Rational Ligand Design for U(VI) and Pu(IV) Page: 18 of 322
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substituents ........................................................................... 221
Figure 4-11. Hoard and Silverton edge notation of trigonal dodecahedral geometry (left)
and coordination polyhedra of the Ce(4-2)4 (middle) and Ce(4-3)4 (right)
complexes ............................................................................ 223
Figure 4-12. Hydroxypyrone ligands used in exploring Ce(IV) coordination
chemistry ............................................................................. 225
Figure 4-13. Top and side views of CeL4 complexes with hydroxypyrone ligands .....228
Figure 4-14. Edge notation for D2d and D4d coordination polyhedra used in Table 4-9 230
Figure 4-15. Design strategy of linear tetrakis-bidentate ligands for coordinative
saturation off-element cations ..................................................... 232
Figure 4-16. Possible coordination modes for the TAM moiety upon mono and bis-
deprotonation ........................................................................ 235
Figure 4-17. (a) Evolution of the luminescence spectrum of Yb(4-17g) upon addition
of DTPA; (b) Competition titration log/log plot for Yb(4-17g) against
DTPA at varying pH ................................................................ 237
Table 4-1. Crystallographic parameters for the Pu(IV)-1,2-HOPO structure ............ 212
Table 4-2. Shape measure values for Pu/Ce(IV) complexes with 4-1 ..................... 215
Table 4-3. Crystallographic parameters for Pu/Ce(4-2/4-3)4 complexes ..................217
Table 4-4. Calculated Pu-O distances in the Pu(4-3)4 crystal structure for each
disordered ligand group ............................................................ 222
Table 4-5. Pu/Ce-O bond distances and bite angles from the Pu/Ce(4-2/4-3)4 crystal
structures ..............................................................................222
Table 4-6. Shape measure (S) values for Pu/Ce(4-2/4-3)4 complexes .....................223
Table 4-7. Crystallographic parameters for Ce(IV)-hydroxypyrone crystal structures 226
Table 4-8. Shape measure (S) values for Ce(IV)-hydroxypyrone complexes in Figure
4-13 ....................................................................................229
Table 4-9. MM3 calculation results on the Ce(4-2/4-3)4 structures ........................229
Scheme 4-1. Synthesis of TAM4 and TAM2HOPO2 ligands ................................233xii
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Szigethy, Geza. Rational Ligand Design for U(VI) and Pu(IV), thesis or dissertation, August 12, 2009; Berkeley, California. (https://digital.library.unt.edu/ark:/67531/metadc932742/m1/18/: accessed April 25, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.