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Open AccessFeature PaperArticle

Iron(III) Azadiphenolate Compounds in a New Family of Spin Crossover Iron(II)–Iron(III) Mixed-Valent Complexes

1
School of Chemistry, 17 Rainforest Walk, Monash University, Clayton, VIC 3800, Australia
2
Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK
*
Author to whom correspondence should be addressed.
Magnetochemistry 2019, 5(2), 37; https://doi.org/10.3390/magnetochemistry5020037
Received: 21 May 2019 / Revised: 4 June 2019 / Accepted: 6 June 2019 / Published: 12 June 2019
(This article belongs to the Special Issue Spin-Crossover Beyond the Immediate Tribute)
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Abstract

A new family of mixed valent, double salt spin crossover compounds containing anionic FeIII and cationic FeII compounds i.e., [FeII{(pz)3CH}2][FeIII(azp)2]2·2H2O (4), [FeII(TPPZ)2][FeIII(azp)2]2]·H2O (5) and [FeII(TPPZ)2][FeIII(azp)2]2]·H2O·3MeCN (6) (where (pz)3CH = tris-pyrazolylmethane, TPPZ = 2,3,5,6, tetrapyridylpyrazine and azp2− = azadiphenolato) has been synthesized and characterised. This is the first time that the rare anionic spin crossover species, [FeIII(azp)2], has been used as an anionic component in double salts complexes. Single crystal structures and magnetic studies showed that compound 6 exhibits a spin transition relating to one of the FeIII centres of the constituent FeII and FeIII sites. Crystal structures of the anionic and cationic precursor complexes were also analysed and compared to the double salt products thus providing a clearer picture for future crystal design in double spin crossover materials. We discuss the effects that the solvent and counterion had on the crystal packing and spin crossover properties. View Full-Text
Keywords: spin crossover; mixed valent; double salts; mixed FeII–FeIII; magnetic properties; crystal structures spin crossover; mixed valent; double salts; mixed FeII–FeIII; magnetic properties; crystal structures
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Phonsri, W.; Macedo, D.S.; Lewis, B.A.I.; Wain, D.F.; Murray, K.S. Iron(III) Azadiphenolate Compounds in a New Family of Spin Crossover Iron(II)–Iron(III) Mixed-Valent Complexes. Magnetochemistry 2019, 5, 37.

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