The principal goal of the La Pierre group’s synthetic, physical, and spectroscopic studies is to disentangle the complex electronic structure of f-block materials. Definitive spectroscopic and thermodynamic signatures of electronic structure phenomena unique to lanthanide, actinide, and transuranic materials are lacking. In particular, the process of establishing a clear correspondence between spectroscopic signature, electronic structure, and physical properties is complicated by competition between multiple electronic phenomena on similar energy scales. Three problems of electron delocalization in f-block materials are driving our current studies including magnetic super-exchange (i.e. exchange coupled systems), multi-configurational electronic structures, and mixed-valence metal ions (i.e. mixed f/d occupancy).