A controlled way of combining relevant/interesting physical properties is important in targeting new magnetic materials. Coordination chemistry, in principle, proffers the possibility to delicately tune the properties of modules (or building blocks) and subsequently acquire synthetic topological control. A shortcut to obtaining the desirable control is to remove or block some of the many degrees of freedom in reactivity of a metal ion unit. For a bridging ligand, the simplest conceivable geometrical requirement would be that of a preference for linear bridging. This is found for the ubiquitous cyanide bridges, but also to quite some extent for oxide and fluoride. New fluoride-based modules of nd transition elements have been synthesized, characterized and assembled by linear �-fluoride bridging with d- or f-block elements into polynuclear complexes (including SMMs) and one-dimensional systems (including SCMs). Thus, for example, reactions of simple lanthanide compounds with various Cr(III)-fluorido complexes yield an extensive series of polynuclear, fluoride-bridged 3d�4f complexes in which the final topology of the material is directed by the structure of the Cr(III) precursor; giving for instance molecular rods, squares or pyramids (Fig. 1). The resulting, structurally simple, systems have allowed for modeling of the magnetic properties and for the first quantification of magnetic coupling between 3d and 4f centers across a fluoride bridge, for orbitally degenerate as well as for orbitally non-degenerate 4f systems.

Fluoride-based modules for magnetic molecular materials

246th National Meeting (2013)

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