Concentration effects on the quenching of tris(2,2'-bipyridine)ruthenium(II) emission in polyvinylsulfate solutions

Journal Article · Thu May 04 04:00:00 EDT 1978 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100498a004· OSTI ID:6730456

Meisel, D; Rabani, J; Meyerstein, D; Matheson, M S

The effect of polyvinylsulfate (PVS) on the photoinitiated electron transfer reaction from the lowest charge transfer state of Ru(bpy)/sub 3//sup 2 +/* to Fe(III) and on its dark back reaction was studied under various conditions. A large acceleration of both reactions was observed which can be attributed to concentrating both reacting cations into the field of the polyelectrolyte. However, for the electron transfer from Ru(bpy)/sub 3//sup 2 +/* to Fe(III), the rate constant (normalized for the concentrating ''volume effect'') was found to increase linearly with the concentration of Fe(III) per polymer molecule up to 25% coverage. Fe(III) complexes with the sulfate groups of PVS, and it seems certain that the increase in the rate constant has its origin in the bonding or chelating of the Fe(III). Possible explanations of the increase are discussed. At high coverage of the polymer by Fe(III) the rate constant starts to drop, most probably due to configurational changes of the polymer induced by the cations. The initial yield of the electron transfer remains unchanged by the addition of PVS while the back reaction was greatly enhanced. In cases where an average of one or less pairs of products were produced per polymer chain a large contribution to the back reaction from a first-order rate law could be observed. As the number of product pairs per polymer molecule increased the dominant portion of this reaction followed a second-order rate law. 2 figures, 2 tables, 31 references.

• Research Organization: Argonne National Lab., IL
• OSTI ID: 6730456
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 82:9; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKALI METAL COMPLEXES
AQUEOUS SOLUTIONS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CONFIGURATION INTERACTION
DECOMPOSITION
DISPERSIONS
ELECTRON TRANSFER
EMISSION SPECTRA
ESTERS
HEAT TREATMENTS
IONS
IRON COMPOUNDS
KINETICS
MEDIUM TEMPERATURE
MIXTURES
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
QUANTITY RATIO
QUENCHING
REACTION KINETICS
RUBIDIUM COMPLEXES
SAMPLE PREPARATION
SOLUTIONS
SOLVENT PROPERTIES
SPECTRA
SULFURIC ACID ESTERS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPOUNDS