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Perturbation of the host and guest excited-state properties of derivatives of the lamellar solid hydrogen uranyl phosphate

Thesis/Dissertation ·
OSTI ID:6771824
Chapter 1. A background of intercalation chemistry of inorganic solids is summarized and a general overview of the excited-state properties of inorganic compounds is provided. In addition, a summary of UO/sub 2//sup 2 +/ excited-state chemistry and the known intercalation chemistry of hydrogen uranyl phosphate (HUP) is presented. Chapter 2. This chapter deals with lanthanon-substituted derivatives of HUP. It has been found that a large number of Ln/sup 3 +/ ions (Ln = La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, and Yb) will fully substitute into HUP, yielding a family of solids with a variety of excited-state properties. Chapter 3. Several types of coordination complexes intercalate into HUP. For example CrL/sub 6//sup 3 +/-substituted (L = N or O donor) derivatives of HUP exhibit photochemistry that can be compared to CrL/sub 6//sup 3 +/ solution chemistry. Substitution with Ru(2,2'-bipyridine)/sub 3//sup 2 +/ leads to redox chemistry in HUP, involving shuttling between the Ru(II) and Ru(III) oxidation states. Lastly, co-intercalation of HUP with two species leads to compounds with novel properties. Chapter 4. The Creutz-Taube (C-T) complex, ((NH/sub 3/)/sub 5/Ru(..mu..-pyrazine)Ru(NH/sub 3/)/sub 5/)/sup 5 +/ can be intercalated into HUP to yield hydrated, partially-substituted lamellar solids of approximate composition H/sub 1-5x/(C-T)/sub x/UO/sub 2/PO/sub 4/ (0.001 < x < 0.01). These solids have intriguing excited-state properties. Furthermore, exposure to Br/sub 2/ causes spectral changes consistent with oxidation of the Creutz-Taube ion.
Research Organization:
Wisconsin Univ., Madison (USA)
OSTI ID:
6771824
Country of Publication:
United States
Language:
English