Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis

Wasinee Phonsri, Phimphaka Harding, Lujia Liu, Shane G Telfer, Keith S Murray, Boujemaa Moubaraki, Tamsyn M Ross, Guy N L Jameson, David J Harding

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Solvent effects in a series of Fe(iii) spin crossover (SCO) complexes [Fe(qsal-I)2]OTf·sol (sol = MeOH 1, EtOH 2, n-PrOH 3, i-PrOH 4, acetone 5 and MeCN 6) are explored. SCO is abrupt in 1 (following MeOH loss) and 2, gradual for 3 (T1/2 = 199 K) and 4 (T1/2 = 251 K) and incomplete, even up to 350 K, for 5 and 6. In [Fe(qsal-I)2]OTf SCO occurs at T1/2↓ = 225 K and T1/2↑ = 234 K (ΔT = 9 K), while aged samples of 2 exhibit an exceptionally wide hysteresis of 80 K (T1/2↓ = 139 K and T1/2↑ = 219 K). In contrast, fresh samples of 2 exhibit stepped SCO with hysteresis varying from 2 to 42 K. VT-PXRD (variable temperature powder X-ray diffraction) studies indicate a new phase, 2b, is formed upon cooling below 180 K along with a minor LS phase 2c. Phase 2c and the HS phase 2a undergo a spin transition at T1/2↓ = 180 K and T1/2↑ = 215 K with phase 2b exhibiting two-step SCO. Structural studies in both spin states, except 6, show the cations are linked through extensive π-π interactions to form 1D chains. A combination of P4AE (parallel fourfold aryl embrace) and I⋯X (X = I, O, π) interactions create tightly packed 3D supramolecular networks. This study emphasizes that while solvent may result in only small structural changes SCO characteristics can be impacted dramatically.

Original languageEnglish
Pages (from-to)3949-3959
Number of pages11
JournalChemical Science
Volume8
Issue number5
DOIs
Publication statusPublished - 2017

Cite this

Phonsri, Wasinee ; Harding, Phimphaka ; Liu, Lujia ; Telfer, Shane G ; Murray, Keith S ; Moubaraki, Boujemaa ; Ross, Tamsyn M ; Jameson, Guy N L ; Harding, David J. / Solvent modified spin crossover in an iron(III) complex : phase changes and an exceptionally wide hysteresis. In: Chemical Science. 2017 ; Vol. 8, No. 5. pp. 3949-3959.
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title = "Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis",
abstract = "Solvent effects in a series of Fe(iii) spin crossover (SCO) complexes [Fe(qsal-I)2]OTf·sol (sol = MeOH 1, EtOH 2, n-PrOH 3, i-PrOH 4, acetone 5 and MeCN 6) are explored. SCO is abrupt in 1 (following MeOH loss) and 2, gradual for 3 (T1/2 = 199 K) and 4 (T1/2 = 251 K) and incomplete, even up to 350 K, for 5 and 6. In [Fe(qsal-I)2]OTf SCO occurs at T1/2↓ = 225 K and T1/2↑ = 234 K (ΔT = 9 K), while aged samples of 2 exhibit an exceptionally wide hysteresis of 80 K (T1/2↓ = 139 K and T1/2↑ = 219 K). In contrast, fresh samples of 2 exhibit stepped SCO with hysteresis varying from 2 to 42 K. VT-PXRD (variable temperature powder X-ray diffraction) studies indicate a new phase, 2b, is formed upon cooling below 180 K along with a minor LS phase 2c. Phase 2c and the HS phase 2a undergo a spin transition at T1/2↓ = 180 K and T1/2↑ = 215 K with phase 2b exhibiting two-step SCO. Structural studies in both spin states, except 6, show the cations are linked through extensive π-π interactions to form 1D chains. A combination of P4AE (parallel fourfold aryl embrace) and I⋯X (X = I, O, π) interactions create tightly packed 3D supramolecular networks. This study emphasizes that while solvent may result in only small structural changes SCO characteristics can be impacted dramatically.",
author = "Wasinee Phonsri and Phimphaka Harding and Lujia Liu and Telfer, {Shane G} and Murray, {Keith S} and Boujemaa Moubaraki and Ross, {Tamsyn M} and Jameson, {Guy N L} and Harding, {David J}",
year = "2017",
doi = "10.1039/c6sc05317c",
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Phonsri, W, Harding, P, Liu, L, Telfer, SG, Murray, KS, Moubaraki, B, Ross, TM, Jameson, GNL & Harding, DJ 2017, 'Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis' Chemical Science, vol. 8, no. 5, pp. 3949-3959. https://doi.org/10.1039/c6sc05317c

Solvent modified spin crossover in an iron(III) complex : phase changes and an exceptionally wide hysteresis. / Phonsri, Wasinee; Harding, Phimphaka; Liu, Lujia; Telfer, Shane G; Murray, Keith S; Moubaraki, Boujemaa; Ross, Tamsyn M; Jameson, Guy N L; Harding, David J.

In: Chemical Science, Vol. 8, No. 5, 2017, p. 3949-3959.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Solvent modified spin crossover in an iron(III) complex

T2 - phase changes and an exceptionally wide hysteresis

AU - Phonsri, Wasinee

AU - Harding, Phimphaka

AU - Liu, Lujia

AU - Telfer, Shane G

AU - Murray, Keith S

AU - Moubaraki, Boujemaa

AU - Ross, Tamsyn M

AU - Jameson, Guy N L

AU - Harding, David J

PY - 2017

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