Direct Synthesis of Spin‐Crossover Complexes: An Unexpectedly Revealed New Iron‐Triazolic Structure. Issue 48 (10th November 2020)

• Record Type: Journal Article
• Authors: Sirenko, Valerii Y.; Kucheriv, Olesia I.; Rotaru, Aurelian; Fritsky, Igor O.; Gural'skiy, Il'ya A.
• Is Part Of: European journal of inorganic chemistry. Issue 48(2020)
• Page Start: 4523
• Page End: 4531
• Publication Date: 2020-11-10
• Subjects: Spin crossover -- Direct synthesis -- Iron -- Coordination compounds -- Triazoles -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000848
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : 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(NH2 trz)3 ]SO4, [Fe(NH2 trz)3 ](BF4 )2 and two polymorphs of [Fe(Htrz)2 (trz)]BF4 . Surprisingly high quality of PXRD pattern of [Fe(NH2 trz)3 ]SO4 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. Abstract : Here we propose a direct synthesis approach for obtaining spin‐crossover materials from metallic iron. According to this route, four Fe II based complexes with 4‐R‐1, 2, 4‐triazole have been synthesized and thoroughly characterized. In addition, by performing Rietveld refinement we managed to obtain a crystal structure of [Fe(NH2 trz)3 ]SO4 complex, revealing its 1D polymeric architecture.