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Abstract The ever‐expanding need for renewable energy can be addressed in part by photocatalytic CO2reduction to give fuels via an artificial photosynthetic process driven by sunlight. A series of rhenium photocatalysts are evaluated in the photocatalytic CO2reduction 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.
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Impact of Internal Charge Transfer on the Photophysical Properties of Pyridine‐Fused Phosphorus‐Nitrogen Heterocycles
Abstract The phosphaquinolinone scaffold has been previously studied as a modular core for a variety of fluorescent species where use of substituent effects has focused on increasing or decreasing electron density in the core rings. We now report the synthesis and analysis of several pyridine‐containing phosphaquinolinone species exhibiting notable linear conjugation from the aryl‐substituent to electron‐withdrawing pyridyl nitrogen. Varying the nature of the aryl substituent from electron‐withdrawing to electron‐donating leads to the generation of an internal charge‐transfer (ICT) band in the absorbance spectrum, which becomes the dominant absorbance in terms of intensity in the most electron‐rich ‐NMe2example. This heterocycle exhibits improved photophysical properties compared to others in the set including high quantum yield and considerably red‐shifted emission. The enhanced ICT can be observed in the X‐ray data where a rare example of molecule co‐planarity is observed. Computational data show increased localization of negative charge on the pyridyl nitrogen as the electron‐donating character of the aryl‐substituent increases.
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- PAR ID:
- 10399890
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 29
- Issue:
- 19
- ISSN:
- 0947-6539
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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