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Mosaicity of Spin-Crossover Crystals

Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds

School of Science and Health, Western Sydney University, Penrith, Sydney, NSW 2751, Australia
Mark Wainwright Analytical Centre, University of New South Wales, Sydney, NSW 2052, Australia
School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia
Author to whom correspondence should be addressed.
Crystals 2018, 8(10), 376;
Received: 11 September 2018 / Revised: 19 September 2018 / Accepted: 19 September 2018 / Published: 23 September 2018
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
This work explores the effect of lattice solvent on the observed solid-state spin-transition of a previously reported dinuclear Fe(II) triple helicate series 13 of the general form [FeII2L3](BF4)4(CH3CN)n, where L is the Schiff base condensation product of imidazole-4-carbaldehyde with 4,4-diaminodiphenylmethane (L1), 4,4′-diaminodiphenyl sulfide (L2) and 4,4′-diaminodiphenyl ether (L3) respectively, and 1 is the complex when L = L1, 2 when L = L2 and 3 when L = L3 (Craze, A.R.; Sciortino, N.F.; Bhadbhade, M.M.; Kepert, C.J.; Marjo, C.E.; Li, F. Investigation of the Spin Crossover Properties of Three Dinuclear Fe(II) Triple Helicates by Variation of the Steric Nature of the Ligand Type. Inorganics. 2017, 5 (4), 62). Desolvation of 1 and 2 during measurement resulted not only in a decrease in T1/2 and completeness of spin-crossover (SCO) but also a change in the number of steps in the spin-profile. Compounds 1 and 2 were observed to change from a two-step 70% complete transition when fully solvated, to a single-step half complete transition upon desolvation. The average T1/2 value of the two-steps in the solvated materials was equivalent to the single T1/2 of the desolvated sample. Upon solvent loss, the magnetic profile of 3 experienced a transformation from a gradual SCO or weak antiferromagnetic interaction to a single half-complete spin-transition. Variable temperature single-crystal structures are presented and the effects of solvent molecules are also explored crystallographically and via a Hirshfeld surface analysis. The spin-transition profiles of 13 may provide further insight into previous discrepancies in dinuclear triple helicate SCO research reported by the laboratories of Hannon and Gütlich on analogous systems (Tuna, F.; Lees, M. R.; Clarkson, G. J.; Hannon, M. J. Readily Prepared Metallo-Supramolecular Triple Helicates Designed to Exhibit Spin-Crossover Behaviour. Chem. Eur. J. 2004, 10, 5737–5750 and Garcia, Y.; Grunert, C. M.; Reiman, S.; van Campenhoudt, O.; Gütlich, P. The Two-Step Spin Conversion in a Supramolecular Triple Helicate Dinuclear Iron(II) Complex Studied by Mössbauer Spectroscopy. Eur. J. Inorg. Chem. 2006, 3333–3339). View Full-Text
Keywords: spin-crossover; dinuclear triple helicate; Fe(II); solvent effects spin-crossover; dinuclear triple helicate; Fe(II); solvent effects
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MDPI and ACS Style

Craze, A.R.; Bhadbhade, M.M.; Kepert, C.J.; Lindoy, L.F.; Marjo, C.E.; Li, F. Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds. Crystals 2018, 8, 376.

AMA Style

Craze AR, Bhadbhade MM, Kepert CJ, Lindoy LF, Marjo CE, Li F. Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds. Crystals. 2018; 8(10):376.

Chicago/Turabian Style

Craze, Alexander R., Mohan M. Bhadbhade, Cameron J. Kepert, Leonard F. Lindoy, Christopher E. Marjo, and Feng Li. 2018. "Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds" Crystals 8, no. 10: 376.

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