New approaches to magnetic clusters with hexacyanometallate building blocks

Abstract

Polymeric cyanide complexes, whose archetype is the well-known Prussian blue mixed valence compound Fe 4[Fe(CN) 6] 3, are key players in the field of molecule-based magnetism. One reason for the popularity of the cyanide ligand is that it effects strong and predictable magnetic exchange interactions between paramagnetic centers. In an effort to produce high-dimensional materials that behave as magnets, researchers in the area have focused on reactions of [M(CN) 6] n− with labile cations that contain few or no protecting groups to limit the growth of polymeric phases. This article reports the 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 cis-M(LL) 2(O 35CF 3) 2. Reactions of these convergent precursors with hexacyanometallate anions yield novel cyanide clusters, described along with key X-ray structures.