Phenoxazine-Sensitized CO2-to-CO Reduction with an Iron Porphyrin Catalyst: A Redox Properties-Catalytic Performance Study: Difference between revisions

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DOI 10.1002/cptc.202200009
Authors Martin Kientz, Grace Lowe, Blaine G. McCarthy, Garret M. Miyake, Julien Bonin, Marc Robert,
Submitted 11.03.2022
Published online 29.03.2022
Licenses http://creativecommons.org/licenses/by/4.0/, http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects Organic Chemistry, Physical and Theoretical Chemistry, Analytical Chemistry
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===Abstract===
====Summary====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron porphyrin complex {{#moleculelink:|link=FAKQJSUSUXMEFI-NGWNFTKISA-M|image=false|width=300|height=200}} as catalyst, screening the effect of different phenoxazine-based photosensitizers on the CO production. Turnover numbers (TONs) of 115 for CO were reached in acetonitrile in combination with the photosensitizer {{#moleculelink:|link=HDOFYEULLIFSQY-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ > 400 nm) using BIH as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
In this study, the authors showed a strong relation between the oxidation potential of the photosensitizer and the CO production whereas no correlation between the CO production and the excited state potential of the photosensitizer was discovered.
====Additional remarks====
===Content of the published article in detail ===
The article contains results for the reduction of CO<sub>2</sub> to CO under visible-light catalysis using an iron complex and different phenoxazine-based photosensitizers . The catalytic system performs best (referring to the TON of CO production) in acetonitrile.
====Catalyst====
====Catalyst====
<chemform smiles="C12C(C3C=CC([N+](C)(C)C)=CC=3)=C3N4~[Fe+3]([Cl-])56~N7C(=C(C8C=CC([N+](C)(C)C)=CC=8)C8N~5C(C(C5C=CC([N+](C)(C)C)=CC=5)=C(N=1~6)C=C2)=CC=8)C=CC=7C(C1C=CC([N+](C)(C)C)=CC=1)=C4C=C3.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/C56H60N8.ClH.4F6P.Fe/c1-61(2,3)41-21-13-37(14-22-41)53-45-29-31-47(57-45)54(38-15-23-42(24-16-38)62(4,5)6)49-33-35-51(59-49)56(40-19-27-44(28-20-40)64(10,11)12)52-36-34-50(60-52)55(48-32-30-46(53)58-48)39-17-25-43(26-18-39)63(7,8)9;;4*1-7(2,3,4,5)6;/h13-36H,1-12H3;1H;;;;;/q+2;;4*-1;+5/p-1/b53-45-,53-46-,54-47-,54-49-,55-48-,55-50-,56-51-,56-52-;;;;;;" inchikey="FAKQJSUSUXMEFI-NGWNFTKISA-M" height="200px" width="300px" float="none">
<chemform smiles="C12C(C3C=CC([N+](C)(C)C)=CC=3)=C3N4~[Fe+3]([Cl-])56~N7C(=C(C8C=CC([N+](C)(C)C)=CC=8)C8N~5C(C(C5C=CC([N+](C)(C)C)=CC=5)=C(N=1~6)C=C2)=CC=8)C=CC=7C(C1C=CC([N+](C)(C)C)=CC=1)=C4C=C3.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/C56H60N8.ClH.4F6P.Fe/c1-61(2,3)41-21-13-37(14-22-41)53-45-29-31-47(57-45)54(38-15-23-42(24-16-38)62(4,5)6)49-33-35-51(59-49)56(40-19-27-44(28-20-40)64(10,11)12)52-36-34-50(60-52)55(48-32-30-46(53)58-48)39-17-25-43(26-18-39)63(7,8)9;;4*1-7(2,3,4,5)6;/h13-36H,1-12H3;1H;;;;;/q+2;;4*-1;+5/p-1/b53-45-,53-46-,54-47-,54-49-,55-48-,55-50-,56-51-,56-52-;;;;;;" inchikey="FAKQJSUSUXMEFI-NGWNFTKISA-M" height="200px" width="300px" float="none">
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====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
 
====Sacrificial Electron Donor ====
====Further Information====
In this study, the experiments were done with the sacrificial electron donor BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}).
==== Additives====
In this study, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} was used as an additive.

Revision as of 15:34, 22 January 2024


Abstract

Summary

A photochemical reduction of CO2 to CO was shown using the iron porphyrin complex [Fe(pTMAPP)Cl][PF6]4 as catalyst, screening the effect of different phenoxazine-based photosensitizers on the CO production. Turnover numbers (TONs) of 115 for CO were reached in acetonitrile in combination with the photosensitizer 100762. The experiments were conducted under visible-light irradiation (λ > 400 nm) using BIH as sacrificial electron donor (see section SEDs below).

Advances and special progress

In this study, the authors showed a strong relation between the oxidation potential of the photosensitizer and the CO production whereas no correlation between the CO production and the excited state potential of the photosensitizer was discovered.

Additional remarks

Content of the published article in detail

The article contains results for the reduction of CO2 to CO under visible-light catalysis using an iron complex and different phenoxazine-based photosensitizers . The catalytic system performs best (referring to the TON of CO production) in acetonitrile.

Catalyst

[Fe(pTMAPP)Cl][PF6]4

Photosensitizer

3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine 1007611007621007634-[7-[4-(diphenylamino)phenyl]-10-naphthalen-2-yl-phenoxazin-3-yl]-N,N-diphenyl-aniline10-naphthalen-2-yl-3,7-di(pyren-1-yl)phenoxazine

Investigation

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aadditives.λexc [nm].TON COTON H2.
1.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100493

0.2

BIH

0.005

MeCN

TFE> 40010325
2.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100761

0.2

BIH

0.005

MeCN

TFE> 4008812
3.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100762

0.2

BIH

0.005

MeCN

TFE> 400115
4.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100763

0.2

BIH

0.005

MeCN

TFE> 40011212
5.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100764

0.2

BIH

0.005

MeCN

TFE> 4003257
6.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100765

0.2

BIH

0.005

MeCN

TFE> 40089
Investigation-Name: Table 1

Sacrificial Electron Donor

In this study, the experiments were done with the sacrificial electron donor BIH (BIH).

Additives

In this study, TFE was used as an additive.

Investigations

  • Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)