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Updated: Feb 11, 2026
10:51
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
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Efficient, Reversible Redox-Switching of Molecular First Hyperpolarizabilities in Ruthenium(II) Complexes Possessing
Benjamin J Coe1, Stephan Houbrechts2, Inge Asselberghs2
1Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (UK), Fax: (+44) 161-275-4598.
Angewandte Chemie (International Ed. in English)
|May 2, 2018
Summary
Switching nonlinear optical (NLO) properties of ruthenium complexes is achieved by altering their oxidation state. This metal-to-ligand charge-transfer (MLCT) switching offers tunable NLO responses for advanced materials.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Photophysics
Background:
- Metal-to-ligand charge-transfer (MLCT) excitations are crucial for large molecular nonlinear optical (NLO) coefficients.
- Ruthenium complexes with bipyridinium ligands exhibit significant NLO properties.
Purpose of the Study:
- To investigate the switching of NLO properties in ruthenium complexes by modulating their oxidation states.
- To quantify the NLO response changes upon chemical oxidation and reduction.
Main Methods:
- Synthesis of [RuII(NH3)5(N-R-4,4'-bipyridinium)]3+ complexes.
- Electrochemical oxidation and re-reduction studies.
- Measurement of nonlinear optical (NLO) coefficients (β).
Main Results:
- Low-energy MLCT excitations correlate with large NLO coefficients (β).
- Chemical oxidation to RuIII bleaches MLCT absorptions and reduces NLO responses.
- Re-reduction fully restores NLO properties, with a 10- to 20-fold switching range.
Conclusions:
- Ruthenium-bipyridinium complexes demonstrate reversible switching of NLO properties via redox control.
- This switching mechanism, based on MLCT band modulation, is promising for developing tunable NLO materials.
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