SYNTHESIS AND CHARACTERIZATION OF NOVEL NITROGEN-CONTAINING LIGANDS FOR METAL ION SEPARATIONS
Hoch, Cortney Leigh
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A serious limiting factor in the continued development of nuclear power is the disposal of high-level radioactive waste from spent nuclear fuel. The PUREX process can be used for the recovery of U and Pu, but it does not separate the products of fission which are potentially useful, but currently cause most of our problems with radioactive waste. An important complicating factor is the presence of large amounts of lanthanides in dissolved spent nuclear fuel. The separation of lanthanides (Ln) from actinides (An) is therefore critical to the future of nuclear power. One approach to recovering these materials and decreasing the volume of the radioactive waste is the development of novel, highly selective organic ligands for the lanthanide and actinide ions. The focus of this dissertation is to design and synthesize new tridentate polyaza-ligands expected to exhibit affinity for first-row transition metals, lanthanides and actinides. In general, these chelating agents are structurally and functionally related to the pyridine and bipyridine bis-triazinyl compounds that have been investigated for potential application as separations agents for radioactive materials. Selected 1,2,3-triazoles have been synthesized using Sharpless' "Click Chemistry". Variation of the backbone and substituents on the triazole ring allows for facile modification of the cation binding pocket and phase compatibility properties of the new compounds. Characterization of the new ligands was performed using conventional analytical methods. Overall, the studies with three different ligands revealed useful information about the continuing effort of ligand design for actinide (III)/lanthanide (III) separations. Crystal structures established the purity of the organic molecules by showing that the PTMP and BDTP ligands are able to bind transition metals. Also, it was shown that the BDTB ligand was able to bind to Nd3+ as observed from the spectrophotometric titrations and the calculated binding constant. To increase the lipophilicity of the ligand, the addition of an alkyl chain on the 4-position of the pyridine ring could be made. This confirms that scientists are advancing in the area of ligand design and hopefully one day the ligand with all of the desired characteristics will be used to close the nuclear fuel cycle.