Energy- and electron-transfer shuttling by a soluble, bifunctional redox polymer

Journal Article · Thu Jan 10 04:00:00 EST 1991 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100154a085· OSTI ID:5796368

Younathan, J N; Jones, Jr, W E; Meyer, T J ^[1]

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1. Univ. of North Carolina, Chapel Hill (USA)

A soluble, bifunctional polymer ((PS-An{sub 28.5}PTZ{sub 1.5})) based on derivatized polystyrene was prepared in which there are both energy-transfer acceptors (modified anthracene, An) and electron-transfer donors (derivatized phenothiazene, PTZ). The polymer was successfully incorporated into a photochemical electron-transfer sequence based on (Ru(BPY){sub 3}){sup 2+} (bpy is 2,2{prime}-bipyridine) in which separate oxidative and reductive equivalents were generated in solution. In the sequence, sensitized formation of the triplet excited state of the polymer-bound anthryl sites ((PS-{sup 3}An*An{sub 27.5}PTZ{sub 1.5})) occurred by diffusion and energy transfer from (Ru(bpy){sub 3}){sup 2+}* following visible excitation of (Ru(bpy){sub 3}){sup 2+}. In the presence of the oxidative quencher paraquat (PQ{sup 2+}), a series of electron-transfer steps led, ultimately, to the appearance of (PS-An{sub 28.5}PTZ{sup +}PTZ{sub 0.5}) and monomeric PQ{sup +} in solution. The recombination rate constant between PQ{sup +} and (PS-An{sub 28.5}PTZ{sup +}PTZ{sub 0.5}) was reduced by a factor of {approximately} 7 relative to back electron transfer between the unbound, 10-methylphenothiazene cation (10-MePTZ{sup +}) and PQ{sup +}.

• DOE Contract Number: FG05-86ER13633
• OSTI ID: 5796368
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 95:1; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
140505* -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTRON TRANSFER
ENERGY TRANSFER
EXPERIMENTAL DATA
INFORMATION
MATERIALS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC POLYMERS
PETROCHEMICALS
PETROLEUM PRODUCTS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PLASTICS
POLYMERS
POLYOLEFINS
POLYSTYRENE
POLYVINYLS
RUTHENIUM COMPLEXES
SYNTHETIC MATERIALS
TRANSITION ELEMENT COMPLEXES