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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.