Structural chemistry of organically-templated metal fluorides.

We present a systematic survey of the structural chemistry of crystalline hybrid fluorides. About a hundred different metal fluoride building units are represented in these systems, predominantly as anionic moieties, ranging from simple tetrahedral or octahedral dimers to larger oligomeric species, complex chains, layers and, ultimately, three-dimensional frameworks. Although a few compositional spaces have been moderately well explored and certain key features of their chemistries are understood, the underlying message is that this is an area still in its infancy, ripe for further and wider exploration, rich in new crystal-chemical characteristics and, perhaps, with great potential for the development of new physical and chemical functionalities.