Advertisement

A variable-temperature Q- and X-band EPR study of spin-crossover iron(III) Schiff base complex

  • Milan MazurEmail author
  • Lukaš Pogány
  • Barbora Brachňaková
  • Ivan Šalitroš
Original Paper
  • 14 Downloads

Abstract

The mononuclear iron(III) Schiff base complex was analysed by EPR spectroscopy. The first derivative Q- and X-band EPR spectra of spin-crossover iron(III) complex exhibit the presence of the high spin (S = 5/2) and low spin (S = 1/2) iron(III) state. The variable-temperature EPR measurement confirmed a gradual spin-crossover transition (S = 5/2 ↔ S = 1/2). The possible hysteresis in the thermally induced spin-crossover effect was not detected. The EPR data are in agreement with observed trends in the magnetic measurements reported previously. Note that the EPR studies of this complex have not been performed before. It is obvious that EPR spectroscopy is a powerful method for investigation of the spin-crossover transition and their temperature evolution in the iron(III) complexes.

Keywords

Iron(III) complex Spin-crossover transition Q- and X-band EPR spectroscopy 

Notes

Acknowledgements

This work was supported by the Slovak Research and Development Agency under the contact No. APVV-15-0053 and by the Scientific Grant Agency of the Slovak Republic (Projects VEGA 1/0026/18 and VEGA 1/0686/17). MM thanks Ministry of Education, Science, Research and Sport of the Slovak Republic for funding within the scheme “Excellent research teams”. This research has been also financially supported by the Ministry of Education, Youth and Sports of the Czech Republic under the project CEITEC 2020 (LQ1601).

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Supplementary material

11696_2019_781_MOESM1_ESM.docx (373 kb)
Supplementary material 1 (DOCX 373 kb)

References

  1. Aasa R (1970) Powder line shapes in the electron paramagnetic resonance spectra of high spin ferric complexes. J Phys Chem 52:3919–3930.  https://doi.org/10.1063/1.1673591 CrossRefGoogle Scholar
  2. Conti AJ, Chadha RK, Sena KM, Rheingold AL, Hendrickson DN (1993) Dynamic and phase transition in spin-crossover complexes: X-ray structures and basic crossover phenomena in the solvate series [Fe(3-Oet-SalAPA)2](ClO4). Inorg Chem 32:2670–2680 (0020-1669/93/1332-26704.00/0) CrossRefGoogle Scholar
  3. Domracheva NE, Pyataev AV, Manopov RA, Gruzdev MS, Chervonova UV, Kolker A (2011) Structural, magnetic and dynamic characterization of liquid crustalline iron(III) schiff base complexes with asymetric ligands. Eur J Inorg Chem 2011:1219–1229.  https://doi.org/10.1002/ejic.201001157 CrossRefGoogle Scholar
  4. Domracheva NE, Pyataev AV, Vorobeva VE, Gruzdev MS, Zueva EM (2013a) Detailed EPR study of spin crossover dendrimeric iron(III) complex. J Phys Chem B 117:7833–7842.  https://doi.org/10.1021/jp403682p CrossRefGoogle Scholar
  5. Domracheva NE, Vorobeva VE, Pyataev AV, Manopov RA, Zueva EM, Gruzdev MS, Chervonova UV (2013b) Stepwise magnetic behavior of the liquid crystal iron(III) complex. J Struct Chem 54:S16–S27 (0022-4766/13/54S1-0016) CrossRefGoogle Scholar
  6. Domracheva NE, Vorobeva VE, Pyataev AV, Tamura R, Suzuki K, Gruzdev MS, Chervonova UV, Kolker A (2016a) Magnetic properties of novel dendrimeric spin crossover iron(III) complex. Inorg Chim Acta 439:186–195.  https://doi.org/10.1016/j.ica.2003.10.024 CrossRefGoogle Scholar
  7. Domracheva NE, Vorobeva VE, Pyataev AV, Ivanova AG (2016b) Magnetic properties of novel dendrimeric spin crossover iron(III) complex of the first generation: EPR and Mossbauer study. Appl Magn Reson 47:903–913.  https://doi.org/10.1007/s00723-016-0792-6 CrossRefGoogle Scholar
  8. Domracheva NE, Vorobeva VE, Ovcharenko VI, Bogomyakov AS, Zueva EM, Gruzdev MS, Chervonova UV, Kolker AM (2017) Counterion effect on the spin-transition properties of the second generation iron(III) dendrimeric complex. Inorg Chim Acta 459:131–142.  https://doi.org/10.1016/j.ica.2017.02.008 CrossRefGoogle Scholar
  9. Doukov T, Li H, Sharma A, Martell JD, Soltis SM, Silverman RB, Pouluos T (2001) Temperature-dependent spin crossover in neuronal nitric oxide syntheses bound with the heme-coordinating thioether inhibitors. J Am Chem Soc 133:8326–8334.  https://doi.org/10.1021/ja201466v CrossRefGoogle Scholar
  10. Federer WD, Hendrickson DN (1984) Dynamic of spin-state interconversion and cooperativity for Ferric spin-crossover complex in the solid state. 2. Perturbations of the fast spin-flipping N4O2 complex [Fe(SalAPA)2] ClO4. Inorg Chem 23:3870–3877 (0020-1669/84/1332-387001.50/0) CrossRefGoogle Scholar
  11. Gutlich P, Goodwin HA (2004) Spin crossover in transition metal compounds. Topics in current chemistry, vol 233. Springer, Berlin.  https://doi.org/10.1007/b83735 Google Scholar
  12. Hadad MS, Lynch MV, Federer WD, Hendrickson DN (1981a) Spin-crossover ferric complex: curiosities observed for unperturbed solids. Inorg Chem 20:123–131 (0020-1669/81/1320-012301.00/0) CrossRefGoogle Scholar
  13. Hadad MS, Federer WD, Lynch MV, Hendrickson DN (1981b) Spin-crossover feric complex: unusual effects of grinding and dopping solids. Inorg Chem 20:131–139 (0020-1669/81/1320-013101.00/0) CrossRefGoogle Scholar
  14. Hagen WR (2009) Biomolecular EPR spectroscopy. CRC Press, Taylor & Francis Group, Boca RatonGoogle Scholar
  15. Halcrow MA (2011) Structure-function relationships in molecular spin-crossover complexes. Chem Soc Rev 40:4119–4142.  https://doi.org/10.1039/clcsl5046d CrossRefGoogle Scholar
  16. Harding JD, Harding P, Phonsri W (2016) Spin crossover in iron(III) complexes. Coord Chem Rev 313:8–61.  https://doi.org/10.1016/j.ccr.2016.01.006 CrossRefGoogle Scholar
  17. Ivanova TA, Ovchinnikov IV, Garipov RR, Ivanova GI (2011a) Spin crossover [Fe(qsal)2]x (X = Cl, SCN, CF3SO3) complexes: EPR and DFT study. Appl Magn Reson 40:1–10.  https://doi.org/10.1007/s00723-010-0168-2 CrossRefGoogle Scholar
  18. Ivanova TA, Turanova OA, Ovchinnikov IV, Andgheevskii B, Augustyniak-Jablokov M (2011b) EPR features of spin-crossover in tris(N, N-dialkyl-dithiocarbamato) Iron(III). Appl Magn Reson 40:21–30.  https://doi.org/10.1007/s00723-010-017-7 CrossRefGoogle Scholar
  19. Koningsbruggen PJ, Maeda Y, Oshio H (2004) Iron(III) spin crossover compounds. Top Curr Chem 233:259–324.  https://doi.org/10.1007/b96409 CrossRefGoogle Scholar
  20. Masárová P, Zoufalý P, Moncol J, Nemec I, Pavlík J, Gembický M, Trávňíček Z, Boča R, Šalitroš I (2015) Spin crossover and high spin electroneutral mononuclear iron(III) Schiff base complexes involving terminal pseudohalido ligands. New J Chem 39:508–519.  https://doi.org/10.1039/c4nj01393h CrossRefGoogle Scholar
  21. Mazur M, Valko M, Klement R, Morris H (1996a) Quantitative EPR spectroscopy with a TE104 double rectangular cavity. Part 1. A simple alignment procedure for the precision positioning of the sample. Anal Chim Acta 333:249–252.  https://doi.org/10.1016/0003-2670(96)00254-1 CrossRefGoogle Scholar
  22. Mazur M, Valko M, Morris H, Klement R (1996b) Quantitative EPR spectroscopy with a TE104 double rectangular cavity. Part 2. An analysis of sample and cavity error sources associated with the measurement of the line-like samples in the TE104 cavity. Anal Chim Acta 333:253–256.  https://doi.org/10.1016/0003-2670(96)00255-3 CrossRefGoogle Scholar
  23. Mazur M, Morris H, Valko M (1997) Analysis of the movement of line-like samples of variable length along the X-axis of a double TE104 and a single TE102 rectangular cavity. J Magnet Reson 129:188–200.  https://doi.org/10.1006/jmre.1997.1248 CrossRefGoogle Scholar
  24. Nihei M, Shiga T, Maeda Y, Oshio H (2007) Spin crossover iron(III) complexes. Coord Chem Rev 251:2606–2621.  https://doi.org/10.2016/j.ccr.2007.08.007 CrossRefGoogle Scholar
  25. Oshio H, Madeda Y, Takashima Y (1983) Rapid electronic relaxation phenomenon in a 2T ↔ 6A spin-equilibrium system. Inorg Chem 22:2684–2689 (0020-1669/83/1322-268401.50/0) CrossRefGoogle Scholar
  26. Ozarowski A (2014) Original program “Spin”, National High Magnetic Field Laboratory, Florida. http://myweb.fsu.edu/aozarows/EPR/. Accessed 11 Aug 2014
  27. Pelikán P, Liška M, Valko M, Mazur M (1996) Quantitative analysis of EPR spectra of powdered samples containing a mixture of various paramagnetic particles. J Magn Reson 122:9–15.  https://doi.org/10.1006/jmra.1996.0169 CrossRefGoogle Scholar
  28. Šalitroš I, Madhu NT, Boča R, Pavlík J (2009) Room-temperature spin-transition iron compounds. Monatsh Chem 140:695–733.  https://doi.org/10.1007/s00706-009-0128-4 CrossRefGoogle Scholar
  29. Tang J, Costa JS, Smulders S, Molnar G, Boursseksou A, Teal SJ, Li Y, Albada GA, Gamez P, Reedjijk J (2009) Two-step spin-transition iron(III) compound with a wide [high spin-low spin] plateau. Inorg Chem 48:2009.  https://doi.org/10.1021/ic801973x Google Scholar
  30. Thiele H, Etstling J, Such P, Hoefer P (1992) WINEPR. Bruker Analytic Gmb, RheinstettenGoogle Scholar
  31. Timken MD, Hendrickson DN, Sinn E (1985) Dynamic of spin-state interconversion and cooperativity for ferric spin-crossover complex in the solid state. 3. Bis[N-(2-(benzylamino)ethyl) salicylaldiminato]iron(III) complex. Inorg Chem 24:3947–3955 (0020-1669/85/1324-394701.50/0) CrossRefGoogle Scholar
  32. Timken MD, Abdel-Maegoud AM, Hendrickson DN (1986) Dynamic of spin-state interconversion and cooperativity for ferric spin-crossover complex in the solid state. 6. Magnetic and spectroscopic characterizations of [Fe(3-Oet-SalAPA)2]X (X = ClO4 , BPh4). Inorg Chem 25:160–164 (0020-1669/86/1325-016001) CrossRefGoogle Scholar
  33. Vishnevskaya GP, Frolova EN, Ovchinikov IV, Petrova IG, Rezinskikh ZG (2010) The spin-transition properties of iron(III) complex with hetarylformazan in an iron-exchange polymer: an EPR study. Russ J Phys Chem 84:1388–1394.  https://doi.org/10.1134/S0036024410080200 CrossRefGoogle Scholar
  34. Vorobeva VE, Domracheva NE, Pyataev AV, Gruzdev MS, Chervonova UV (2015) Coexistence of spin crossover and magnetic ordering in a dendrimetric iron(III) complex. Low Temp Phys 41:15–19.  https://doi.org/10.1063/1.4906311 CrossRefGoogle Scholar
  35. Weber RT (1995) WINEPR SimFonia. EPR Division, Bruker Instr. Inc, BillericaGoogle Scholar
  36. Wickman HH, Klein PM, Shirley DA (1965) Paramagnetic resonance of Fe3+ in polycrystalline ferrichrome A. J Chem Phys 42:2113–2117.  https://doi.org/10.1063/1.1696253 CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Department of Physical Chemistry, Faculty of Chemical and Food TechnologySlovak University of Technology in BratislavaBratislavaSlovakia
  2. 2.Department of Inorganic Chemistry, Faculty of Chemical and Food TechnologySlovak University of Technology in BratislavaBratislavaSlovakia
  3. 3.Central European Institute of TechnologyBrno University of TechnologyBrnoCzech Republic

Personalised recommendations