Contemporary Chemistry of Berkelium and Californium

AbstractThe merging of small‐scale syntheses and rapid crystallization methods have provided access to crystalline samples of berkelium (Z=97) and californium (Z=98) coordination complexes and compounds that can be interrogated with a suite of spectroscopic tools and structural elucidation approaches that have come online over the last 20 years. The combination of this experimental data with relativistic theoretical methods that capture the effects of spin‐orbit coupling and scalar relativistic effects have allowed us to understand the electronic structure of berkelium and californium compounds at a level of detail that was not previously possible. The harbinger of this new era of post‐curium chemistry was the synthesis and characterization of [Cf{B6O8(OH)5}]. This compound possesses a structure type that is distinct from earlier actinide borates, a reduction in coordination number for californium, contracted Cf−O bond lengths, a substantially reduced magnetic moment with respect to the calculated free‐ion moment and, most importantly, vibronically coupled broadband photoluminescence. Ligand‐field analysis also showed that the splitting of the ground state was larger than typically