Perplexing EPR Signals from 5f36d1 U(II) Complexes.
Article
Wedal, Justin C, Moore, William NG, Lukens, Wayne W et al. (2024). Perplexing EPR Signals from 5f36d1 U(II) Complexes.
. INORGANIC CHEMISTRY, 63(6), 2945-2953. 10.1021/acs.inorgchem.3c03449
Wedal, Justin C, Moore, William NG, Lukens, Wayne W et al. (2024). Perplexing EPR Signals from 5f36d1 U(II) Complexes.
. INORGANIC CHEMISTRY, 63(6), 2945-2953. 10.1021/acs.inorgchem.3c03449
Metal complexes with unpaired electrons in orbitals of different angular momentum quantum numbers (e.g., f and d orbitals) are unusual and opportunities to study the interactions among these electrons are rare. X-band electron paramagnetic resonance (EPR) data were collected at <10 and 77 K on 10 U(II) complexes with 5f36d1 electron configurations and on some analogous Ce(II), Pr(II), and Nd(II) complexes with 4fn5d1 electron configurations. The U(II) compounds unexpectedly display similar two-line axial signals with g||= 2.04 and g⊥ = 2.00 at 77 K. In contrast, U(II) complexes with 5f4 configurations are EPR-silent. Unlike U(II), the congenic 4f35d1 Nd(II) complex is EPR-silent. The Ce(II) complex with a 4f15d1 configuration is also EPR-silent, but a signal is observed for the Pr(II) complex, which has a 4f25d1 configuration. Whether or not an EPR signal is expected for these complexes depends on the coupling between f and d electrons. Since the coupling in U(II) systems is expected to be sufficiently strong to preclude an EPR signal from compounds with a 5f36d1 configuration, the results are viewed as unexplained phenomena. However, they do show that 5f36d1 U(II) samples can be differentiated from 5f4 U(II) complexes by EPR spectroscopy.
