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Single crystal diffraction analysis of the thermal spin conversion in [Fe(btr)\(\mathsf{_{2}}\)(NCS)\(\mathsf{_{2}}\)](H\(\mathsf{_{2}}\)O): evidence for spin-like domain formation

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An Erratum to this article was published on 01 January 2006

Abstract.

The structural properties of the spin crossover compound [Fe(btr)2(NCS)2](H2O), where btr stands for 4,4’-bis-1,2,4-triazole, are investigated by single crystal X-ray diffraction at different temperatures in the thermal spin transition regime. The 104.0(5) K low spin (LS) crystal structure is compared to the room temperature high spin (HS) crystal structure. The C2/c space group is retained in the LS state with an abrupt anisotropic shortening of the b and c cell parameters and a lengthening of a at the transition temperature. The major structural modifications related to the spin transition are a shortening of the Fe-N bond lengths (\(\Delta d_{{\rm Fe}-NCS} = -0.175\)(4) Å, \(\Delta d_{{\rm Fe-N}(btr)} = -0.213\)(3) Å) and a reorientation of the NCS groups with a more linear Fe-N-C-S geometry on going from HS to LS. Diffraction measurements have also been performed at 124 K on a trapped mixed spin state. The observed diffraction pattern shows the coexistence of two crystal lattices corresponding to ordered LS and HS species, which is a direct evidence of spin-like domain formation during the transition. The corresponding fraction of HS species (\(\gamma_{\it HS}\approx 0.10\)) has been determined by structural refinement using several reference temperature measurements. To investigate dynamical aspects, X-ray data were collected versus time during the spin transition at constant temperature (T = 117.2(2) K). No evidence has been found for any putative presence of an intermediate structural state during the spin transition.

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Authors and Affiliations

  1. Laboratoire de Cristallographie et Modélisation des Matériaux Minéraux et Biologiques, Université Henri Poincaré, UMR CNRS 7036, 54506, Vandœuvre les Nancy, France

    S. Pillet, J. Hubsch & C. Lecomte

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  1. S. Pillet
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  2. J. Hubsch
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  3. C. Lecomte
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Correspondence to C. Lecomte.

Additional information

Received: 15 January 2004, Published online: 8 June 2004

PACS:

75.30.Wx Spin crossover - 61.50.Ks Crystallographic aspects of phase transformations; pressure effects - 61.10.Nz X-ray diffraction

An erratum to this article is available at http://dx.doi.org/10.1140/epjb/e2006-00054-8.

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Supplementary material to S. Pillet, J. Hubsch, and C. Lecomte, Single crystal diffraction analysis of the thermal spin conversion in [Fe(btr)\(\mathsf{_{2}}\)(NCS)\(\mathsf{_{2}}\)](H\(\mathsf{_{2}}\)O): evidence for spin-like domain formation

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Pillet, S., Hubsch, J. & Lecomte, C. Single crystal diffraction analysis of the thermal spin conversion in [Fe(btr)\(\mathsf{_{2}}\)(NCS)\(\mathsf{_{2}}\)](H\(\mathsf{_{2}}\)O): evidence for spin-like domain formation. Eur. Phys. J. B 38, 541–552 (2004). https://doi.org/10.1140/epjb/e2004-00150-9

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