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Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn–Teller Distortion

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journal contribution
posted on 06.07.2015, 00:00 by Laurence J. Kershaw Cook, Flora L. Thorp-Greenwood, Tim P. Comyn, Oscar Cespedes, Guillaume Chastanet, Malcolm A. Halcrow
The synthesis of 4-methyl-2,6-di­(pyrazol-1-yl)­pyridine (L) and four salts of [FeL2]­X2 (X = BF4, 1; X = ClO4, 2; X = PF6, 3; X = CF3SO3, 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T1/2↓ = 204 and T1/2↑ = 209 K (1), and T1/2↓ = 175 and T1/2↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn–Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T1/2, exposing both compounds to 10–5 Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn–Teller distortion.