Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction: Difference between revisions

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DOI 10.1039/c6sc01913g
Authors Jana Rohacova, Osamu Ishitani,
Submitted 05.07.2016
Published online 2016
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===Abstract===
===Abstract===
==== Summary====
==== Summary====
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink: |link=WCQGNVNGTWFVLO-UHFFFAOYSA-N|image=false|width=300|height=200}} in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of  up to 290 for formic acid were reached in DMA with the ruthenium complex {{#moleculelink:|link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} and photosensitizer {{#moleculelink:|link=KSOIVZAANOLODS-UHFFFAOYSA-T|image=false|width=300|height=200}}. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}} and photosensitizer {{#moleculelink:|link=LOLRMPNEYKEGPF-UHFFFAOYSA-T|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below).
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink: |link=OMERWMHUIAGAOR-UHFFFAOYSA-N|image=false|width=300|height=200}} in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of  up to 290 for formic acid were reached in DMA with the ruthenium complex {{#moleculelink:|link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} and photosensitizer {{#moleculelink:|link=KSOIVZAANOLODS-UHFFFAOYSA-T|image=false|width=300|height=200}}. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}} and photosensitizer {{#moleculelink:|link=LOLRMPNEYKEGPF-UHFFFAOYSA-T|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
====Advances and special progress====
Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO<sub>2</sub> reduction attempts with different bipyridine-based catalysts.
Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO<sub>2</sub> reduction attempts with different bipyridine-based catalysts.
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M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C(C(C)(C)C)1C=C2C3C=C(C(C)(C)C)C=CN=3[Mn+](C#O)(C#O)(C#O)(N#CC)N2=CC=1.F[P-](F)(F)(F)(F)F" inchi="1S/C18H24N2.C2H3N.3CHO.F6P.Mn/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;1-2-3;3*1-2;1-7(2,3,4,5)6;/h7-12H,1-6H3;1H3;3*1H;;/q;;;;;-1;+1" inchikey="WCQGNVNGTWFVLO-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C(C(C)(C)C)1C=C2C3C=C(C(C)(C)C)C=CN=3[Mn+]([C-]#[O+])([C-]#[O+])([C-]#[O+])(N#CC)N2=CC=1.F[P-](F)(F)(F)(F)F" inchikey="OMERWMHUIAGAOR-UHFFFAOYSA-N" inchi="1S/C18H24N2.C2H3N.3CO.F6P.Mn/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;1-2-3;3*1-2;1-7(2,3,4,5)6;/h7-12H,1-6H3;1H3;;;;;/q;;;;;-1;+1" float="none" width="200" height="200">
   -INDIGO-02192415192D
   -INDIGO-02192415212D


   0  0  0  0  0  0  0  0  0  0  0 V3000
   0  0  0  0  0  0  0  0  0  0  0 V3000
Line 157: Line 157:
M  V30 COUNTS 37 38 0 0 0
M  V30 COUNTS 37 38 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 5.54029 -0.252784 0.0 0
M  V30 1 F 11.8253 -4.67831 0.0 0
M  V30 2 C 7.12769 -0.252344 0.0 0
M  V30 2 P 12.6827 -4.19071 0.0 0 CHG=-1 VAL=6
M  V30 3 C 6.3355 0.206014 0.0 0
M  V30 3 F 12.6945 -5.18061 0.0 0
M  V30 4 N 7.12769 -1.17062 0.0 0
M  V30 4 F 13.5447 -4.67885 0.0 0
M  V30 5 C 5.54029 -1.17474 0.0 0
M  V30 5 F 12.6888 -3.2002 0.0 0
M  V30 6 C 6.3375 -1.62887 0.0 0
M  V30 6 F 13.541 -3.69224 0.0 0
M  V30 7 C 6.3375 -2.54628 0.0 0
M  V30 7 F 11.8296 -3.68535 0.0 0
M  V30 8 C 7.13251 -3.92025 0.0 0
M  V30 8 C 5.27521 -4.13902 0.0 0
M  V30 9 N 7.13275 -3.00501 0.0 0
M  V30 9 C 6.98617 -4.13854 0.0 0
M  V30 10 C 6.33756 -4.37993 0.0 0
M  V30 10 C 6.13231 -3.64451 0.0 0
M  V30 11 C 5.53938 -3.00779 0.0 0
M  V30 11 N 6.98617 -5.12829 0.0 0
M  V30 12 C 5.5453 -3.92525 0.0 0
M  V30 12 C 5.27521 -5.13273 0.0 0
M  V30 13 C 4.74579 0.205922 0.0 0
M  V30 13 C 6.13447 -5.62221 0.0 0
M  V30 14 C 3.85964 -0.0315228 0.0 0
M  V30 14 C 6.13447 -6.61103 0.0 0
M  V30 15 C 3.95129 0.664629 0.0 0
M  V30 15 C 6.99136 -8.09195 0.0 0
M  V30 16 C 4.50834 1.09207 0.0 0
M  V30 16 N 6.99162 -7.10547 0.0 0
M  V30 17 C 4.75081 -4.38396 0.0 0
M  V30 17 C 6.13453 -8.5874 0.0 0
M  V30 18 C 3.9563 -4.84267 0.0 0
M  V30 18 C 5.27422 -7.10846 0.0 0
M  V30 19 C 3.86465 -4.14651 0.0 0
M  V30 19 C 5.28061 -8.09733 0.0 0
M  V30 20 C 4.51336 -5.27012 0.0 0
M  V30 20 C 4.41886 -3.64461 0.0 0
M  V30 21 Mn 7.75598 -2.06461 0.0 0 CHG=1
M  V30 21 C 3.56252 -3.1502 0.0 0
M  V30 22 N 7.75598 -1.1472 0.0 0
M  V30 22 C 4.42427 -8.59174 0.0 0
M  V30 23 C 8.55048 -1.6059 0.0 0
M  V30 23 C 3.56792 -9.08615 0.0 0
M  V30 24 C 8.55048 -2.52332 0.0 0
M  V30 24 Mn 8.13836 -6.06687 0.0 0 CHG=1
M  V30 25 C 7.99343 -2.95077 0.0 0
M  V30 25 N 8.13836 -5.07805 0.0 0
M  V30 26 C 7.75598 -0.229785 0.0 0
M  V30 26 C 8.9947 -5.57246 0.0 0 CHG=-1
M  V30 27 C 7.75598 0.687628 0.0 0
M  V30 27 C 8.9947 -6.56128 0.0 0 CHG=-1
M  V30 28 O 9.34499 -1.1472 0.0 0
M  V30 28 C 8.39429 -7.02199 0.0 0 CHG=-1
M  V30 29 O 9.34499 -2.98202 0.0 0
M  V30 29 C 8.13836 -4.08923 0.0 0
M  V30 30 O 8.23087 -3.83691 0.0 0
M  V30 30 C 8.13836 -3.10041 0.0 0
M  V30 31 F 11.3568 2.70594 0.0 0
M  V30 31 O 9.85105 -5.07805 0.0 0 CHG=1
M  V30 32 P 12.5485 3.394 0.0 0 CHG=-1 VAL=6
M  V30 32 O 9.85105 -7.05569 0.0 0 CHG=1
M  V30 33 F 12.5485 2.01788 0.0 0
M  V30 33 O 8.65021 -7.97712 0.0 0 CHG=1
M  V30 34 F 13.7404 2.70594 0.0 0
M  V30 34 C 4.41886 -2.64461 0.0 0
M  V30 35 F 12.5485 4.77012 0.0 0
M  V30 35 C 3.55284 -4.14461 0.0 0
M  V30 36 F 13.7404 4.08206 0.0 0
M  V30 36 C 4.42427 -9.59174 0.0 0
M  V30 37 F 11.3568 4.08206 0.0 0
M  V30 37 C 3.55825 -8.09174 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 1 1 1 2
M  V30 2 2 4 2
M  V30 2 1 2 3
M  V30 3 1 1 5
M  V30 3 1 2 4
M  V30 4 1 2 3
M  V30 4 1 2 5
M  V30 5 2 5 6
M  V30 5 1 2 6
M  V30 6 1 6 4
M  V30 6 1 2 7
M  V30 7 1 6 7
M  V30 7 2 10 8
M  V30 8 2 9 7
M  V30 8 2 11 9
M  V30 9 2 10 8
M  V30 9 1 8 12
M  V30 10 1 7 11
M  V30 10 1 9 10
M  V30 11 1 8 9
M  V30 11 2 12 13
M  V30 12 2 11 12
M  V30 12 1 13 11
M  V30 13 1 12 10
M  V30 13 1 13 14
M  V30 14 1 1 13
M  V30 14 2 16 14
M  V30 15 1 13 14
M  V30 15 2 17 15
M  V30 16 1 13 15
M  V30 16 1 14 18
M  V30 17 1 13 16
M  V30 17 1 15 16
M  V30 18 1 12 17
M  V30 18 2 18 19
M  V30 19 1 17 18
M  V30 19 1 19 17
M  V30 20 1 17 19
M  V30 20 1 8 20
M  V30 21 1 17 20
M  V30 21 1 20 21
M  V30 22 10 4 21
M  V30 22 1 19 22
M  V30 23 10 9 21
M  V30 23 1 22 23
M  V30 24 10 21 22
M  V30 24 10 11 24
M  V30 25 10 21 23
M  V30 25 10 16 24
M  V30 26 10 21 24
M  V30 26 10 24 25
M  V30 27 10 21 25
M  V30 27 10 24 26
M  V30 28 3 22 26
M  V30 28 10 24 27
M  V30 29 1 26 27
M  V30 29 10 24 28
M  V30 30 3 23 28
M  V30 30 3 25 29
M  V30 31 3 24 29
M  V30 31 1 29 30
M  V30 32 3 25 30
M  V30 32 3 26 31
M  V30 33 1 31 32
M  V30 33 3 27 32
M  V30 34 1 32 33
M  V30 34 3 28 33
M  V30 35 1 32 34
M  V30 35 1 20 34
M  V30 36 1 32 35
M  V30 36 1 20 35
M  V30 37 1 32 36
M  V30 37 1 22 36
M  V30 38 1 32 37
M  V30 38 1 22 37
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB

Revision as of 15:22, 19 February 2024


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Abstract

Summary

A photochemical reduction of CO2 to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts [Re(bpy)(CO)3(MeCN)][PF6], Ru(dtBubpy)(CO)2Cl2 or [Mn(dtBubpy)(CO)3(MeCN)][PF6] in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of up to 290 for formic acid were reached in DMA with the ruthenium complex Ru(dtBubpy)(CO)2Cl2 and photosensitizer Molecule with key KSOIVZAANOLODS-UHFFFAOYSA-T does not exist.. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex [Re(bpy)(CO)3(MeCN)][PF6] and photosensitizer Molecule with key LOLRMPNEYKEGPF-UHFFFAOYSA-T does not exist.. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below).

Advances and special progress

Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO2 reduction attempts with different bipyridine-based catalysts.

Additional remarks

Content of the published article in detail

The article contains results for the reduction of CO2 to CO or formic acid under visible-light catalysis using bipyridine-based complexes and rhenium-based trinuclear rings as photosensitizers. The catalytic system performs best in DMA for formic acid production (referring to the TON of formic acid production) and in DMF for CO production.

Catalyst

[Re(bpy)(CO)3(MeCN)][PF6] Ru(dtBubpy)(CO)2Cl2 [Mn(dtBubpy)(CO)3(MeCN)][PF6]

Photosensitizer

Investigation

catcat conc [µM]PSPS conc [mM]solvent A..λexc [nm].TON CO...
1.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100878

0.05

DMF

43627
2.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100878

0.05

DMF

43698
3.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100877

0.05

DMF

43622
4.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100877

0.05

DMF

43671
5.


Molecule:100877

0.05

DMF

4366
6.


Molecule:100877

0.05

DMF

4368
7.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100879

0.05

DMF

43620
8.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100879

0.05

DMF

43632
9.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100880

0.05

DMF

43611
10.

[Re(bpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100880

0.05

DMF

43648
Investigation-Name: Table 1
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A..λexc [nm].TON COTON H2TON HCOOH...
1.

Ru(dtBubpy)(CO)2Cl2

0.05

Molecule:100877

0.05


DMF

4362072290
2.

Ru(dtBubpy)(CO)2Cl2

0.05

Molecule:100877

0.05

BI(OH)H

0.03

DMF

4361649280
3.

[Mn(dtBubpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100877

0.05


DMF

4363285
4.

[Mn(dtBubpy)(CO)3(MeCN)][PF6]

0.05

Molecule:100877

0.05

BI(OH)H

0.03

DMF

4368060
Investigation-Name: Table 2

Sacrificial Electron Donor

In this study, the experiments were done with the sacrificial electron donor TEOA (100507).

Additives

In this study, no additives were tested.

Investigations

  • Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
  • Table 2 (Molecular process, Photocatalytic CO2 conversion experiments)
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