Synthesis, structure, and photochemistry of a novel rhenium (I) enolate and photochemistry and second harmonic generation in Langmuir-Blodgett films
A background of cyclopentadienyl ring-slippage reactions is presented along with a brief discussion of the transformations of the related indenyl and fluorenyl ligands. Subsequently a review of oxygen-bonded transition metal enolate complexes is given. Synthesis, structure, and photochemistry of fac-(CO)/sub 3/(P(CH/sub 3/)/sub 3/)/sub 2/Re(OC(CH/sub 3/)C/sub 5/H/sub 4/), 5, is presented. The Re(I) enolate complex was prepared from the reaction of (eta/sup 5/-C/sub 5/H/sub 4/C(O)CH/sub 3/)Re(CO)/sub 3/, 4, with P(CH/sub 3/)/sub 3/. Compound 5 was characterized structurally in the solid state by x-ray crystallography and in solution by ir, and /sup 1/H, /sup 13/C, and /sup 31/P NMR spectroscopy. Photolysis of 5 at 337 nm in CH/sub 2/Cl/sub 2/ solution cleaves the Re-O bond: smooth conversion to fac-(CO)/sub 3/(P(CH/sub 3/)/sub 3/)/sub 2/ReCl, 6, is observed with a quantum yield of 0.04. The photochemistry of 5 in benzene solution and the synthesis and photochemistry of fac-(CO)/sub 3/(P(CH/sub 3/)/sub 2/-Re(OC(CH/sub 3/)C/sub 5/H/sub 3/CH/sub 3/), 14, is also presented. The Langmuir-Blodgett method of monolayer film formation, characteristics of good film formation and structure of the supported film are reviewed. The basics of second harmonic generation are also presented along with useful applications of the Langmuir-Blodgett films to these studies. Synthesis, structure, and photochemistry of Langmuir-Blodgett stearate films incorporated the emissive Eu/sup 3 +/ and UO/sub 2//sup 2 +/ cations are described. A mixed film containing UO/sub 2/2/sup +//stearate and Eu/sup 3 +//stearate in alternating layers exhibited energy transfer from the UO/sub 2//sup 2 +/ ions to the Eu/sup 3 +/ ions.
- Research Organization:
- Wisconsin Univ., Madison (USA)
- OSTI ID:
- 5774484
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CATIONS
MOLECULAR STRUCTURE
PHOTOCHEMISTRY
SYNTHESIS
ENOLS
EUROPIUM COMPOUNDS
FILMS
RHENIUM COMPLEXES
URANYL COMPOUNDS
ACTINIDE COMPOUNDS
ALCOHOLS
CHARGED PARTICLES
CHEMISTRY
COMPLEXES
HYDROXY COMPOUNDS
IONS
ORGANIC COMPOUNDS
RARE EARTH COMPOUNDS
TRANSITION ELEMENT COMPLEXES
URANIUM COMPOUNDS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials
400201 - Chemical & Physicochemical Properties
400500 - Photochemistry