Frontiers in divalent f-block chemistry

Divalent f -block chemistry has undergone rapid expansion in recent years, driven by advances in the stabilization of low-valent lanthanide and actinide complexes. Although f -elements were historically accessed in the +3 or higher oxidation states, the isolation of +2 species has revealed unusual spectroscopic signatures, distinct bonding motifs, and multiple accessible electronic configurations that influence their chemical and physical properties. These developments have generated opportunities in areas including quantum information science, molecular magnetism, catalysis, and luminescence. Computational chemistry has played a pivotal role in interpreting the electronic structure and reactivity of these systems. However, accurately modeling divalent f -block complexes remains challenging because of strong electronic correlation, multiconfigurational character, and the presence of close-in-energy competing electronic states. As experimental capabilities and theoretical methodologies continue to advance, a comprehensive assessment of divalent chemistry is both timely and needed. In this Review, we integrate experimental and theoretical perspectives to provide a systematic analysis of divalent lanthanide and actinide complexes across the f -block series. We critically assess the role of ligands in determining competing ground-state configurations ( f n d 1 vs. f n+ 1 ) resulting in their distinct spectroscopic, magnetic, and bonding properties. Finally, we discuss emerging strategies for predictive modeling and rational design of low-valent f -block molecular systems, with potential applications ranging from dinitrogen reduction to quantum technologies.