Incorporation of Substitutionally Labile [VIII(CN)6]3− into Prussian Blue Type Magnetic Materials

• Published in: Inorganic chemistry Vol. 47; no. 7; pp. 2526 - 2533
• Main Authors: Nelson, Kendric J, Miller, Joel S
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07.04.2008
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic701845p

A Prussian blue (PB) type material containing hexacyanovanadate(III), MnII 1.5[VIII(CN)6]·0.30MeCN (1), was formed from the reaction of [VIII(CN)6]3− with [Mn(NCMe)6]2+ in MeCN. This new material exhibits ferrimagnetic spin- or cluster-glass behavior below a T c of 12 K with observed magnetic hysteresis at 2 K (H cr = 65 Oe and M rem = 730 emu·Oe/mol). Reactions of [VIII(CN)6]3− with [MII(NCMe)6]2+ (M = Fe, Co, Ni) in MeCN lead to either partial (M = Co) or complete (M = Fe, Ni) linkage isomerization, resulting in compounds of FeII 0.5VIII[FeII(CN)6]·0.85MeCN (2), (NEt4)0.10CoII 1.5−a VII a [CoIII(CN)6] a [VIII(CN)6]1−a (BF4)0.10·0.35MeCN (3), and (NEt4)0.20VIII[NiII(CN)4]1.6·0.10MeCN (4) compositions. Compounds 2–4 do not magnetically order as a consequence of diamagnetic cyanometalate anions being present, i.e., [FeII(CN)6]4−, [CoIII(CN)6]3−, and [NiII(CN)4]2−. Incorporation of [VIII(CN)6]3− into PB-type materials is synthetically challenging because of the lability of the cyanovanadate(III) anion.