Chemistry - A European Journal
10.1002/chem.201903685
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successfully used in previous studies of actinide complexes.[30]
Comparison of the energies of the complexes relative to the
respective free ligand conformations of lowest energy enabled
the relative complexation energies of the ligands to be
determined. The results indicate that the binding energy of 3
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2 3
(NO
)]2+ was 1.76 kJ mol−1 less favorable
when forming [Am(3)
than the binding of 10 when forming [Am(10)
2
+
2
3
(NO )] in an
acetonitrile solvent field (see Supporting Information section 7).
Similar values were obtained from calculations in the gas phase
and in a 1-octanol solvent field. This suggests that the 1:2
complex of 10 is marginally more stable than that of 3, but that
neither has a significantly greater binding energy than the other.
This may indicate that there is little difference between the
inherent metal binding energies of the ligands 3 and 10, and that
the differences in extraction properties observed above arise
instead from specific solvent interactions.
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Conclusions
In conclusion, we report three novel bis-1,2,4-triazine ligands
derived from a 5-membered ring diketone, and we show for the
first time how tuning the aliphatic ring size of bis-1,2,4-triazine
ligands leads to subtle changes in the speciation of the ligands
with trivalent f-block metal ions, the thermodynamic stabilities of
the formed metal complexes, and the trivalent actinide extraction
affinities of the ligands. We propose that this insight could
enable a more rational design of actinide-selective ligands with
tailored solvent extraction properties suitable for future spent
nuclear fuel reprocessing to close the nuclear fuel cycle.
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We thank the EPSRC (EP/P004873/1) and Northumbria
University for funding this research, and the Royal Society of
Chemistry for awarding a Researcher Mobility Grant to Rachel
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Spectrometry Facility at Swansea University for recording high-
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generous
gift
of
a
sample
of
2,2,4,4-
tetramethylcyclopentanone.
Keywords: actinide • triazine ligand • spent nuclear fuel •
solvent extraction • lanthanide
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