The ability to synthetically tune the ligand frameworks of redox-active molecules is of critical importance to the economy of solar fuels because manipulating their redox properties can afford control over the operating potentials of sustained electrocatalytic or photoelectrocatalytic processes. The electronic and steric properties of 2,2′:6′,2″-terpyridine (Terpy) ligand frameworks can be tuned by functional group substitution on ligand backbones, and these correlate strongly to their Hammett parameters. The synthesis of a new series of tridentate meridional ligands of 2,4,6-trisubstituted pyridines that engineers the ability to finely tune the redox potentials of cobalt complexes to more positive potentials than that of their Terpy analogs is achieved by aryl-functionalizing at the four-position and by including isoquinoline at the two- and six-positions of pyridine (Aryl-DiQ). Their cobalt complex syntheses, their electronic properties, and their catalytic activity for carbon dioxide (CO2) reduction are reported and compared to their Terpy analogs. The cobalt derivatives generally experience a positive shift in their redox features relative to the Terpy-based analogs, covering a complementary potential range. Although those evaluated fail to produce any quantifiable products for the reduction of CO2 and suffer from long-term instability, these results suggest possible alternate strategies for stabilizing these compounds during catalysis. We speculate that lower equilibrium association constants to the cobalt center are intrinsic to these ligands, which originate from a steric interaction between protons on the pyridine and isoquinoline moieties. Nevertheless, the new Aryl-DiQ ligand framework has been engineered to selectively tune homoleptic cobalt complexes’ redox potentials.
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21 November 2023
Research Article|
November 20 2023
Sterically attenuated electronic communication in cobalt complexes of meridional isoquinoline-derived ligands for applications in electrocatalysis Available to Purchase
Special Collection:
The Physical Chemistry of Solar Fuels Catalysis
Amelia G. Reid
;
Amelia G. Reid
(Data curation, Formal analysis, Investigation, Writing – review & editing)
1
Department of Chemistry, University of Virginia
, Charlottesville, Virginia 22904-4319, USA
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Megan E. Moberg
;
Megan E. Moberg
(Investigation)
1
Department of Chemistry, University of Virginia
, Charlottesville, Virginia 22904-4319, USA
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Connor A. Koellner
;
Connor A. Koellner
(Investigation)
1
Department of Chemistry, University of Virginia
, Charlottesville, Virginia 22904-4319, USA
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Charles W. Machan
;
Charles W. Machan
a)
(Data curation, Formal analysis, Funding acquisition, Supervision, Writing – review & editing)
1
Department of Chemistry, University of Virginia
, Charlottesville, Virginia 22904-4319, USA
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Diana A. Thornton
;
Diana A. Thornton
(Data curation, Formal analysis, Resources, Writing – review & editing)
2
Virginia Tech, Department of Chemistry
, Blacksburg, Virginia 24060, USA
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John C. Dickenson
;
John C. Dickenson
(Formal analysis, Investigation, Writing – original draft)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
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Jeffry J. Stober
;
Jeffry J. Stober
(Investigation)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
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David A. Turner
;
David A. Turner
(Data curation)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
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Travis J. Tarring
;
Travis J. Tarring
(Investigation, Writing – original draft)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
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Caleb A. Brown
;
Caleb A. Brown
b)
(Data curation, Formal analysis, Visualization, Writing – review & editing)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
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Daniel P. Harrison
Daniel P. Harrison
c)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Project administration, Visualization, Writing – original draft, Writing – review & editing)
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
c)Author to whom correspondence should be addressed: [email protected]
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Amelia G. Reid
1
Megan E. Moberg
1
Connor A. Koellner
1
Charles W. Machan
1,a)
Diana A. Thornton
2
John C. Dickenson
3
Jeffry J. Stober
3
David A. Turner
3
Travis J. Tarring
3
Caleb A. Brown
3,b)
Daniel P. Harrison
3,c)
1
Department of Chemistry, University of Virginia
, Charlottesville, Virginia 22904-4319, USA
2
Virginia Tech, Department of Chemistry
, Blacksburg, Virginia 24060, USA
3
Virginia Military Institute, Department of Chemistry
, Lexington, Virginia 24450, USA
c)Author to whom correspondence should be addressed: [email protected]
a)
Electronic mail: [email protected]
b)
Present address: Sweet Briar College, Division of Science, Technology, Engineering and Math, Sweet Briar, Virginia 24595, USA.
J. Chem. Phys. 159, 194306 (2023)
Article history
Received:
August 28 2023
Accepted:
October 19 2023
Citation
Amelia G. Reid, Megan E. Moberg, Connor A. Koellner, Charles W. Machan, Diana A. Thornton, John C. Dickenson, Jeffry J. Stober, David A. Turner, Travis J. Tarring, Caleb A. Brown, Daniel P. Harrison; Sterically attenuated electronic communication in cobalt complexes of meridional isoquinoline-derived ligands for applications in electrocatalysis. J. Chem. Phys. 21 November 2023; 159 (19): 194306. https://doi.org/10.1063/5.0174177
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