Skip to main content
SpringerLink
Log in

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

  • Published:
Hyperfine Interactions Aims and scope Submit manuscript

Abstract

[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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Gütlich, P., Gaspar, A.B., Garcia, Y.: Spin state switching in iron coordination compounds. Beilstein J. Org. Chem. 9, 342 (2013)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  3. Garcia, Y., Ksenofontov, V., Gütlich, P.: Spin transition molecular materials: new sensors. Hyperfine Interact. 139/140, 543 (2002)

    Article  Google Scholar 

  4. Linares, J., Codjovi, E., Garcia, Y.: Pressure and temperature spin crossover sensors with optical detection. Sensors 12, 4479 (2012)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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. 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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  Google Scholar 

  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. 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. 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)

    Article  Google Scholar 

  17. Kamiya, T., Saito, Y.: Process for preparing 1H-tetrazole compounds. US 3767667 A (1973)

  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. 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)

    Article  Google Scholar 

  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. Slichter, C.P., Drickamer, H.G.: Pressure-induced electronic changes in compounds of iron. J. Chem. Phys. 56, 2142–2160 (1972)

    Article  ADS  Google Scholar 

  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)

Download references

Acknowledgements

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.

Author information

Authors and Affiliations

  1. Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348, Louvain-la-Neuve, Belgium

    N. N. Adarsh, Marinela M. Dîrtu & Yann Garcia

  2. Department of Electrical Engineering and Computer Science & Research Center MANSiD, “Stefan cel Mare” University, University Street, No. 13, Suceava, 720229, Romania

    Aurelian Rotaru

Authors
  1. N. N. Adarsh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Marinela M. Dîrtu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Aurelian Rotaru
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yann Garcia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yann Garcia.

Additional information

This article is part of the Topical Collection on Proceedings of the 3rd Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME 2017), Jerusalem, Israel, 5–7 June 2017

Edited by Mira Ristic, Stjepko Krehula, Israel Nowik and Israel Felner

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Adarsh, N.N., Dîrtu, M.M., Rotaru, A. et al. 57Fe Mössbauer spectroscopy study of a 2D spin transition coordination polymer built from a tris-1R-tetrazole ligand. Hyperfine Interact 238, 60 (2017). https://doi.org/10.1007/s10751-017-1431-9

Download citation

  • Published:

  • DOI: https://doi.org/10.1007/s10751-017-1431-9

Keywords

Search

Navigation