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Spin crossover in two 1D Fe(II) polymers with 1,2,4-triazole thiourea building blocks

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Abstract

The 1D chain [Fe(Etutrz)3](ClO4)2 ⋅ 1.5H2O (2) (Etutrz = 1-ethyl-3-(4H-1,2,4-triazol-4-yl) thiourea), displays pronounced thermochromism with a purple color at 77 K while the sample is white at 300 K. Investigation of magnetic properties reveal an abrupt spin transition around 227 K. Differential scanning calorimetry studies on cooling display a first order phase transition at around 200 K with an entropy variation of ΔS = 61.3 J mol− 1 K− 1. 57Fe Mössbauer spectroscopy of 2 confirms a complete spin transition with a 100% high-spin population at 300 K (isomer shift δHS = 1.04(1) mm/s, quadrupole splitting ΔEQ = 2.86(2) mm/s). The Fe(II) ions convert to the low-spin state at 78K (δLS = 0.53(2) mm/s). The quadrupole splitting, ΔEQ = 0.29(2) mm/s, confirms the presence of distorted octahedra within the 1D chain. The 1D chain [Fe(Etutrz)3](BF4)2 ⋅2MeOH (1) exhibits a different magnetic behavior with a gradual spin conversion at T1/2 = 221 K, whereas thermochromic properties are maintained.

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Acknowledgements

We acknowledge support from the Fonds National de la Recherche Scientifique-FNRS (PDR T.0102.15), WBI-Romanian Academy, WBI (stipendium of excellence for H. B.) CNCS-UEFISCDI, project number PN-II-RU-TE-2014-4-2695 (Contract No. 267/01.10.2015) CNFIS-FDI-2018-058 project and COST action CA15128. We thank GFSM for supporting attendance of H.B. to GFSM 2017 (Béni-Mellal) and GFSM 2018 (Bordeaux).

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Authors and Affiliations

  1. Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, Place L. Pasteur 1, 1348, Louvain-la-Neuve, Belgium

    Houria Benaissa & 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. Houria Benaissa
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  2. Aurelian Rotaru
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  3. Yann Garcia
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Correspondence to Yann Garcia.

Additional information

This article is part of the Topical Collection on Proceedings of the 4th Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME 2018), Zadar, Croatia, 27–31 May 2018

Edited by Mira Ristic and Stjepko Krehula

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Benaissa, H., Rotaru, A. & Garcia, Y. Spin crossover in two 1D Fe(II) polymers with 1,2,4-triazole thiourea building blocks. Hyperfine Interact 239, 37 (2018). https://doi.org/10.1007/s10751-018-1511-5

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  • DOI: https://doi.org/10.1007/s10751-018-1511-5

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