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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
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Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis
Winald R Kitzmann1, Maria-Sophie Bertrams1, Pit Boden2
1Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
Journal of the American Chemical Society
|July 21, 2023
Summary
We developed a stable, photoactive molybdenum complex using simple ligands, enabling sustainable photochemistry. This earth-abundant metal complex demonstrates potential in photon upconversion and photoredox catalysis.
Area of Science:
- Inorganic Chemistry
- Photochemistry
- Sustainable Chemistry
Background:
- Earth-abundant metal complexes are crucial for sustainable photochemistry.
- Sophisticated ligands are often needed for photoactivity in nonprecious metals.
- Developing simpler synthetic routes to photoactive complexes is highly desirable.
Purpose of the Study:
- To synthesize an easily accessible, photoactive complex using a cheap metal and simple ligands.
- To investigate the photophysical properties and stability of the synthesized complex.
- To demonstrate the utility of the complex in photon upconversion and photoredox catalysis.
Main Methods:
- Two-step synthesis of molybdenum(0) carbonyl complex Mo(CO)3(tpe).
- Characterization using time-resolved infrared spectroscopy and laser flash photolysis.
- Photophysical studies including temperature-dependent luminescence and DFT calculations.
- Application studies in photon upconversion and photoredox catalysis.
Main Results:
- Successfully synthesized Mo(CO)3(tpe) with high yield.
- Observed intense deep-red phosphorescence with long excited state lifetimes.
- Identified the lowest excited state as a triplet metal-to-ligand charge-transfer (3MLCT) state.
- Demonstrated high photostability due to ligand configuration.
- Showcased applications in green-to-blue photon upconversion and photoredox dehalogenation.
Conclusions:
- Tripodal carbonyl complexes offer a promising strategy for designing stable photoactive complexes of nonprecious metals.
- This approach avoids complex multi-step syntheses.
- The developed molybdenum complex is versatile for photochemical applications.
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