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Crystals 2019, 9(1), 19; https://doi.org/10.3390/cryst9010019

Anion Influence on Spin State in Two Novel Fe(III) Compounds: [Fe(5F-sal2333)]X

1
Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin (UCD), Belfield, Dublin 4, Ireland
2
Institute for Inorganic Chemistry (AOC), KIT (Karlsruhe Institute of Technology), Engessterstr. 15, 76131 Karlsruhe, Germany
3
Institute for Nanotechnology (INT), KIT (Karlsruhe Institute of Technology), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
*
Author to whom correspondence should be addressed.
Received: 12 December 2018 / Revised: 21 December 2018 / Accepted: 22 December 2018 / Published: 29 December 2018
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
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Abstract

Structural and magnetic data on two iron (III) complexes with a hexadentate Schiff base chelating ligand and Cl or BPh4 counterions are reported. In the solid state, the Cl complex [Fe(5F-sal2333)]Cl, 1, is high spin between 5–300 K while the BPh4 analogue [Fe(5F-sal2333)]BPh4, 2, is low spin between 5–250 K, with onset of a gradual and incomplete spin crossover on warming to room temperature. Structural investigation reveals different orientations of the hydrogen atoms on the secondary amine donors in the two salts of the [Fe(5F-sal2333)]+ cation: high spin complex [Fe(5F-sal2333)]Cl, 1, crystallizes with non-meso orientations while the spin crossover complex [Fe(5F-sal2333)]BPh4, 2, crystallizes with a combination of meso and non-meso orientations disordered over one crystallographic site. Variable temperature electronic absorption spectroscopy of methanolic solutions of 1 and 2 suggests that both are capable of spin state switching in the solution. View Full-Text
Keywords: Fe(III) coordination complexes; hexadentate ligand; Schiff base; spin crossover; UV-Vis spectroscopy; SQUID; EPR spectroscopy Fe(III) coordination complexes; hexadentate ligand; Schiff base; spin crossover; UV-Vis spectroscopy; SQUID; EPR spectroscopy
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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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Sundaresan, S.; Kühne, I.A.; Kelly, C.T.; Barker, A.; Salley, D.; Müller-Bunz, H.; Powell, A.K.; Morgan, G.G. Anion Influence on Spin State in Two Novel Fe(III) Compounds: [Fe(5F-sal2333)]X. Crystals 2019, 9, 19.

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