Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes

Version 1 : Received: 17 April 2021 / Approved: 19 April 2021 / Online: 19 April 2021 (12:03:37 CEST)

How to cite: Cuza, E.; Benmansour, S.; Cosquer, N.; Conan, F.; Gómez-García, C.J.; Triki, S. Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes. Preprints 2021, 2021040467 (doi: 10.20944/preprints202104.0467.v1). Cuza, E.; Benmansour, S.; Cosquer, N.; Conan, F.; Gómez-García, C.J.; Triki, S. Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes. Preprints 2021, 2021040467 (doi: 10.20944/preprints202104.0467.v1).

Abstract

Reactions of Fe(II) with the tris-(pyridin-2-yl)ethoxymethane (py3C-OEt) tripodal ligand in presence of the pseudohalide ancillary NCE- (E = S, Se, BH3) ligands led to a series of three mononuclear complexes formulated as [Fe(py3C-OEt)2][Fe(py3C-OEt)(NCE)3]2·2CH3CN, with E = S (1), BH3 (2) and Se (3). Single crystal characterizations (complexes 1-2) and X-ray powder diffraction (complexes 1-3) reveal monomeric isomorph structures formed by the spin crossover (SCO) anionic [Fe(py3C-OEt)(NCE)3] complex, associated with the low spin (LS) cationic [Fe(py3C-OEt)2]2+ complex and two solvent acetonitrile molecules. In the [Fe(py3C-OEt)2]2+ cation, the Fe(II) is coordinated by two py3C-OEt tridentate ligands, while the [Fe(py3C-OEt)(NCE)3] anion displays a hexacoordinated environment involving three N-donor atoms of one py3C-OEt ligand and three nitrogen atoms arising from of the three (NCE) coligands. The magnetic studies show the presence of gradual SCO behavior for the three complexes: a one-step transition around 205 K for 1 and two step-transitions for compounds 2 and 3, centred at 245 K and 380 K for 2, and at 170 K and 298 K for 3. The magnetic behaviors of complexes 1 and 2 remain unchanged when heating up to 500 K, while complex 3 shows significant changes which are caused by the crystallisation solvent loss above room temperature.

Subject Areas

Tripodal Ligands; pseudohalide coligands; Iron Complex; Spin crossover; Magnetic properties

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