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Exploring the Photophysics and Photocatalytic Activity of Heteroleptic Rh(III) Transition-Metal Complexes Using
Stephen DiLuzio1, Mitchell Baumer1, Rafael Guzman1
1Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
Inorganic Chemistry
|July 20, 2024
Summary
High-throughput synthesis revealed novel Rh(III) complexes with long-lived phosphorescence. These rhodium complexes show potential as photocatalysts, outperforming iridium counterparts in water reduction systems.
Area of Science:
- Inorganic Chemistry
- Photochemistry
- Materials Science
Background:
- Transition metal photophysics, particularly for 4d metals like Rh(III), are often limited by metal-centered deactivation pathways.
- Heteroleptic complexes offer tunable photophysical properties, but Rh(III) complexes are less explored than Ir(III) counterparts.
- Efficient photoactive chromophores are crucial for applications in catalysis and light-harvesting.
Purpose of the Study:
- To investigate the photophysical properties of a large library of heteroleptic Rh(III) complexes.
- To discover Rh(III) complexes with long-lived phosphorescence and potential photocatalytic activity.
- To compare the photophysical and photocatalytic performance of Rh(III) complexes with well-established Ir(III) complexes.
Main Methods:
- High-throughput synthesis and screening (HTSS) of 576 heteroleptic Rh(III) complexes.
- Measurement of UV-visible absorption, excited-state lifetime, and phosphorescence emission spectra.
- Photophysical, electrochemical, and photocatalytic (water reduction) investigations.
Main Results:
- Discovery of photoactive Rh(III) complexes with long-lived charge-transfer phosphorescence (0.15-0.95 μs) in the visible region (546-620 nm) at room temperature.
- Identification of Rh(III) complexes with properties suitable for photocatalysis.
- Rh(III) photocatalysts demonstrated activity in a water reduction system, sometimes surpassing that of analogous Ir(III) photocatalysts.
Conclusions:
- Structurally diverse ligands in heteroleptic Rh(III) complexes can overcome typical deactivation pathways, leading to efficient photoactivity.
- Rhodium(III) complexes represent a promising, yet often overlooked, class of transition metals for developing advanced photoactive materials and photocatalysts.
- This study highlights the potential of Rh(III) complexes as efficient chromophores and photocatalysts, particularly in water reduction systems.
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