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**

被引：5

作者：

Shirley, Hunter ^{[1
]}

Sexton, Thomas More ^{[1
]}

Liyanage, Nalaka P. ^{[1
]}

Perkins, Morgan A. ^{[1
]}

Autry, Shane A. ^{[1
]}

McNamara, Louis E. ^{[1
]}

Hammer, Nathan I. ^{[1
]}

Parkin, Sean R. ^{[2
]}

Tschumper, Gregory S. ^{[1
]}

Delcamp, Jared H. ^{[1
]}

机构：

[1] Univ Mississippi, Dept Chem & Biochem, 322 Coulter Hall, University, MS 38677 USA

[2] Univ Kentucky, Dept Chem, 125 Chem Phys Bldg, Lexington, KY 40506 USA

来源：

CHEMPHOTOCHEM | 2021年 / 5卷 / 04期

基金：

美国国家科学基金会;

关键词：

carbene ligands; carbon dioxide; catalysis; density functional calculations; photocatalysis; rhenium; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; EXCITATION-ENERGIES; ELECTROCATALYTIC REDUCTION; METAL-COMPLEXES; EXCITED-STATES; CARBON; APPROXIMATION; CONVERSION; CATALYSIS;

D O I：

10.1002/cptc.202000296

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：353 / 361

页数：9

共 65 条

[1] Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].

Adamo, C ;

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170

[2]

Agarwal J., 2014, Angew. Chem, V126, P5252

[3] NHC-Containing Manganese(I) Electrocatalysts for the Two-Electron Reduction of CO2 [J].

Agarwal, Jay ;

Shaw, Travis W. ;

Stanton, Charles J., III ;

Majetich, George F. ;

Bocarsly, Andrew B. ;

Schaefer, Henry F., III .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (20) :5152-5155

[4]

[Anonymous], 2016, ANGEW CHE

[5] Catalysis for the Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials, and Fuels. Technological Use of CO2 [J].

Aresta, Michele ;

Dibenedetto, Angela ;

Angelini, Antonella .

CHEMICAL REVIEWS, 2014, 114 (03) :1709-1742

[6] Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis? [J].

Artero, Vincent ;

Fontecave, Marc .

CHEMICAL SOCIETY REVIEWS, 2013, 42 (06) :2338-2356

[7] Ruthenium(II) complexes of pyridinol and N-heterocyclic carbene derived pincers as robust catalysts for selective carbon dioxide reduction [J].

Boudreaux, Chance M. ;

Liyanage, Nalaka P. ;

Shirley, Hunter ;

Siek, Sopheavy ;

Gerlach, Deidra L. ;

Qu, Fengrui ;

Delcamp, Jared H. ;

Papish, Elizabeth T. .

CHEMICAL COMMUNICATIONS, 2017, 53 (81) :11217-11220

[8] A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen [J].

Carpenter, Casey A. ;

Brogdon, Phillip ;

McNamara, Louis E. ;

Tschumper, Gregory S. ;

Hammer, Nathan I. ;

Delcamp, Jared H. .

INORGANICS, 2018, 6 (01)

[9] Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold [J].

Casida, ME ;

Jamorski, C ;

Casida, KC ;

Salahub, DR .

JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (11) :4439-4449

[10] Highly Active Ruthenium CNC Pincer Photocatalysts for Visible-Light-Driven Carbon Dioxide Reduction [J].

Das, Sanjit ;

Rodrigues, Roberta R. ;

Lamb, Robert W. ;

Qu, Fengrui ;

Reinheimer, Eric ;

Boudreaux, Chance M. ;

Webster, Charles Edwin ;

Delcamp, Jared H. ;

Papish, Elizabeth T. .

INORGANIC CHEMISTRY, 2019, 58 (12) :8012-8020

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