Oligomer and mixed-metal compounds potential multielectron transfer catalysts

Technical Report · Mon Mar 30 04:00:00 EST 1992

DOI:https://doi.org/10.2172/5573583· OSTI ID:5573583

Rillema, D. P.

Projects related to the design and characterization of multimetallic complexes has proceeded forward with a number of achievements. First, photoprocesses in hydrogel matrices lead to the conclusion that cationic metallochromophores could be ion exchanged into a hydrogel matrix ({kappa}-carageenan) and substantial photocurrents could be generated. Second, X-ray structures of Ru(bpy){sub 3}{sup 2+}, Ru(bpm){sub 3}{sup 2+} and Ru(bpz){sub 3}{sup 2+}, where bpy is 2,2{prime}-bipyridine, bpm is 2,2{prime}-bipyrimidine and bpz is 2,2{prime}-bipyrizine, were obtained and revealed similar Ru-N bond distances in each complex even though their {sigma}-donor and {pi}-acceptor character differ markedly. The structure parameters are expected to provide theoreticians with the information needed to probe the electronic character of the molecular systems and provide us with direction in our synthetic strategies. Third, a copper(I) complex was synthesized with a dimeric-ethane-bridged, 1,10-phenanthroline ligand that resulted in isolation of a bimetallic species. The copper(I) complex did luminesce weakly, suggesting that the dimer possesses potential electron transfer capability. Fourth, the photophysical properties of (Re(CO){sub 4}(L-L)){sup +}, where L-L = heterocyclic diimine ligands, and Pt(bph)X{sub 2}, where bph = the dianion of biphenyl and X = CH{sub 3}CN, py or ethylendiamine, displayed luminescence at high energy and underwent excited-state electron transfer. Such high energy emitters provide high driving forces for undergoing excited-state electron transfer. Fifth, both energy and electron transfer were observed in mixed-metal complexes bridged by 1,2-bis(2,2{prime}-bipyridyl-4{prime}-yl) ethane.

• Research Organization: North Carolina Univ., Charlotte, NC (United States). Dept. of Chemistry
• Sponsoring Organization: DOE; USDOE, Washington, DC (United States)
• DOE Contract Number: FG05-84ER13263
• OSTI ID: 5573583
• Report Number(s): DOE/ER/13263-8; ON: DE92011347
• Country of Publication: United States
• Language: English

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AROMATICS
AZAARENES
AZINES
BIPYRIDINES
BOND LENGTHS
CHEMICAL PREPARATION
COMPLEXES
COPPER COMPLEXES
CURRENTS
DIMENSIONS
DOCUMENT TYPES
ELECTRIC CURRENTS
ELECTRON TRANSFER
HETEROCYCLIC COMPOUNDS
LENGTH
LUMINESCENCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENANTHROLINES
PHOTOCURRENTS
PROGRESS REPORT
PYRIDINES
RHENIUM COMPLEXES
RUTHENIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES