Electron-transfer kinetics of contacting monolayers
- Univ. of North Carolina, Chapel Hill (USA)
The rates of electron-transfer reactions between the monolayers of metal complexes in contact at polymer/polymer interfaces have been evaluated for the thermodynamically disfavored cross-reactions poly(Os(bpy){sub 2}(vpy)Cl){sup 2+} + poly(Os(bpy){sub 2}(vpy){sub 2}){sup 2+}, poly(Os(bpy){sub 2}(vpy){sub 2}){sup 3+} + poly(Ru(vbpy){sub 3}){sup 2+}, and poly(Os(bpy){sub 2}(vpy){sub 2}){sup 3+} + poly(Ru(bpy){sub 2}(vpy){sub 2}){sup 2+}. An analysis of the interfacial electron-transfer rates that accounts for the thermodynamically favored back-reaction gives rate constants 2.8 {times} 10{sup 3}, 1.1 {times} 10{sup 3}, and 2 {times} 10{sup 2} M{sup {minus}1} s{sup {minus}1}. The second of these three reactions was studied with the two polymer films both in contact and separated by a metal junction, with no discernable difference in the results. The metal-separated experiment allowed examination of the polymer/polymer junction's interfacial potential, which is interpreted as a mixed potential.
- OSTI ID:
- 6949595
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:3; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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360104* -- Metals & Alloys-- Physical Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400 -- Electrochemistry
COMPLEXES
DATA
DATA ANALYSIS
ELECTRON TRANSFER
ELEMENTS
EXPERIMENTAL DATA
FILMS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
NUMERICAL DATA
OSMIUM COMPLEXES
PLATINUM METALS
POLYMERS
REACTION KINETICS
RUTHENIUM
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
VOLTAMETRY