Hyperfine Interactions

, 238:60 | Cite as

57Fe Mössbauer spectroscopy study of a 2D spin transition coordination polymer built from a tris-1R-tetrazole ligand

  • N. N. Adarsh
  • Marinela M. Dîrtu
  • Aurelian Rotaru
  • Yann GarciaEmail author
Part of the following topical collections:
  1. Proceedings of the 3rd Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME 2017), Jerusalem, Israel, 5-7 June 2017


[Fe{N(entz)3}2](ClO4)2 (N(entz)3 = tris(2-(1H-tetrazol-1-yl)ethyl)-amine) is a 2D FeII coordination polymer built from a tris-1-R tetrazole building block. This thermochromic FeII complex which was investigated by variable temperature 57Fe Mossbauer spectroscopy (78–300 K) displays on cooling a complete, abrupt and hysteretic spin transition at \(T_{c}^{\uparrow } = 170(1)\) K and \(T_{c}^{\downarrow } = 149(1)\) K. The reversibility of the spin transition over several thermal cycles was deduced from SQUID magnetometry. Differential scanning calorimetry reveals a reversible first order phase transition on cooling below room temperature, with entropy data consistent with the highly cooperative character of the spin transition.


57Fe Mossbauer spectroscopy Coordination polymers Spin transition Tetrazole Molecular bistability 



We acknowledge support from the the Fonds de la Recherche Scientifique-FNRS (PDR T.0102.15), WBI-Romanian Academy, CNCS-UEFISCDI, project number PN-II-RU-TE-2014-4-2695 (Contract No. 267/01.10.2015) and COST actions CM1305 and CA15128. M. M. D. is recipient of the GFSM 2016 thesis prize, and chargé de recherches from the F.R.S. - FNRS.


  1. 1.
    Gütlich, P., Gaspar, A.B., Garcia, Y.: Spin state switching in iron coordination compounds. Beilstein J. Org. Chem. 9, 342 (2013)CrossRefGoogle Scholar
  2. 2.
    Garcia, Y., Adarsh, N.N., Naik, A.D.: Crystal engineering of Fe II spin crossover coordination polymers derived from triazole or tetrazole ligands. Chimia 67, 411 (2013)CrossRefGoogle Scholar
  3. 3.
    Garcia, Y., Ksenofontov, V., Gütlich, P.: Spin transition molecular materials: new sensors. Hyperfine Interact. 139/140, 543 (2002)CrossRefGoogle Scholar
  4. 4.
    Linares, J., Codjovi, E., Garcia, Y.: Pressure and temperature spin crossover sensors with optical detection. Sensors 12, 4479 (2012)CrossRefGoogle Scholar
  5. 5.
    Vreugdenhil, W., van Diemen, J.A., de Graaff, R.A.G., Haasnoot, J.G., Reedijk, J., van der Kraan, A.M., Kahn, O., Zarembowitch, J.: HS-LS transition in [Fe(NCS)2(4,4\(^{\prime }\)-bis-1,2,4-triazole)2] ⋅H 2O. X-ray crystal structure and magnetic, Mössbauer and EPR properties. Polyhedron 9, 2971 (1990)CrossRefGoogle Scholar
  6. 6.
    Ozarowski, A., Shunzhong, Y., McGarvey, B.R., Mislankar, A., Drake, J.E.: EPR and NMR study of the spin crossover transition in bis(4,4\(^{\prime }\)-bi-1,2,4-triazole)bis(thiocyanato)iron hydrate and bis(4,4\(^{\prime }\)-bi-1,2,4-triazole)bis(selenocyanato)iron hydrate. X-ray structure determination of Fe(4,4\(^{\prime }\)-bi-1,2,4-triazole)2(SeCN) ⋅H 2O. Inorg. Chem. 30, 3167 (1991)CrossRefGoogle Scholar
  7. 7.
    Chuang, Y.-C., Liu, C.-T., Sheu, C.-F., Ho, W.-L., Lee, G.-H., Wang, C.-C., Wang, Y.: New iron(II) spin crossover coordination polymers [Fe(μ-atrz)3]X2 ⋅ 2H2O (X = ClO\(_{4}^{-}\), BF\(_{4}^{-}\)) and [Fe(μ-atrz)(μ-pyz)(NCS)2] ⋅ 4H2O with an interesting solvent effect. Inorg. Chem. 51, 4663 (2012)CrossRefGoogle Scholar
  8. 8.
    Bronisz, R.: 1,4-di(1,2,3-triazol-1-yl)butane as building block for the preparation of the iron(II) spin crossover 2D coordination polymer. Inorg. Chem. 44, 4463 (2005)CrossRefGoogle Scholar
  9. 9.
    Kusz, J., Bronisz, R., Zubko, M., Bednarek, G.: On the role of intermolecular interactions on structural and spin crossover properties of 2D coordination networks, [Fe(bbtr)3]A2 (bbtr = 1,4-bis(1,2,3-triazol-1-yl)butane; A = ClO\(_{4}^{\mathrm {-}}\), BF\(_{4}^{\mathrm {-}})\). Chem. Eur. J. 17, 6807 (2011)CrossRefGoogle Scholar
  10. 10.
    Quesada, M., Prins, F., Roubeau, O., Gamez, P., Teat, S.J., van Koningsbruggen, P.J., Haasnoot, J.G., Reedijk, J.: A 2D [FeII-bistetrazole] coordination polymer exhibiting spin crossover properties Inorg. Chim. Acta 360, 3787 (2007)Google Scholar
  11. 11.
    Bialonska, A., Bronisz, R.: HS and spin crossover 2D coordination polymers containing FeII(tetrazol-2-yl)4(solv)2 (solv = Ethanol, Acetonitrile) cores linked by flexible/elastic spacers. Inorg. Chem. 49, 4534 (2010)CrossRefGoogle Scholar
  12. 12.
    Ksiazek, M., Kusz, J., Bialonska, A., Bronisz, R., Weselski, M.: Influence of conformational changes on spin crossover properties and superstructure formation in 2D coordination polymers [Fe(hbtz)2(RCN)2](ClO4)2. Dalton Trans. 44, 18563 (2015)CrossRefGoogle Scholar
  13. 13.
    Bialonska, A., Bronisz, R., Kusz, J., Zubko, M.: Two-step spin transition in an iron(II) coordination network based on flexible bitopic ligand 1-(tetrazol-1-yl)-3-(1,2,3-triazol-1-yl)propane. Eur. J. Inorg. Chem 5–6, 884 (2013)CrossRefGoogle Scholar
  14. 14.
    Bronisz, R., Ciunik, Z., Drabent, K., Rudolf, M.F.: New type of 2-D nets in iron(II) spin crossover systems - [Fe{N(entz)3}2](BF4)2. Conf. Proc., ICAME-95 50, 15 (1996)Google Scholar
  15. 15.
    Boland, Y., Herstens, P., Marchand-Brynaert, J., Garcia, Y.: New ditopic and tripodal 1,2,4-triazole- and tetrazole-based ligands for coordination chemistry. Synthesis 9, 1504 (2006)Google Scholar
  16. 16.
    Bialonska, A., Bronisz, R., Rudolf, M.F., Weselski, M.: HSLS transition in Iron(II) 2D coordination networks containing tris(tetrazol-1-ylmethyl)methane as triconnected building block. Inorg. Chem. 51, 237 (2012)CrossRefGoogle Scholar
  17. 17.
    Kamiya, T., Saito, Y.: Process for preparing 1H-tetrazole compounds. US 3767667 A (1973)Google Scholar
  18. 18.
    Lagarec, K., Rancourt, D.G.: Mössbauer Spectral Analysis Software for Windows 1.0. Department of Physics, University of Ottawa, Canada (1998)Google Scholar
  19. 19.
    Rotaru, A., Dîrtu, M.M., Enachescu, C., Tanasa, R., Linares, J., Stancu, A., Garcia, Y.: Calorimetric measurements of diluted spin crossover complexes [FexM1−x(btr)2(NCS)2] ⋅ H2O with MII = and Ni. Polyhedron 28, 2531 (2009)CrossRefGoogle Scholar
  20. 20.
    Garcia, Y., Ksenofontov, V., Gütlich, P.: New polynuclear 4,4\(^{\prime }\)-bis-1,2,4-triazole FeII spin crossover compounds. C. R. Acad. Sci. Chim. IIC 4, 227 (2001)Google Scholar
  21. 21.
    Slichter, C.P., Drickamer, H.G.: Pressure-induced electronic changes in compounds of iron. J. Chem. Phys. 56, 2142–2160 (1972)ADSCrossRefGoogle Scholar
  22. 22.
    Suarez-Garcia, S., Adarsh, N.N., Molnar, G., Bousseksou, A., Garcia, Y., Dîrtu, M.M., Pobles, R., Ordejón, P., Ruiz-Molina, D.: Spin crossover on an exfoliated 2-D coordination polymer (submitted) (2017)Google Scholar

Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  1. 1.Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST)Université catholique de LouvainLouvain-la-NeuveBelgium
  2. 2.Department of Electrical Engineering and Computer Science & Research Center MANSiD“Stefan cel Mare” UniversitySuceavaRomania

Personalised recommendations