Study of the Electronic Spin-State Crossover in {Fe[HC(3,4,5-Me₃pz)₃]₂}(BF₄)₂


The synthesis, structural, magnetic, and Mössbauer spectroscopic properties of {Fe[HC(3,4,5-Me3pz)3]2}(BF4)2 are reported. The single-crystal X-ray structure results indicate that at 150 K {Fe[HC(3,4,5-Me3pz) 3]2}(BF4)2 has a structure which is very similar to that observed at 220 K for the trigonally distorted octahedral, high-spin {Fe[HC(3,5-Me2pz)3]2}(BF4)2 complex. Both the magnetic and Mössbauer spectroscopic results indicate that {Fe[HC(3,4,5-Me3pz) 3]2}(BF4)2 is high spin between 160 and 296 K. Upon cooling, {Fe[HC(3,4,5-Me3pz)3]2}(BF4)2 exhibits a complete electronic spin-state crossover from the high-spin to the low-spin state at approximately 110 K and remains completely low spin down to 4.2 K; upon subsequent warming from 4.2 K, the transition from the low-spin to the high-spin state occurs at 148 to 150 K. {Fe[HC(3,4,5-Me3pz)3]2}(BF4)2 exhibits a rather large thermal hysteresis of 38 K in its spin-state crossover. Thus, {Fe[HC(3,4,5-Me3pz)3]2}(BF4)2 behaves differently from both {Fe[HC(3,5-Me2pz)3]2}(BF4) 2 which is known to show a unique spin-state crossover of one-half of its iron(II) ions associated with a phase transition, and Fe[HB(3,4,5-Me 3pz)3]2, which is known to remain high-spin even upon cooling to 1.7 K.




National Science Foundation of Belgium
Ministere de la Region Wallonne
National Science Foundation (U.S.)

Keywords and Phrases

Boron Derivative; Fluorine Derivative; Iron; Acceleration; Cooling; Hysteresis; Magnetism; Mössbauer Spectroscopy; Phase Transition; Structure Analysis; Synthesis; Temperature Measurement; X Ray Crystallography; Magnetic Properties; N Ligands; Spin Crossover

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Article - Journal

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© 2004 John Wiley & Sons, All rights reserved.

Publication Date

01 Aug 2004