Related Experiment Videos
Subnanosecond isomerization in an osmium-dimethyl sulfoxide complex
Nicholas V Mockus1, Jeffrey L Petersen, Jeffrey J Rack
1Department of Chemistry and Biochemistry, Ohio University, Athens, 45701, USA.
Inorganic Chemistry
|January 5, 2006
Summary
This study details the structure and photo-reactivity of a novel osmium complex. Visible light triggers rapid S-to-O isomerization in the excited state of cis-bis(2,2′-bipyridine)bis(dimethyl sulfoxide)osmium(II).
Area of Science:
- Inorganic Chemistry
- Photochemistry
- Coordination Chemistry
Background:
- Osmium complexes with bipyridine and sulfoxide ligands are of interest for their photophysical properties.
- Understanding ligand isomerization in metal complexes is crucial for developing new photoactive materials.
Purpose of the Study:
- To characterize the structure, spectroscopy, and electrochemistry of cis-[Os(bpy)(2)(DMSO)(2)](OTf)(2).
- To investigate the photoinduced S-to-O isomerization of the dimethyl sulfoxide (DMSO) ligand in the osmium complex.
Main Methods:
- Synthesis and structural determination of the osmium complex.
- Electrochemical measurements to determine oxidation potentials.
- UV-Vis spectroscopy and luminescence studies to probe excited-state dynamics.
- Time-resolved spectroscopy to analyze isomerization kinetics.
Main Results:
- The structure of cis-[Os(bpy)(2)(DMSO)(2)](OTf)(2) was determined.
- Electrochemical oxidation of Os(2+) occurred at 1.8 V vs Ag/AgCl, preceding S-to-O isomerization.
- Visible light irradiation induced an emissive S-bonded excited state.
- S-to-O isomerization was observed on a subnanosecond timescale in both solid and solution states.
Conclusions:
- The osmium complex exhibits photoinduced S-to-O isomerization of the DMSO ligand.
- The isomerization occurs rapidly from an emissive excited state.
- These findings provide insights into the photochemistry of osmium-sulfoxide systems.