Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand

Sergei V. Lymar, Mehmed Z. Ertem, Anna Lewandowska-Andralojc, Dmitry E. Polyansky

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Electron-proton transfer (EPT) from phenols to a triplet metal-to-ligand charge transfer (MLCT)-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to inconsistent data analysis. Control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.

Original languageEnglish
Pages (from-to)4043-4048
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume8
Issue number17
DOIs
Publication statusPublished - Sep 7 2017

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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