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The positive impact of having access to well-defined starting materials for applied actinide technologies - and for technologies based on other elements - cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac3+ and Cm3+ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H2O)6 (1)(O2CMe)3 (1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1- ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

The positive impact of having access to well-defined starting materials for applied actinide technologies - and for technologies based on other elements - cannot be overstated. Of numerous relevant 5f-element starting materials, those in complexing aqueous media find widespread use. Consider acetic acid/acetate buffered solutions as an example. These solutions provide entry into diverse technologies, from small-scale production of actinide metal to preparing radiolabeled chelates for medical applications. However, like so many aqueous solutions that contain actinides and complexing agents, 5f-element speciation in acetic acid/acetate cocktails is poorly defined. Herein, we address this problem and characterize Ac3+ and Cm3+ speciation as a function of increasing acetic acid/acetate concentrations (0.1 to 15 M, pH = 5.5). Results obtained via X-ray absorption and optical spectroscopy show the aquo ion dominated in dilute acetic acid/acetate solutions (0.1 M). Increasing acetic acid/acetate concentrations to 15 M increased complexation and revealed divergent reactivity between early and late actinides. A neutral Ac(H2O)6 (1)(O2CMe)3 (1) compound was the major species in solution for the large Ac3+. In contrast, smaller Cm3+ preferred forming an anion. There were approximately four bound O2CMe1- ligands and one to two inner sphere H2O ligands. The conclusion that increasing acetic acid/acetate concentrations increased acetate complexation was corroborated by characterizing (NH4)2M(O2CMe)5 (M = Eu3+, Am3+ and Cm3+) using single crystal X-ray diffraction and optical spectroscopy (absorption, emission, excitation, and excited state lifetime measurements).

The isolation of [K(2.2.2-cryptand)][Ln(C5H4SiMe3)3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C5H4SiMe3)31- (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular LnII complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-order perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C5H4SiMe3)31- (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f6 5d0 (SmII), 4f13 5d0 (TmII), 4f14 5d0 (YbII), 4f14 5d1 (LuII), and 4d1 (YII) electronic configurations. Additionally, our results suggest that Ln(C5H4SiMe3)31- (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain LnII ions, but with 4f n 5d1 configurations (not 4f n+1 5d0). In these 4f n 5d1 complexes, the C3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d1 electronic configurations lower in energy than the more typical 4f n+1 5d0 configuration.

The isolation of [K(2.2.2-cryptand)][Ln(C5H4SiMe3)3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C5H4SiMe3)31- (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular LnII complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-order perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C5H4SiMe3)31- (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f6 5d0 (SmII), 4f13 5d0 (TmII), 4f14 5d0 (YbII), 4f14 5d1 (LuII), and 4d1 (YII) electronic configurations. Additionally, our results suggest that Ln(C5H4SiMe3)31- (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain LnII ions, but with 4f n 5d1 configurations (not 4f n+1 5d0). In these 4f n 5d1 complexes, the C3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d1 electronic configurations lower in energy than the more typical 4f n+1 5d0 configuration.

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear-fuel cycles. Herein, we describe the preparation of (NBu4 )Am[S2 P((t) Bu2 C12 H6 )]4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., Nd(III) ) and an isoelectronic one (Eu(III) ). The results include the first measurement of an Am-S bond length, with a mean value of 2.921(9) Å, by single-crystal X-ray diffraction. Comparison with the Eu(III) and Nd(III) complexes revealed subtle electronic differences between the complexes of Am(III) and the lanthanides.

Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear-fuel cycles. Herein, we describe the preparation of (NBu4 )Am[S2 P((t) Bu2 C12 H6 )]4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., Nd(III) ) and an isoelectronic one (Eu(III) ). The results include the first measurement of an Am-S bond length, with a mean value of 2.921(9) Å, by single-crystal X-ray diffraction. Comparison with the Eu(III) and Nd(III) complexes revealed subtle electronic differences between the complexes of Am(III) and the lanthanides.