Complexation of Lanthanide(III) and Actinide(III) Cations with Tridentate Nitrogen-Donor Ligands: A Luminescence and Spectrophotometric Study

DFT modeling of the relative affinity of nitrogen ligands for trivalent f elements: an energetic point of view

“…Such studies, usually based on structural comparisons between actinide and lanthanide complexes, have been enriched by several thermodynamic works. [17][18][19][20][21][22][23][24] The exploited techniques-e.g. microcalorimetry, spectrophotometry, NMR and mass spectroscopies-have reached sufficient accuracy to differentiate americium and curium behavior from that of lanthanides.…”

Development of highly selective compounds for solvent extraction processes: partitioning and transmutation of long-lived radionuclides from spent nuclear fuels

“…These tridentate nitrogen-donor ligands all provided moderate selectivity of complexation toward An(III), with selectivity factors versus Ln(III), SF An/Ln , ranging from 5 to 20 at most, as demonstrated by Miguirditchian et al (2005Miguirditchian et al ( , 2006, who investigated the thermodynamics of M(III): ADPTZ complex formation (M = An or Ln) and pointed out the more exothermic complexation reactions of An(III) than Ln(III), thus highlighting the assumed greater covalent character of the N-An(III) bonds, which is supported by quantum chemistry calculations. The X-ray crystal structures of metal : terpyridine solvates resolved by Berthet et al (2002a) also revealed that the U-N(central pyridine) distances are shorter than the U-N(distal pyridines) distances, while the reverse is true for lanthanide compounds.…”

“…These investigations are carried out both at molecular and supramolecular scales implementing analytical methods adapted to the nuclear environment to probe radioactive complexes. Analytical techniques used to investigate complexes at molecular scale include NMR (Wietzke et al, 1998, Lefrançois et al, 1999, Dozol and Berthon, 2007, UV-Visible spectrophotometry (Miguirditchian et al, 2006), X-ray crystallography (Wietzke et al, 1998, Berthet et al, 2005, Baaden et al, 2003, Coupez et al, 2003, Gaunt et al, 2008, X-ray absorption spectroscopy , Denning et al, 2002, Den Auwer et al, 2004, Gannaz et al, 2006, time-resolved laserinduced fl uorescence spectroscopy (Colette et al, 2004, Pathak et al, 2009, microcalorimetry (Miguirditchian et al, 2005), gas chromatography and electrospray ionization mass spectrometry (Lamouroux et al, 2006, Leclerc et al, 2008, Antonio et al, 2008. Examples of analytical techniques used to investigate complexes at supra-molecular scale are vapour pressure osmometry, small-angle neutron scattering, and small-angle X-ray scattering , Erlinger et al, 1999.…”

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

“…[11][12][13][14] Time-resolved laser-induced fluorescence and UV-Vis spectroscopy illuminated coordination chemistry, stability constants, and thermodynamics of [M(BTP)3] 3+ in solution, confirming a relationship between selectivity and metal-ligand bonding. [11][12][13][15][16][17][18][19][20] Evidence for enhanced covalence of Am-N versus Ln-N bonds in [M(BTP)3] 3+…”