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Open AccessArticle

Solvent Effects on the Spin Crossover Properties of Iron(II) Imidazolylimine Complexes

1
Functional Materials and Nanotechnology Center of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand
2
School of Chemistry, Monash University, Clayton, VIC 3800, Australia
3
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
4
MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, Massey University, Palmerston North 4442, New Zealand
*
Author to whom correspondence should be addressed.
Crystals 2019, 9(2), 116; https://doi.org/10.3390/cryst9020116
Received: 23 January 2019 / Revised: 19 February 2019 / Accepted: 20 February 2019 / Published: 22 February 2019
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
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Abstract

A series of Fe(II) complexes, fac-[Fe(4-ima-Bp)3](Y)2⋅sol (Y = ClO4; sol = 3EtOH 1, 3MeOH 2; Y= BF4; sol = EtOH⋅4H2O 3, 4H2O 4 and 3.5MeCN 5) have been prepared and structurally and magnetically characterized. The low temperature structures of 1, 2 and 5 have been determined by X-ray crystallography with LS Fe(II) centres found in all cases. Extensive C–H···π interactions between the cations form 2D layers, which are linked to one another through N-H···O and O-H···O hydrogen bonds, resulting in high cooperativity. Despite 5 containing MeCN, N-H···O/F hydrogen bonds, and C–H···π and π-π interactions combine to give similar 2D layers. Magnetic measurements reveal moderately abrupt spin crossover for 1-4; becoming more gradual and only 50% complete in 1 due to solvent loss. The MeCN solvate shows more gradual SCO and reinforces how subtle changes in packing can significantly influence SCO behaviour. View Full-Text
Keywords: spin crossover; iron(II) complexes; C–H···π interactions; magnetic properties; thermochromism spin crossover; iron(II) complexes; C–H···π interactions; magnetic properties; thermochromism
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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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Sertphon, D.; Harding, P.; Murray, K.S.; Moubaraki, B.; Neville, S.M.; Liu, L.; Telfer, S.G.; Harding, D.J. Solvent Effects on the Spin Crossover Properties of Iron(II) Imidazolylimine Complexes. Crystals 2019, 9, 116.

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