar 

  34. Landrum GA, Goldberg N, Hoffmann R. Bonding in the trihalides (X3), mixed trihalides (X2Y) and hydrogen bihalides (X2H). The connection between hypervalent, electron-rich three-center, donor-acceptor and strong hydrogen bonding. Dalton Trans. 1997;19:3605–13.

    Article  Google Scholar 

  35. Chase MW. NIST-JANAF themochemical tables, fourth edition. J Phys Chem Ref Data Monogr. 1998;9(1):1951.

    Google Scholar 

  36. Yushina ID, Kolesov BA, Bartashevich EV. Raman spectroscopy study of new thia- and oxazinoquinolinium triodides. New J Chem. 2015;39:6163–70.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by grant of Ministry of Education and Science of the Russian Federation (Award No 4.1157.2017/4.6) and by the Government of the Russian Federation, Act 211, contract No. 02.A03.21.0011.

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Correspondence to Irina D. Yushina.

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Yushina, I.D., Pikhulya, D.G. & Bartashevich, E.V. The features of iodine loss at high temperatures. J Therm Anal Calorim 139, 1017–1023 (2020). https://doi.org/10.1007/s10973-019-08442-y

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