The ever-expanding need for renewable energy can be addressed in part by photocatalytic CO2 reduction to give fuels via an artificial photosynthetic process driven by sunlight. A series of rhenium photocatalysts are evaluated in the photocatalytic CO2 reduction reaction and via photophysical, electrochemical, and computational studies. The impact of various electron withdrawing substituents on the aryl group of the pyNHC-aryl ligand along with the impact of extending conjugation along the backbone of the ligand is analyzed. A strong correlation between excited-state lifetimes, photocatalytic rates, and computationally determined dissociation energy of the labile ligand of these complexes is observed. Additionally, computed orbital analysis provides an added understanding, which allows for prediction of the potential impact of an electron withdrawing substituent on photocatalysis.
|Number of pages||9|
|State||Published - Apr 2021|
Bibliographical noteFunding Information:
HS and JHD thank the National Science Foundation (NSF) for supporting this work with award 1800281. NL, LEM, SAA, NIH, and JHD thank NSF for award 1539035 under which initial data was collected. TMS, MAP, and GST acknowledge supported from the National Science Foundation (CHE‐1338056 and CHE‐1664998) and also thank the Mississippi Center for Supercomputing Research (MCSR) for a generous allocation of time on their computational resources. The D8 Venture diffractometer was funded by the NSF (MRI CHE1625732 to SP).
© 2021 Wiley-VCH GmbH
- carbene ligands
- carbon dioxide
- density functional calculations
ASJC Scopus subject areas
- Analytical Chemistry
- Physical and Theoretical Chemistry
- Organic Chemistry