Study of the effects of polyelectrolytes on the photochemical system containing a Ru(bpy)/sub 3//sup 2 +/ derivative, methylviologen, and ferricyanide

Journal Article · Thu Dec 05 04:00:00 EST 1985 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100271a037· OSTI ID:6035995

Sassoon, R E; Rabani, J

A photosensitized electron-transfer system is described in which charge separation of redox products on separate like-charged polyelectrolytes is achieved and considerable retardation of their back reaction is observed. The process of quenching of a polyelectrolyte-anchored Ru(bpy)/sub 3//sup 2 +/ derivative by methylviologen (MV/sup 2 +/) and the quantum yields of electron-transfer products escaping charge recombination followed by their back electron-transfer reaction were studied. Quantum yields were found to be lower and rate constants for the back reaction about the same as the well-studied Ru(bpy)/sub 3//sup 2 +/-MV/sup 2 +/ system. The addition of Fe(CN)/sub 6//sup 3 -/ and the polyelectrolyte, polybrene, to the system was also studied. The rate of electron transfer from MV/sup +/. to ferricyanide in the presence of polybrene was measured and it was found that the rate of back electron transfer from Fe(CN)/sub 6//sup 4 -/ trapped in polybrene to the highly positively charged polyelectrolyte-anchored Ru(bpy)/sub 3//sup 3 +/ could be inhibited by more than 2 orders of magnitude compared to the rate of this reaction in homogeneous solution. This is attributed to the slow diffusion and high electrostatic repulsion between the polyelectrolyte-trapped species. The role played by counterions in this system is also critically assessed and ways to achieve more effective inhibition in two-polyelectrolyte systems are discussed. 25 references, 5 figures, 4 tables.

• Research Organization: Hebrew Univ. of Jerusalem, Israel
• OSTI ID: 6035995
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:25; ISSN JPCHA
• Country of Publication: United States
• Language: English

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AZINES
BIPYRIDINES
CHEMICAL REACTION KINETICS
COMPLEXES
DATA
DE-EXCITATION
ELECTROLYTES
ELECTRON TRANSFER
ENERGY STORAGE
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXPERIMENTAL DATA
FERRICYANIDES
HETEROCYCLIC COMPOUNDS
INFORMATION
IRON COMPLEXES
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PERFORMANCE
PHOTOCHEMICAL ENERGY STORAGE
PYRIDINES
RADIATIONLESS DECAY
REACTION KINETICS
RUTHENIUM COMPLEXES
STORAGE
TRANSITION ELEMENT COMPLEXES