Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis
AuthorPhonsri, W; Harding, P; Liu, L; Telfer, SG; Murray, KS; Moubaraki, B; Ross, TM; Jameson, GNL; Harding, DJ
Source TitleChemical Science
PublisherRoyal Society of Chemistry
University of Melbourne Author/sJameson, Guy
AffiliationSchool of Chemistry
Document TypeJournal Article
CitationsPhonsri, W., Harding, P., Liu, L., Telfer, S. G., Murray, K. S., Moubaraki, B., Ross, T. M., Jameson, G. N. L. & Harding, D. J. (2017). Solvent modified spin crossover in an iron(III) complex: phase changes and an exceptionally wide hysteresis. Chemical Science, 8 (5), pp.3949-3959. https://doi.org/10.1039/c6sc05317c.
Access StatusOpen Access
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.
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