2003 | OriginalPaper | Buchkapitel
Polymorphism and Pressure Driven Thermal Spin Crossover Phenomenon in [Fe(abpt)2(NCX)2] (X=S, and Se): Synthesis,Structure and Magnetic Properties
verfasst von : Ana B. Gaspar, M. Carmen Muñoz, Nicolás Moliner, Vadim Ksenofontov, Georgii Levchenko, Philipp Gütlich, José Antonio Reall
Erschienen in: Molecular Magnets Recent Highlights
Verlag: Springer Vienna
Enthalten in: Professional Book Archive
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The monomeric compounds [Fe(abpt2(NCX)2(X = S (1), Se (2) and abpt = 4-amino- 3,5-bis(pyridin-2-yl)-1,2,4-triazole) have been synthesized and characterized. They crystallize in the monoclinic P21/n space group with a = 11.637(2) Å, b = 9.8021(14) Å, c = 12.9838(12) Å, β = 101.126(14)°, and Z=2 for 1, and a= 11.601(2) Å, b = 9.6666(14) Å, c = 12.883(2) Å, β = 101.449(10)°, and Z = 2 for 2. The unit cell contains a pair mononuclear [Fe(abpt)2(NCX)21 units related by a center of symmetry. Each iron atom, located at a molecular inversion center, is in a distorted octahedral environment. Four of the six nitrogen atoms coordinated to the Fe(II) ion belong to the pyridine-N(1) and triazole-N(2) rings of two abpt ligands. The remaining trans positions are occupied by two nitrogen atoms, N(3), belonging to the two pseudo-halide ligands. The magnetic susceptibility measurements at ambient pressure have revealed that they are in the high-spin range in the 2 K300 K temperature range. The pressure study has revealed that compound 1 remains in high-spin as pressure is increased up to 4.4kbar, where an incomplete thermal spin crossover appears at around T1/2 = 65 K.. Quenching experiments at 4.4 kbar have shown that the incomplete character of the conversion is a consequence of slow kinetics. Relatively sharp spin transition takes place at T1/2 = 106, 152 and 179 K, as pressure attains 5.6, 8.6 and 10.5 kbar, respectively.