Incorporation of 4d and 5d Transition Metal Cyanometallates into Magnetic Clusters and Materials.
Hilfiger, Matthew Gary
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The work presented herein describes efforts to synthesize and characterize new types of cyanide-bridged molecular materials encompassing both discrete clusters and extended solids. This investigation focused on the incorporation of anisotropic 4d and 5d transition metal ion building blocks into such materials. In this vein, systematic studies on the magnetic properties of families of these cyano-bridges species were conducted and these new materials represent a new addition to the field of cyanide chemistry incorporating for the first time the hexacyanometallates of [Ru(CN)6]3- and [Os(CN)6]3- into discrete molecules and extended networks. These compounds will serve as models for new theoretical studies in understanding the role of magnetic exchange interactions, both isotropic and anisotropic, in the study of nanomagnetic materials. Results were obtained from using the well known octacyanometallates of MoV and WV as building blocks for the synthesis and the magnetic investigation of both trigonal bipyramidal and pentadecanuclear clusters including the discovery of a new SMM. By expanding the research to previously unused hexacyanometallates, the synthesis and characterization of the first known examples of clusters based on hexacyanoosmate(III) and hexacyanoruthenate(III) building blocks and their use in preparing new theoretical models of magnetic species. A novel pair of clusters is further detailed in the study of the trigonal bipyramidal clusters of [Fe(tmphen)2]3[Os(CN)6]2 and [Fe(tmphen)2]3[Ru(CN)6]2 and an in depth study of the CTIST behavior of these clusters using Mossbauer spectroscopy, variable temperature crystallography, epr, and variable temperature IR measurements. Finally, this work discusses new magnetic Prussian Blue analogs prepared from the hexacyanoosmate(III) and hexacyanoruthenate(III) anions with a comparison to the trigonal bipyramidal clusters presented based on these hexacyanoosmate(III) and hexacyanoruthenate(III) building blocks.