Structural and Bonding Analysis in Monomeric Actinide(IV) Oxalate from Th(IV) to Pu(IV): Comparison with the An(IV) Nitrate Series.

Single-crystal X-ray diffraction (SC-XRD) structures and Raman spectra of a series of new isomorphous molecular An(IV)-oxalate compounds (Th, U, Np, and Pu) are reported. These complexes are crystallized with cobalt(III) hexamine ([Co(NH3)6]3+) as the counter cations, [Co(NH3)6]2[An(C2O4)5]·4H2O, revealing five bidentate nonbridging oxalate ligands in the first coordination sphere (CN = 10). The nonbridging oxalate is rather uncommon for An(IV)-oxalate systems, which are widely characterized as polymeric compounds. Density functional theory (DFT) calculations were performed to examine the bonding between An(IV) cations and oxalate ligands. For comparison, we also report results obtained for the An(IV)-hexanitrate series, [(C2H5)4N]2[An(NO3)6] (with An = Th, U, Np, Pu, and Ce), which consists of O-donor ligands as well but with a larger coordination number (CN = 12). The bonding analysis confirms that the actinide-oxygen bond is predominantly ionic with a minor increase in covalency from Th to U and slight variations from U to Pu. Further comparison showed that the charge transfer increases slightly when increasing the number of anions in the coordination sphere (C2O42-: CN = 10; NO3-: CN = 12), but covalent effects as indicated by the amount of internuclear electron density accumulation are small and similar for oxalate and nitrate.

Dipolar and Contact Paramagnetic NMR Chemical Shifts in AnIV Complexes with Dipicolinic Acid Derivatives.

Actinide +IV complexes (AnIV = ThIV, UIV, NpIV, and PuIV) with two dipicolinic acid derivatives (DPA and Et-DPA) have been studied by 1H and 13C NMR spectroscopies and first-principles calculations. The Fermi contact and dipolar contributions to the actinide-induced shifts (AIS) are evaluated from a temperature dependence analysis, combined with ab initio results. It allows an experimental estimation of the axial anisotropy of the magnetic susceptibility Δχax and of the hyperfine coupling constants of the NMR-active nuclei. Due to the compactness of the coordination sphere, the magnetic anisotropy of the paramagnetic center is small, and this makes the contact contribution to be the dominant one, even on the remote atoms. The sign of the hyperfine coupling constants and related spin densities is alternating on the nuclei of the ligand cycle, denoting a preponderant spin polarization mechanism. This is well reproduced by unrestricted density functional theory (DFT) calculations. Those values are furthermore slightly decreasing in the actinide series, which indicates a small decrease of the covalency from UIV to PuIV.

Temperature Dependence of 1 H Paramagnetic Chemical Shifts in Actinide Complexes, Beyond Bleaney's Theory: The AnVI O2 2+ -Dipicolinic Acid Complexes (An=Np, Pu) as an Example.

Actinide +VI complexes ( A n V I = U V I , N p V I and P u V I ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, N p V I and P u V I complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1 H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans' method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the N p V I complex. The temperature dependence of the pNMR chemical shifts has a strong 1 / T contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the N p V I complex and a non-Kramers-doublet model for the P u V I complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.

Crystallographic structure and crystal field parameters in the [AnIV(DPA)3]2- series, An = Th, U, Np, Pu.

The [AnIV(DPA)3]2- series with An = Th, U, Np, Pu has been synthesized and characterized using SC-XRD and vibrational spectroscopy. First principles calculations were performed, the total electron density is analyzed using the Quantum Theory of Atoms in Molecules. Crystal field parameters and strength parameters are deduced following a previous work on the LnIII analog series e.g. [J. Jung et al., Chem. - Eur. J., 2019, 25, 15112]. The trends in the parameters along the series are compared to the LnIII complexes. They evidence larger covalent interactions and larger J mixing.

Insight of the Metal-Ligand Interaction in f-Element Complexes by Paramagnetic NMR Spectroscopy.

The magnetic properties of LnIII and AnIII complexes formed with dipicolinate ligands have been studied by NMR spectroscopy. To know precisely the geometries of these complexes, a crystallographic study by single-crystal X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) in solution was performed. Several methods to separate the paramagnetic shifts observed in the NMR spectra were applied to these complexes. Methods using a number of nuclei of the dipicolinate ligands revealed an abrupt change in the geometries of the complexes and a metal-ligand interaction in the middle of the lanthanide series. A study of the variation of the paramagnetic shifts with temperature demonstrated that higher-order terms of the dipolar and contact contributions are required, especially for the lightest LnIII and almost all the studied AnIII . Bleaney's parameters a and C a D relating to the contact and dipolar terms, respectively, were deduced from experimental data and compared with the results of ab initio calculations. Quite a good agreement was found for the temperature dependencies of a and C a D . However, the C a D values obtained from cation magnetic anisotropy calculations showed some discrepancies with the values derived from Bleaney's equation defined for LnIII . Other parameters, such as the crystal field parameter and the hyperfine constants Fi obtained from the experimental data of the [An(ethyl-dpa)3 ]3- complexes (ethyl-dpa=4-ethyl-2,6-dipicolinic acid), are at odds with the assumptions underlying Bleaney's theory.

Paramagnetism of Aqueous Actinide Cations. Part II: Theoretical Aspects and New Measurements on An(IV).

The magnetic properties of actinide(IV) (An(IV)) cations are investigated in various solutions (HClO4, HCl, and HNO3) by the Evans NMR method. The magnetic susceptibilities measured in noncomplexing medium are compared with the previous studies, and the influence of the medium is verified with new measurements in complexing solutions. To rationalize these results, spin-orbit complete active space perturbation theory at second order calculations are performed on the free ions and on the aquo complexes to determine the nature of electronic states, the magnetic susceptibility, and the UV-visible-near-IR spectra. The different factors contributing to the An(IV) magnetic properties were identified. The ligand field effect on the magnetic behavior (Curie constant and temperature-independent susceptibilities) was analyzed by considering different solvation environments. These results indicate a significant effect of the zero-field splitting of the ground J manifold on the An(IV) magnetic susceptibility.

Magnetic susceptibility of actinide(iii) cations: an experimental and theoretical study.

In a previous paper, the influence of radioactive decay (α and ß(-)) on magnetic susceptibility measurements by the Evans method has been demonstrated by the study of two americium isotopes. To characterize more accurately this phenomenon and particularly its influence on the Curie law, a new study has been performed on two uranium isotopes ((238)U and (233)U) and on tritiated water ((3)H2O). The results on the influence of α emissions have established a relationship between changes in the temperature dependence and the radioactivity in solution. Regarding the ß(-) emissions, less influence was observed while no temperature dependence linked to this kind of radioactive emission could be identified. Once magnetic susceptibility measurements of actinide(iii) cations were corrected from radioactivity effects, methods of quantum chemistry have been used on free ions and aquo complexes to calculate the electronic structure explaining the magnetic properties of Pu(iii), Am(iii) and Cm(iii). The ligand field effect on the magnetic behavior (the Curie constant and temperature-independent susceptibilities) was analyzed by considering different solvation environments.

Paramagnetism of aqueous actinide cations. Part I: Perchloric acid media.

A comprehensive study of actinide cation paramagnetism in acidic aqueous solution has been completed in perchlorate media. Employing the Evans method, all the readily accessible actinide cations have been studied using our specially outfitted NMR spectrometer equipped for use with radioactive samples. The effective magnetic moments observed, ranging from 0 to 13 µB, differ from the isoelectronic lanthanides, previous solid actinide studies, and older solution studies. Actinide (IV) and (V) ions show less paramagnetic character, while some actinide (III) ions exhibit greater paramagnetic behavior than predicted from free-ion calculation. Temperature dependence of actinide magnetic susceptibilities from 5 to 80 °C are in good agreement with a Curie-like law except for U(VI), which appears to be temperature-independent. Diamagnetic behavior of Th(IV) exhibits a very low temperature dependence of the magnetic susceptibility. Some explanations for the observations are offered, and the 5f electron behavior is compared to the 4f analogues.

The influence of radioactive decay on actinide magnetic susceptibility measurements obtained using the Evans method.

In order to explain the higher magnetic susceptibility of some aquo actinide ions than predicted by Hund's rules, the molar magnetic susceptibilities of two americium isotopes ((241)Am and (243)Am) were measured using the Evans method. The results obtained show a growing change in the magnetic susceptibility with α and also a ß(-) activity increase in solution. ß(-) particle effects appear to be stronger than radicals formed by α particles on the experimental values. The temperature dependence of Am(iii) magnetic susceptibility has been observed but from experiments carried out here, it appears to be difficult to prove whether this effect arises from radicals or ß(-). Finally, magnetic susceptibilities of americium recorded in different media (HClO4, HCl, and HNO3) have been compared to alpha and beta emissions' impact.