Probing the Effects of Electron Deficient Aryl Substituents and a π-System Extended NHC Ring on the Photocatalytic CO2 Reduction Reaction with Re-pyNHC-Aryl Complexes**

Hunter Shirley; Thomas More Sexton; Nalaka P. Liyanage; Morgan A. Perkins; Shane A. Autry; Louis E. McNamara; Nathan I. Hammer; Sean R. Parkin; Gregory S. Tschumper; Jared H. Delcamp

doi:10.1002/cptc.202000296

Probing the Effects of Electron Deficient Aryl Substituents and a π-System Extended NHC Ring on the Photocatalytic CO₂ Reduction Reaction with Re-pyNHC-Aryl Complexes**

Hunter Shirley, Thomas More Sexton, Nalaka P. Liyanage, Morgan A. Perkins, Shane A. Autry, Louis E. McNamara, Nathan I. Hammer, Sean R. Parkin, Gregory S. Tschumper, Jared H. Delcamp

Chemistry

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	353-361
Number of pages	9
Journal	ChemPhotoChem
Volume	5
Issue number	4
DOIs	https://doi.org/10.1002/cptc.202000296
State	Published - Apr 2021

Bibliographical note

Funding 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).

Publisher Copyright:
© 2021 Wiley-VCH GmbH

Keywords

carbene ligands
carbon dioxide
catalysis
density functional calculations
photocatalysis
rhenium

ASJC Scopus subject areas

Analytical Chemistry
Physical and Theoretical Chemistry
Organic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/cptc.202000296

Cite this

Shirley, H., Sexton, T. M., Liyanage, N. P., Perkins, M. A., Autry, S. A., McNamara, L. E., Hammer, N. I., Parkin, S. R., Tschumper, G. S., & Delcamp, J. H. (2021). Probing the Effects of Electron Deficient Aryl Substituents and a π-System Extended NHC Ring on the Photocatalytic CO₂ Reduction Reaction with Re-pyNHC-Aryl Complexes**. ChemPhotoChem, 5(4), 353-361. https://doi.org/10.1002/cptc.202000296

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abstract = "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.",

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author = "Hunter Shirley and Sexton, {Thomas More} and Liyanage, {Nalaka P.} and Perkins, {Morgan A.} and Autry, {Shane A.} and McNamara, {Louis E.} and Hammer, {Nathan I.} and Parkin, {Sean R.} and Tschumper, {Gregory S.} and Delcamp, {Jared H.}",

note = "Funding 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). Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

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Shirley, H, Sexton, TM, Liyanage, NP, Perkins, MA, Autry, SA, McNamara, LE, Hammer, NI, Parkin, SR, Tschumper, GS & Delcamp, JH 2021, 'Probing the Effects of Electron Deficient Aryl Substituents and a π-System Extended NHC Ring on the Photocatalytic CO₂ Reduction Reaction with Re-pyNHC-Aryl Complexes**', ChemPhotoChem, vol. 5, no. 4, pp. 353-361. https://doi.org/10.1002/cptc.202000296

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