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Issue 31, 2018
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Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure–function relationship

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Abstract

This paper reports firstly the syntheses, crystal structures, and thermal and magnetic properties of spin crossover salts of formulae [Fe(bpp)2]3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·H2O (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 located 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 air. The influence of the lattice water on the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented. In most cases, it stabilises the LS state over the HS one. In other cases, it is rather the contrary. The second part of this paper is devoted to unravelling the reasons why the lattice solvent stabilises one form over the other through magneto-structural correlations of [Fe(bpp)2]2+ salts bearing anions with different charge/size ratios (Xn). The [Fe(bpp)2]2+ stacking explaining these two different behaviours is correlated here with the composition of the 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.

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

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Article information


Submitted
31 Mar 2018
Accepted
27 Apr 2018
First published
02 May 2018

Dalton Trans., 2018,47, 10453-10462
Article type
Paper

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

M. D. C. Giménez-López, M. Clemente-León and C. Giménez-Saiz, Dalton Trans., 2018, 47, 10453
DOI: 10.1039/C8DT01269E

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