The principle 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 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).