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Structure and Properties of [CrIIIF(NCMe)5](BF4)2·MeCN: A Nonaqueous Source of CrIIIF2+ and a Building Block for New Prussian-Blue-Like Magnetic Materials

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posted on 01.09.2008, 00:00 by Kendric J. Nelson, Antonio G. DiPasquale, Arnold L. Rheingold, Matthew C. Daniels, Joel S. Miller
[CrIIIF(NCMe)5](BF4)2·MeCN (1) was synthesized from a prolonged dissolution of [CrIII(NCMe)6](BF4)3 in MeCN via fluoride abstraction from BF4. Complex 1 exhibits a crystal field splitting, Δo, of 17 470 cm−1 and is a nonaqueous source of CrIIIF2+. The reaction of 1 with (NEt4)3[CrIII(CN)6] formed a new Prussian-blue-like magnetic material of (NEt4)0.04[CrIIIF]1.54[CrIII(CN)6](BF4)0.12·0.10(MeCN) (2) composition. Complex 2 magnetically orders at a critical temperature, Tc, of 85 K and at 2 K exhibits magnetic hysteresis with a coercive field, Hcr, of 60 Oe and a remanent magnetization, Mrem, of 1880 emuOe/mol.