Abstract
Extraction complexes of Eu(III), Tb(III), Tm(III), and Am(III) with three 1,10-phenanthroline-type ligands have been studied, primarily using density functional theory (DFT). The same accuracies and optimized structural geometries were obtained whether optimization of the [ML2(NO3)]2+ complexes was performed at the B3LYP/6-31G(d)/RECP or the MP2/6-31G(d)/RECP level of theory. Calculations carried out at the B3LYP/6-311G(d, p)/RECP level of theory indicated that solvation does not favor the formation of these complexes. Moreover, the ΔG g and ΔG solv values for the reactions leading to the formation of [LnL2(NO3)]2+ complexes were seen to decrease with increasing atomic number of the lanthanide (from Eu to Tb to Tm). In addition, when a strongly hydrophobic benzo[e][1,2,4]triazine group was created in each ligand, ligand selectivity for actinides/lanthanides in acidic media improved. Even greater ligand selectivity for actinides/lanthanides in acidic media was obtained when a 5,6-diphenyl-1,2,4-triazine group was created in each ligand instead of a benzo[e][1,2,4]triazine group. Vibrational analysis and NMR spectroscopic analysis were also performed on all of the studied ligands and the metal complexes that included them. Further in-depth investigations should be undertaken in this field.
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This work was supported by the National Major Scientific and Technological Special Project for “Significant New Drugs Development” (grant nos. 2014ZX09507007-001 and 2014ZX09507007-003) and the National Natural Science Foundation of China (grant nos. 21371026)
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Yang, Y., Fang, Y., Liu, J. et al. Complexation behavior of Eu(III), Tb(III), Tm(III), and Am(III) with three 1,10-phenanthroline-type ligands: insights from density functional theory. J Mol Model 21, 185 (2015). https://doi.org/10.1007/s00894-015-2721-2
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DOI: https://doi.org/10.1007/s00894-015-2721-2