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Cooperative Large-Hysteresis Spin-Crossover Transition in the Iron(II) Triazolate [Fe(ta)2] Metal-Organic Framework
Maciej Grzywa1, Richard Röß-Ohlenroth1, Christoph Muschielok2
1Chair of Solid State and Materials Chemistry, Institute of Physics, University of Augsburg, Universitätsstrasse 1, D-86159 Augsburg, Germany.
Abstract:
The metal-organic framework [Fe(ta)2] (Hta = 1H-1,2,3-triazole) containing Fe(II) ions and 1,2,3-triazolate ligands shows a reversible phase transition while retaining the cubic crystal symmetry and space group Fd3m (no. 227). The phase transition between room temperature (RT-[Fe(ta)2]; a = 16.6315(2) Å, V = 4600.39(8) Å3) and high temperature (HT-[Fe(ta)2]; a = 17.7566(4) Å, V = 5598.6(1) Å3) phases occurs at a temperature above 290 °C, whereas the phase transition between HT- and RT-[Fe(ta)2] starts at a temperature below 210 °C. Both [Fe(ta)2] polymorphs have identical bond topologies, but they differ by a large increase of the unit cell's volume of 22% for HT-[Fe(ta)2]. The compounds are characterized by powder X-ray diffraction, differential scanning calorimetry, and thermogravimetric analyses. Additionally, Mössbauer spectroscopy, magnetic studies, and the electronic structure of both phases are discussed in detail with respect to the spin-crossover transition from the low-spin (RT-[Fe(ta)2]) to the high-spin phase (HT-[Fe(ta)2]).
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