A study of the effects of polyelectrolytes on the photochemical system containing a Ru(bpy)32+ derivative, methylviologen, and ferricyanide

Richard E. Sassoon*, Joseph Rabani

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

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)32+ derivative by methylviologen (MV2+) 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)32+-MV2+ system. The addition of Fe(CN)63- and the polyelectrolyte, polybrene, to the system was also studied. The rate of electron transfer from MV+• to ferricyanide in the presence of polybrene was measured and it was found that the rate of back electron transfer from Fe(CN)64- trapped in polybrene to the highly positively charged polyelectrolyte-anchored Ru(bpy)33+ 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.

Original languageEnglish
Pages (from-to)5500-5504
Number of pages5
JournalJournal of Physical Chemistry
Volume89
Issue number25
DOIs
StatePublished - 1985

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