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Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure-function relationship

Abstract

This paper reports firstly the syntheses, crystal structures thermal and magnetic properties of spin crossover salts of formula [Fe(bpp)2] 3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·1H2O (2) (bpp = 2,6-bis(pyrazol-3-yl)pyridine) exhibiting hydrogen-bonded networks of low-spin Fe(bpp)2]2+ complexes and [Cr(CN)6]3- or [N(CN)2]- anions, with solvent molecules sitting in the voids. Desolvation of 1 is accompanied by a complete low-spin (LS) to a high-spin (HS) transformation that becomes reversible after rehydration by exposing the sample to the humidity of the air. The influence of the lattice water in the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented. In most cases, it stabilises the LS sate over HS one. In other cases, it is rather the contrary. The second part of this paper is devoted to unravel the reasons why the lattice-solvent stabilise one form over the other through magneto-structural correlations of [Fe(bpp)2]2+ salts bearing anions with different charge/size ratio (Xn-). The [Fe(bpp)2]2+ stacking explaining these two different behaviours is correlated here with the composition of second coordination sphere of the Fe centers and the ability of these anions to form hydrogen bonds and/or π- π stacking interactions between them or the bpp ligand.

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Publication details

The article was received on 31 Mar 2018, accepted on 27 Apr 2018 and first published on 02 May 2018


Article type: Paper
DOI: 10.1039/C8DT01269E
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure-function relationship

    M. D. C. Gimenez Lopez, M. Clemente Leon and C. Giménez-Saiz, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT01269E

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