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Magnetochemistry 2016, 2(1), 1;

A Spin Crossover Transition in a Mn(II) Chain Compound

Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/ Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain
UMR CNRS 6521, Chimie, Electrochimie Moléculaires, Chimie Analytique, Université de Bretagne Occidentale, BP 809, 29285 Brest Cedex, France
Author to whom correspondence should be addressed.
Academic Editor: Melanie Pilkington
Received: 1 December 2015 / Revised: 14 December 2015 / Accepted: 21 December 2015 / Published: 29 December 2015
(This article belongs to the Special Issue Magnetochemistry: From Fundamentals to Applications)
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Three new compounds have been synthesized and characterized with Fe(II), Co(II) and Mn(II), the polynitrile anionic ligand 1,1,3,3-tetracyano-2-(3-hydroxypropoxy)-propenide (tcnopr3OH) and the co-ligand 4,4′-bipyridine (4,4′-bpy). The Fe(II) compound, formulated as [FeII(tcnoprOH)2(H2O)2(4,4′-bpy)2] (1), contains monomeric complexes where the Fe(II) ion is coordinated to two trans polynitrile ligands, two trans 4,4′-bpy ligands and two trans water molecules. Compounds [MII(H2O)4(µ-4,4′-bpy)][MII(tcnoprOH)4(µ-4,4′-bpy)].3H2O, M = Mn (2) and Co (3), are isostructural and crystallize in segregated cationic and anionic chains that can be formulated as [MII(H2O)4(µ-4,4′-bpy)]n2n+ and [MII(tcnoprOH)4(µ-4,4′-bpy)]n2n, respectively with M = Mn (2) and Co (3). The magnetic properties of Compound 1 show the expected paramagnetic behavior for an isolated high spin S = 2 Fe(II) ion with a zero field splitting of |D| = 4.0(1) cm−1. Compound 3 presents the expected behavior for isolated Co(II) centers, whereas Compound 2 shows an unexpected partial smooth spin crossover (SCO) transition in the anionic [MnII(tcnoprOH)4(µ-4,4′-bpy)]n2n chain together with a paramagnetic contribution of the cationic [MnII(H2O)4(µ-4,4′-bpy)]n2n+ chain. This behavior has been confirmed with DSC measurements. This is one of the very few examples of SCO transition observed in a Mn(II) complex and the first one in a Mn(II) chain. View Full-Text
Keywords: Mn(II) spin crossover; low spin Mn(II); chain compounds; magnetic coordination polymers; polynitrile ligands Mn(II) spin crossover; low spin Mn(II); chain compounds; magnetic coordination polymers; polynitrile ligands

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Benmansour, S.; Triki, S.; Gómez-García, C.J. A Spin Crossover Transition in a Mn(II) Chain Compound. Magnetochemistry 2016, 2, 1.

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