Mechanism of the quenching of the tris(bipyridine)ruthenium(II) emission by persulfate

Implications for photoinduced oxidation reactions

A. Lewandowska-Andralojc, Dmitry Polyansky

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

A revised mechanism for the oxidation of the excited state of Ru(bpy) 3 2+ with the persulfate anion is described in this work. The formation of the precursor complex in the electron transfer reaction involves ion pairing between the metal complex in ground and excited states and S2O8 2-. The equilibrium constant for the ion-pair formation (KIP = 2.7 M-1) was determined from electrochemical measurements and analysis of thermal reaction between Ru(bpy)3 2+ and persulfate. It was found to be consistent with the calculated value estimated from the Debye-Hückel model. The analysis of rate constants for reactions between persulfate and various metal complexes indicates that thermal and photochemical reactions most likely proceed through a common pathway. Extremely high reorganization energy (ca. 3.54 eV) for the electron transfer obtained from fitting experimental data with the Marcus equation is indicative of significant nuclear reorganization during the electron transfer step. In view of these results the electron transfer can be described as dissociative probably involving substantial elongation or complete scission of the O-O bond. The proposed model accurately describes experimental results for the quenching of Ru(bpy)3 2+ over a wide range of persulfate concentrations and resolves some discrepancies between the values of KIP and ket previously reported. The implications of various factors such as the ionic strength and dielectric constant of the medium are discussed in relation to measurements of the quantum yields in photodriven oxidation reactions employing the Ru(bpy)3 2+/persulfate couple.

Original languageEnglish
Pages (from-to)10311-10319
Number of pages9
JournalJournal of Physical Chemistry A
Volume117
Issue number40
DOIs
Publication statusPublished - Oct 10 2013

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Ruthenium
ruthenium
Quenching
quenching
electron transfer
Oxidation
oxidation
Electrons
Coordination Complexes
Excited states
Ions
Photochemical reactions
Equilibrium constants
Quantum yield
Ionic strength
Ground state
Anions
Elongation
Rate constants
Permittivity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Mechanism of the quenching of the tris(bipyridine)ruthenium(II) emission by persulfate : Implications for photoinduced oxidation reactions. / Lewandowska-Andralojc, A.; Polyansky, Dmitry.

In: Journal of Physical Chemistry A, Vol. 117, No. 40, 10.10.2013, p. 10311-10319.

Research output: Contribution to journalArticle

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