New approaches to magnetic clusters with hexacyanometallate building blocks

Polymeric cyanide complexes, whose archetype is the well-known Prussian blu e mixed valence compound Fe-4[Fe(CN)(6)](3), are key players in the field o f molecule-based magnetism. One reason for the popularity of the cyanide li gand is that it effects strong and predictable magnetic exchange interactio ns between paramagnetic centers. In an effort to produce high-dimensional m aterials that behave as magnets, researchers in the area have focused on re actions of [M(CN)(6)](n-) with labile cations that contain few or no protec ting groups to limit the growth of polymeric phases. This article reports t he syntheses and characterization of new ligand protected precursors of the types cis-[M(L-L)(2)(S)(2)](2+) (S = solvent), cis-M(L-L)(2)(CN)(2) and ci s-M(L-L)(2)(O(3)5CF(3))(2). Reactions of these convergent precursors with h exacyanometallate anions yield novel cyanide clusters, described along with key X-ray structures. (C) 2001 Elsevier Science Ltd. All rights reserved.