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Pyrazine-Functionalized Ru(II)-Complexes as Visible-Light Activated Photobases.

Niklas Klosterhalfen1,2, Nishi Singh3,4, Michael Jäger3,4

  • 1Department Functional Interfaces, Leibniz Institute of Photonic Technology (Leibniz-IPHT), Albert-Einstein-Str. 9, Jena, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|April 29, 2025
PubMed
Summary

Ruthenium complexes enable reversible excited-state proton transfer (ESPT) in visible light. These novel metal photobases exhibit a significant pKa change and rapid proton transfer within picoseconds.

Keywords:
Ru(II) complexes as photobasesexcited‐state proton transferphotophysical and theoretical studiessynthesis and characterizationultrafast spectroscopy

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Area of Science:

  • Photochemistry
  • Coordination Chemistry
  • Physical Chemistry

Background:

  • Excited-state proton transfer (ESPT) significantly alters acid/base properties (up to 10 pKa units) upon photoexcitation.
  • Organic photobases have limitations like single use or UV absorption dependence.
  • Metal complex-based photobases offer advantages, including visible light activation and reversible processes.

Purpose of the Study:

  • To synthesize novel Ruthenium(II)-complexes with pyrazine-functionalized polypyridyl ligands.
  • To investigate the photobasic properties and ESPT mechanisms of these complexes.
  • To explore the potential of metal complexes for reversible photobase generation.

Main Methods:

  • Synthesis of two novel Ruthenium(II)-complexes.
  • Ultrafast spectroscopy to study excited-state proton transfer dynamics.
  • Theoretical calculations to complement experimental findings.

Main Results:

  • Metal-to-ligand charge transfer (MLCT) excitation in aqueous solution induced a ΔpKa of 9 units.
  • The ESPT process was observed to occur within approximately 300 picoseconds.
  • Ruthenium complexes demonstrated efficient and reversible photobasic properties.

Conclusions:

  • Novel Ruthenium(II)-complexes are effective visible-light-activated photobases.
  • These complexes facilitate rapid and reversible excited-state proton transfer.
  • Metal complex-based photobases present a promising alternative to organic counterparts.