Investigation of the Spin Crossover Properties of Three Dinulear Fe(II) Triple Helicates by Variation of the Steric Nature of the Ligand Type

Craze, Alexander R.; Sciortino, Natasha F.; Badbhade, Mohan M.; Kepert, Cameron J.; Marjo, Christopher E.; Li, Feng

doi:10.3390/inorganics5040062

Cited by 24 publications

(25 citation statements)

References 45 publications

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“…− , BF 4 − and ClO 4 − , being present [58]. The [Fe 2 (L) 3 [ClO 4 ] 4 structure they obtained displayed a gradual, incomplete single-step transition like the desolvated samples in our previous study [57] and also the unsealed samples in this study. A later study by Gütlich and co-workers further explored the ClO 4 salt of this compound that led to an in-depth analysis of its magnetic behaviour and Mössbauer spectra [59].…”

Section: Magneto-structural Correlationssupporting

confidence: 66%

“…For a full structural description of 1 at 100 K, for which a solvatomorph was previously reported by Hannon and co-workers [58], see our previous study mentioned above [57]; a crystallographic summary of the variable temperature SCXRD analysis of 1-3 can be found in Table 1 below and further crystallographic details can be found in the supporting information (Tables S1-S3). At 298 K, 1 presents triclinic symmetry crystallising in the space group P1.…”

Section: Magneto-structural Correlationsmentioning

confidence: 93%

“…The single-crystal X-ray diffraction results at 100 K for 1-3 were presented in our previous report of the magnetic properties exhibited by completely dried samples [57]. Here, variable temperature single-crystal structures are presented in order to further explore the magneto-structural characteristics of these compounds.…”

Section: Magneto-structural Correlationsmentioning

confidence: 93%

“…All reagents and solvents were purchased from commercial sources (Sigma-Aldrich, Sydney, Australia and Alfa Aesar by Thermo Fisher Scientific, Australia and Tokyo Chemical Industry Co., Ltd., Adelaide, Australia), with no further purification being undertaken. Compounds 1-3 were prepared using the previously reported method [57]. Thermal gravimetric analysis (TGA) measurements were performed using a simultaneous thermal analysis (STA) 449 C Jupiter instrument (NETZSCH, Selb, Germany) using aluminium crucibles, nitrogen was used as both the protective and purge gas; the temperature range of 30-200 • C was cycled at a rate of 10 K•min −1 .…”

Section: Methodsmentioning

confidence: 99%

“…Previously, we reported the SCO of three desolvated Fe(II) dinuclear triple helicate compounds 1-3, that displayed single-step spin-transitions of ca. 50% completion [57]. Herein we report the effects of acetonitrile solvent molecules on the spin-transitions in this series of dinuclear triple helicates, which have the general formula [Fe II 2 L 3 ](BF 4 ) 4 (CH 3 CN) n and which differ in the steric nature of L (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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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 1–3 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 1–3 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).

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Section: Magneto-structural Correlationssupporting

confidence: 66%

Section: Magneto-structural Correlationsmentioning

confidence: 93%

Section: Magneto-structural Correlationsmentioning

confidence: 93%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from Pd^II to Ni^II in a Face‐Centered Fe^II₈M^II₆ Cubic Cage**

Min

Craze

Wallis

et al. 2023

Chemistry A European J

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Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in nextgeneration molecular transport and catalysis. Previous investigations of cubic cage [Fe 8 Pd 6 L 8 ] 28 + constructed using semirigid metalloligands, found that Fe II centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X-ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter-and intramolecular interactions associated with SCO in the Ni II analogue, 1 ([Fe 8 Ni 6 L 8 (CH 3 CN) 12 ] 28 + ). The distorted octahedral coordination environment, as well as the occupation of the CH 3 CN in the Ni II axial positions of 1, prevented close packing of cages observed in the Pd II analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.

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Conformational investigations on three large dinuclear triple helicates by single crystal X-ray diffraction

Howard-Smith,

Wallis,

Flood

et al. 2024

J Incl Phenom Macrocycl Chem

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Three new dinuclear triple helicates were synthesised using a ditopic semi-rigid pyridylylimine ligand L, separated by a diphenoxy-biphenol spacer providing considerable length to the backbone. L and the new large dinuclear triple helicate complexes [Fe2L3](BF4)4 (1), [Ni2L3](BF4)4 (2) and [Zn2L3](BF4)4 (3) have been characterised in solution and solid state. Single crystal X-ray diffraction was used to investigate overall complex ion shape as the coordination sphere was modulated by metal ion selection. Small differences in complex shape were seen to arise due to subtle distortions in coordination sphere environments. This study sheds light on how the length and twist of dinuclear triple helicates can be tuned by selection of coordinating metal ion.

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Investigation of the Spin Crossover Properties of Three Dinulear Fe(II) Triple Helicates by Variation of the Steric Nature of the Ligand Type

Cited by 24 publications

References 45 publications

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

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

Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from Pd^II to Ni^II in a Face‐Centered Fe^II₈M^II₆ Cubic Cage**

Conformational investigations on three large dinuclear triple helicates by single crystal X-ray diffraction

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Investigation of the Spin Crossover Properties of Three Dinulear Fe(II) Triple Helicates by Variation of the Steric Nature of the Ligand Type

Cited by 24 publications

References 45 publications

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

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

Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from PdII to NiII in a Face‐Centered FeII8MII6 Cubic Cage**

Conformational investigations on three large dinuclear triple helicates by single crystal X-ray diffraction

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Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from Pd^II to Ni^II in a Face‐Centered Fe^II₈M^II₆ Cubic Cage**