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Magnetochemistry 2016, 2(1), 1; doi:10.3390/magnetochemistry2010001

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

1
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/ Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain
2
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)
View Full-Text   |   Download PDF [3211 KB, uploaded 29 December 2015]   |  

Abstract

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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