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Direct Synthesis of Spin‐Crossover Complexes: An Unexpectedly Revealed New Iron‐Triazolic Structure
Author(s) -
Sirenko Valerii Y.,
Kucheriv Olesia I.,
Rotaru Aurelian,
Fritsky Igor O.,
Gural'skiy Il'ya A.
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000848
Subject(s) - spin crossover , chemistry , raman spectroscopy , differential scanning calorimetry , crystallography , rietveld refinement , metal , coordination complex , powder diffraction , magnetic susceptibility , crystal structure , organic chemistry , physics , optics , thermodynamics
Spin‐crossover complexes form one of the biggest families of switchable compounds. Here we show a new way to obtain spin‐crossover materials by direct synthesis from metallic iron. Four complexes of Fe II with 4‐R‐1,2,4‐triazoles have been synthesized by a direct metal oxidation: [Fe(NH 2 trz) 3 ]SO 4 , [Fe(NH 2 trz) 3 ](BF 4 ) 2 and two polymorphs of [Fe(Htrz) 2 (trz)]BF 4 . Surprisingly high quality of PXRD pattern of [Fe(NH 2 trz) 3 ]SO 4 allowed to perform Rietveld refinement and obtain reliable crystal structure of the latter. All compounds have been studied by magnetic susceptibility measurements, optical reflectivity, differential scanning calorimetry and Raman spectroscopy. Importantly, spin‐crossover characteristics of the complexes obtained by this unusual method are preserved, thus revealing a new effective approach of “direct synthesis” towards switchable coordination compounds.