Polyazines emerge as highly selective ligands toward actinide versus lanthanide separation. Electronic structures of several mono- and polyazine f-complexes of general formula MX3L (M(+3) = Ce, Nd, Eu, U, Am, and Cm; X = RCp(-) or NO3(-); L = N-donor ligand) related to Ln(III)/An(III) differentiation have been investigated using scalar relativistic ZORA/DFT calculations. In all cases, DFT calculations predict shorter An-N bonds than Ln-N ones whatever the azine used, in good agreement with available experimental data. The An-N bonds are also characterized by higher stretching frequencies than Ln-N bonds. The electronic structures of all species have been studied using different population analyses, among them natural population (NPA) and the quantum theory of atoms in molecule approach (QTAIM), as well as using different bond indices. The ability for Ln(III)/An(III) differentiation of the terdentate bipyrazolate BPPR ligand in the M(BPPR)(NO3)3 complexes (M(3+) = Ce, Eu, U and Am ; R = H, 2,2-dimethylpropyl) where BPP = 2,6-bis(dialkyl-1H-pyrazol-3-yl)pyridine has been studied, with a special emphasis on the total metal-ligand bonding energy (TBE). The ZORA/DFT approach was found to properly reproduce the higher selectivity of the polyazine BPP ligand compared to monoazines, especially for the Eu(III)/Am(III) pair operating in spent nuclear fuel, using computed TBEs as criterion. Moreover, the orbital part of the total bonding energy appears also to rationalize well the observed selectivity.
International audienceMagnetic exchange couplings in bis(ketimide) binuclear UIV/UIV complexes [Cp′2UCl]2(μ-ketimide) diuranium(IV) and [(C5H5)2(Cl)An]2(μ-ketimide) (Cp′ = C5Me4Et; ketimide = N=CMe-(C6H4)-MeC=N) have been investigated computationally using relativistic density functional theory (DFT) combined with the broken symmetry (BS) approach. Using the B3LYP hybrid functional, the BS ground state of these UIV/UIV 5f 2-5f 2 complexes has been found of lower energy than the high spin (HS) quintet state, indicating an antiferromagnetic character (estimated coupling constant |J| < 5 cm−1) which has not yet been evidenced unambiguously experimentally. On the contrary, the BP86 GGA functional overestimates greatly the antiferromagnetic character of the complexes (|J| > 100 cm−1). As recently reported for para-bis(imido) [(C5H5)3U]2(μ-imido) uranium(V) complex, spin polarization is mainly responsible for the antiferromagnetic coupling through the π-network orbital pathway within the bis(ketimide) bridge. Furthermore, spin polarization is exalted by the combined roles of the 5f metal orbitals and of the π-conjugated ketimide bridging ligand which permit electronic communication between the two uranium atoms albeit separated by a distance of the order of 10 Å. The MO analysis clarifies which MOs contribute to the antiferromagnetic coupling in the binuclear complexes under consideration and brings to light the 5f orbitals driving contribution
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