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Spin Cross-Over (SCO) Anionic Fe(II) Complexes Based on the Tripodal Ligand Tris(2-pyridyl)ethoxymethane

Abstract : Reactions of Fe(II) with the tripodal chelating ligand 1,1,1-tris(2-pyridyl)ethoxymethane (py 3 C-OEt) and (NCE) − co-ligands (E = S, Se, BH 3) give a series of mononuclear complexes formulated as [Fe(py 3 C-OEt) 2 ][Fe(py 3 C-OEt)(NCE) 3 ] 2 ·2CH 3 CN, with E = S (1) and BH 3 (2). These compounds are the first Fe(II) spin cross-over (SCO) complexes based on the tripodal ligand tris(2-pyridyl)ethoxymethane and on the versatile co-ligands (NCS) − and (NCBH 3) −. The crystal structure reveals discrete monomeric isomorph structures formed by a cationic [Fe(py 3 C-OEt) 2 ] 2+ complex and by two equivalent anionic [Fe(py 3 C-OEt)(NCE) 3 ] − complexes. In the cations the Fe(II) is facially coordinated by two py 3 C-OEt tripodal ligands whereas in the anion the three nitrogen atoms of the tripodal ligand are facially coordinated and the N-donor atoms of the three (NCE) − co-ligands occupy the remaining three positions to complete the distorted octahedral environment of the Fe(II) centre. The magnetic studies show the presence of gradual SCO for both complexes: A one-step transition around 205 K for 1 and a two-step transition for compound 2, centered around 245 K and 380 K.
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Emmelyne Cuza, Samia Benmansour, Nathalie Cosquer, Françoise Conan, Sébastien Pillet, et al.. Spin Cross-Over (SCO) Anionic Fe(II) Complexes Based on the Tripodal Ligand Tris(2-pyridyl)ethoxymethane. Magnetochemistry, MDPI, 2020, ⟨10.3390/magnetochemistry6020026⟩. ⟨hal-02903801⟩

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