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.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2010-05-7692 |
| Date | 2010 May 1900 |
| Creators | Hilfiger, Matthew Gary |
| Contributors | Dunbar, Kim R. |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | thesis, text |
| Format | application/pdf |
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