Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

The CeTIn_5 superconductors (T=Co, Rh, or Ir) have generated great interest due to their relatively high transition temperatures, non-Fermi liquid behavior, and their proximity to antiferromagnetic order and quantum critical points. In contrast to small changes with the T-species, electron doping in CeT(In_1-x M_x)_5 with $M$=Sn and hole doping with Cd or Hg have a dramatic effect on the electronic properties at very low concentrations. The present work reports local structure measurements using the extended x-ray absorption fine-structure (EXAFS) technique that address the substituent atom distribution as a function of T, M, and x, in the vicinity of the superconducting phase. Together with previous measurements for M=Sn, the proportion of the $M$ atom residing on the In(1) site, f_\textrm In(1), increases in the order M=Cd, Sn, and Hg, ranging from about 40\percent to 70percent, showing a strong preference for each of these substituents to occupy the In(1) site (random occupation = 20percent). In addition, f_In(1) ranges from 70percent to 100percent for M=Hg in the order T=Co, Rh, and Ir. These fractions track the changes in the atomic radii of the various species, and help explain the sharp dependence of $T_c$ on substituting into the In site. However, it is difficult to reconcile the small concentrations of M with the dramatic changes in the ground state in the hole-doped materials with only an impurity scattering model. These results therefore indicate that while such substitutions have interesting local atomic structures with important electronic and magnetic consequences, other local changes in the electronic and magnetic structure are equally important in determining the bulk properties of these materials.