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Open AccessFeature PaperArticle

Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes

by Ivan Šalitroš 1,2,*, Olaf Fuhr 1,3 and Mario Ruben 1,4,*
Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, Karlsruhe 76021, Germany
Faculty of Chemical and Food Technology, Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Bratislava 812 37, Slovakia
Karlsruhe Nano Micro Facility (KNMF), Karlsruher Institut für Technologie, Postfach 3640, Karlsruhe 76021, Germany
Institute de Physique et Chimie de Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg, 23, rue du Loess BP 43, F-67034 Strasbourg cedex 2, France
Authors to whom correspondence should be addressed.
Academic Editor: Wolfgang Linert
Materials 2016, 9(7), 585;
Received: 30 June 2016 / Revised: 13 July 2016 / Accepted: 14 July 2016 / Published: 19 July 2016
(This article belongs to the Special Issue Advances in Molecular Magnets and related Phenomena)
Two new mononuclear iron(II) compounds (1) and (2) of the general formula [Fe(L)2](BF4)2·nCH3CN (L = 4-(2-bromoethyn-1-yl)-2,6-bis(pyrazol-1-yl)pyridine, n = 1 for (1) and n = 2 for compound (2)), were synthesized. The room temperature crystallization afforded concomitant formation of two different solvent analogues: compound (1) exhibiting triclinic P-1 and compound (2) monoclinic C2/c symmetry. Single-crystal X-ray studies confirmed the presence of the LS (low-spin) state for both compounds at 180 K and of the HS (high-spin) state for compound (2) at 293 K, in full agreement with the magnetic investigations for both solvent polymorphs. Compound (1) exhibits spin transition above 293 K followed by subsequent solvent liberation, while the spin transition of (2) takes already place at 237 K. After complete solvent removal from the crystal lattice, compound (1d) (the desolvated polymorph derived from (1)) exhibits spin transition centered at 342 K accompanied by a thermal hysteresis loop, while the analogous compound (2d) (the desolvated derivate of compound (2)) remains blocked in the HS state over all the investigated temperature range. View Full-Text
Keywords: spin crossover; iron(II) complexes; molecular magnetism; polymorphism spin crossover; iron(II) complexes; molecular magnetism; polymorphism
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Šalitroš, I.; Fuhr, O.; Ruben, M. Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes. Materials 2016, 9, 585.

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