Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials

Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr⁴⁺-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f ¹ configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr⁴⁺, which departs from the J _eff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr⁴⁺ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.