Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Rice, Natalie T.
Publications and source records attributed to Rice, Natalie T..
Influence of Linker Identity on the Photochemistry of Uranyl-Organic Frameworks
While uranyl-based metal–organic frameworks (MOFs) boast impressive photocatalytic abilities, significant questions remain regarding their excitation pathways and methods to fine-tune their performance due to the lack of information regarding heterogeneous uranyl catalysis. Herein, we investigated how linker identity and photoexcitation impact uranyl photocatalysis when the uranyl coordination environment remains constant. Toward this end, we prepared three uranyl-based MOFs (NU-1301, NU-1307, and ZnTCPP-U2) and then examined the structural and photochemical properties of each through X-ray diffraction, X-ray absorption, and photoluminescence. We then correlated our observations to the photocatalytic performance for fluorination of cyclooctane. The excitation profile from NU-1301 and NU-1307 exhibited spin-forbidden linker transitions and uranyl vibronic progressions, with uranyl excitation and emission being most dominant in NU-1301. Consequently, NU-1301 was a more active photocatalyst than NU-1307. In contrast, the excitation profile from ZnTCPP-U2 contained transitions associated with the porphyrin linker exclusively. Photocatalytic activity from ZnTCPP-U2 significantly underperformed in comparison to that of the other two MOFs. Furthermore, these data suggest that linkers’ photophysical properties can be used to predict the photocatalytic behavior of uranyl-containing MOFs.
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Spectroscopic and electrochemical characterization of a Pr 4+ imidophosphorane complex and the redox chemistry of Nd 3+ and Dy 3+ complexes
Tetravalent praseodymium in a homoleptic imidophosphorane complex is identified and characterized in solution via UV-vis-NIR, cyclic voltammetry, theoretical calculations, and X-band EPR.
Rice, Natalie T.↗
Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field
A redox pair of Ce 4+ and Ce 3+ complexes, isotypic to previously prepared Tb 4+ and Tb 3+ complexes, respectively, is reported to establish a comparative physical and spectroscopic analysis of tetravalent lanthanide ions.
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The chemical and physical properties of tetravalent lanthanides: Pr, Nd, Tb, and Dy
The fundamental redox chemistry and valence electronic structure of the lanthanides in molecular complexes and extended solids continues to be a fertile area of research. The contemporary understanding of the accessible oxidation states of the lanthanide elements and the variability in their electronic structure is the result of several paradigm shifts. While the lanthanide elements have already found widespread use in technical and consumer applications, the continued reevaluation of basic redox properties is a central chemical concern to establish a more complete description of periodic properties. This fundamental understanding of valence electronic structure as it is derived from oxidation state and coordination environment is essential for the continued development of lanthanides in quantum information science and quantum materials research. This review presents the chemical and physical properties of tetravalent lanthanide ions in extended solids and molecules with a focus on the elements apart from cerium: praseodymium, neodymium, terbium, and dysprosium.
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Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex
Not provided.
Chemistry↗