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Updated: May 15, 2026

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Published on: July 19, 2019

Accelerating slow excited state proton transfer.

David J Stewart1, Javier J Concepcion, M Kyle Brennaman

  • 1Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599, USA.

Proceedings of the National Academy of Sciences of the United States of America
|January 2, 2013
PubMed
Summary
This summary is machine-generated.

This study investigates a ruthenium complex

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Area of Science:

  • Inorganic Chemistry
  • Photochemistry
  • Physical Chemistry

Background:

  • Ruthenium polypyridyl complexes are widely studied for their photophysical properties.
  • Ligand-bridged dinuclear ruthenium assemblies offer tunable electronic and redox properties.
  • Understanding excited-state dynamics and proton transfer is crucial for developing functional materials.

Purpose of the Study:

  • To investigate the excited-state properties and proton transfer dynamics of a specific ligand-bridged dinuclear ruthenium assembly.
  • To determine the quenching mechanisms and kinetics of the excited state by anions.
  • To illustrate kinetically limiting proton transfer processes.

Main Methods:

  • Visible light excitation of the ruthenium assembly.
  • Emission spectroscopy and lifetime measurements.
  • Stern-Volmer analysis for quenching studies.
  • pH control and buffering for proton transfer investigations.

Main Results:

  • The excited state exhibits a lifetime of 13 ± 1 ns.
  • Quenching by phosphate and acetate anions was observed, with rate constants determined.
  • An estimated pK(a)* of ~5 ± 1 for the excited state was determined.
  • Kinetically limiting proton transfer rates were measured, demonstrating slow proton transfer.

Conclusions:

  • The ligand-bridged dinuclear ruthenium assembly displays interesting photophysical and proton transfer behavior.
  • Anion interactions significantly influence the excited-state lifetime and decay pathways.
  • The study provides a clear example of slow proton transfer relevant to various chemical and biological systems.