Investigating the structure-property relationships of solid state materials can help improve many of the materials we use each day in life. It can also lead to the discovery of materials with interesting and unforeseen properties. In this work the structure property relationships of newly discovered layered oxypnictide phases are presented and discussed. There has generally been worldwide interest in layered oxypnictide materials following the discovery of superconductivity up to 55 K for iron arsenides such as LnFeAsO[subscript 1-x]F[subscript x] (where Ln = Lanthanoid). This work presents efforts to understand the structure and physical property changes which occur to LnFeAsO materials when Fe is replaced with Rh or Ir and when As is replaced with Sb. As part of this work the solid solution between LaFeAsO and LaRhAsO was examined and superconductivity is observed for low Rh content with a maximum critical temperature of 16 K. LnRhAsO and LnIrAsO compositions are found to be metallic; however Ce based compositions display a resistivity temperature dependence which is typical of Kondo lattice materials. At low temperatures a sudden drop in resistivity occurs for both CeRhAsO and CeIrAsO compositions and this drop coincides with an antiferromagnetic transition. The Kondo scattering temperatures and magnetic transition temperatures observed for these materials can be rationalized by considering the expected difference in N(E[subscript F])J parameters between them, where N(E[subscript F]) is the density of states at the Fermi level and J represents the exchange interaction between the Ce 4f¹ electrons and the conduction electrons. In addition to studying these 4d and 5d substituted systems the LaFeSbO compositional system was investigated. While LaFeSbO has not been successfully synthesized the transition metal free layered oxypnictide composition La₂SbO₂ was discovered and its structural and physical properties have been examined along with the properties of La₂BiO₂. Density functional theory was used to calculate the heats of formation for competing phases within the LaFeSbO system, in order to better understand the stability of LaFeSbO and why it has not yet been observed. The materials La₂SbO₂ and La₂BiO₂ were investigated for the presence of oxygen vacancies using powder neutron diffraction. Structure refinement reveals that there is significant disorder within the a-b plane for Sb compositions. / Graduation date: 2012

Nuclear Magnetic Resonance (NMR) has been a fundamental player in the studies of superconducting materials for many decades. This local probe technique allows for the study of the static electronic properties as well as the low energy excitations of the electrons in the normal and the superconducting state. On that account it has also been widely applied to Fe-based superconductors from the very beginning of their discovery in February 2008. This dissertation comprises some of these very first NMR results, reflecting the unconventional nature of superconductivity and its strong link to magnetism in the investigated compounds LaO(1-x)F(x)FeAs and LiFeAs.

Nuclear Magnetic Resonance (NMR) has been a fundamental player in the studies of superconducting materials for many decades. This local probe technique allows for the study of the static electronic properties as well as the low energy excitations of the electrons in the normal and the superconducting state. On that account it has also been widely applied to Fe-based superconductors from the very beginning of their discovery in February 2008. This dissertation comprises some of these very first NMR results, reflecting the unconventional nature of superconductivity and its strong link to magnetism in the investigated compounds LaO(1-x)F(x)FeAs and LiFeAs.:1. Introduction 2. Basic Principles of NMR 3. NMR in the Superconducting State 4. Iron-based Superconductors 5. Experimental Setup 6. NMR on LaO(1-x)F(x)FeAs in the Normal State 7. MR and NQR on LaO(1-x)F(x)FeAs in the Superconducting State 8. NMR and NQR on LiFeAs 9. Conclusions