Editing Mn-carbonyl molecular catalysts containing a redox-active phenanthroline-5,6-dione for selective electro- and photoreduction of CO2 to CO or HCOOH

{{#doiinfobox: 10.1016/j.electacta.2017.04.080}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
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===Abstract===
==== Summary====
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the manganese complexes as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of 58 for formic acid were reached in xx. The experiments were conducted under visible-light irradiation (λ = 480 or 500 nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below).
====Advances and special progress====
====Additional remarks====
In electrochemical CO<sub>2</sub> reduction experiments, a selectivity for CO formation was observed, contrary to the preferential formation of formic acid in the photocatalytic CO<sub>2</sub> reduction.

===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) in xx using catalyst xx.
==== Catalyst====
<chemform smiles="C1C=CN2[Mn+]([Br-])([C-]#[O+])([C-]#[O+])([C-]#[O+])N3=CC=CC4C(=O)C(=O)C=1C=2C=43" inchikey="KOYXLRUHHLMCRS-UHFFFAOYSA-M" inchi="1S/C12H6N2O2.3CO.BrH.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;3*1-2;;/h1-6H;;;;1H;/q;;;;;+1/p-1" float="none" width="200" height="200">
  -INDIGO-01102415542D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 24 27 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 6.40083 -3.01814 0.0 0
M  V30 2 C 7.89956 -3.88287 0.0 0
M  V30 3 C 7.40155 -3.01842 0.0 0
M  V30 4 N 7.39909 -4.74971 0.0 0
M  V30 5 C 5.89836 -3.88844 0.0 0
M  V30 6 C 6.40341 -4.75162 0.0 0
M  V30 7 C 7.90019 -2.15789 0.0 0
M  V30 8 C 8.89805 -2.15853 0.0 0
M  V30 9 C 8.90142 -3.88351 0.0 0
M  V30 10 C 9.39546 -3.01753 0.0 0
M  V30 11 C 10.3894 -3.01305 0.0 0
M  V30 12 C 10.8927 -3.87395 0.0 0
M  V30 13 N 9.40673 -4.74785 0.0 0
M  V30 14 C 10.403 -4.73667 0.0 0
M  V30 15 O 7.40019 -1.29186 0.0 0
M  V30 16 O 9.39805 -1.2925 0.0 0
M  V30 17 Mn 8.375 -5.525 0.0 0 CHG=1
M  V30 18 C 7.50897 -6.025 0.0 0 CHG=-1
M  V30 19 C 9.24102 -6.025 0.0 0 CHG=-1
M  V30 20 C 8.375 -6.525 0.0 0 CHG=-1
M  V30 21 Br 8.375 -4.525 0.0 0 CHG=-1
M  V30 22 O 6.64295 -6.525 0.0 0 CHG=1
M  V30 23 O 8.375 -7.525 0.0 0 CHG=1
M  V30 24 O 10.1071 -6.525 0.0 0 CHG=1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 1 8 7
M  V30 8 1 2 9
M  V30 9 1 7 3
M  V30 10 2 9 10
M  V30 11 1 10 8
M  V30 12 2 12 11
M  V30 13 1 9 13
M  V30 14 1 11 10
M  V30 15 2 13 14
M  V30 16 1 14 12
M  V30 17 2 7 15
M  V30 18 2 8 16
M  V30 19 10 4 17
M  V30 20 10 13 17
M  V30 21 10 17 18
M  V30 22 10 17 19
M  V30 23 10 17 20
M  V30 24 10 17 21
M  V30 25 3 18 22
M  V30 26 3 20 23
M  V30 27 3 19 24
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C12N3[Mn+]([C-]#[O+])([C-]#[O+])([C-]#[O+])(N#CC)N4=CC=CC(C(=O)C(=O)C=1C=CC=3)=C24.F[P-](F)(F)(F)(F)F" inchikey="JWEFEWAAUDGGIH-UHFFFAOYSA-N" inchi="1S/C12H6N2O2.C2H3N.3CO.F6P.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;1-2-3;3*1-2;1-7(2,3,4,5)6;/h1-6H;1H3;;;;;/q;;;;;-1;+1" float="none" width="200" height="200">
  -INDIGO-01102415522D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 33 35 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 8.22511 -3.34193 0.0 0
M  V30 2 C 8.22463 -1.61163 0.0 0
M  V30 3 C 7.72501 -2.47514 0.0 0
M  V30 4 C 9.22557 -1.61163 0.0 0
M  V30 5 C 9.23006 -3.34193 0.0 0
M  V30 6 C 9.72507 -2.47296 0.0 0
M  V30 7 N 7.72549 -4.20544 0.0 0
M  V30 8 C 6.72455 -4.20544 0.0 0
M  V30 9 C 6.72006 -2.47514 0.0 0
M  V30 10 C 6.22505 -3.34411 0.0 0
M  V30 11 C 10.7221 -2.46783 0.0 0
M  V30 12 C 11.2275 -3.33106 0.0 0
M  V30 13 N 9.73749 -4.20861 0.0 0
M  V30 14 C 10.7369 -4.19675 0.0 0
M  V30 15 O 7.72503 -0.74537 0.0 0
M  V30 16 O 9.72474 -0.745122 0.0 0
M  V30 17 Mn 8.75 -4.975 0.0 0 CHG=1
M  V30 18 N 10.8 -4.975 0.0 0
M  V30 19 C 7.76789 -5.55711 0.0 0 CHG=-1
M  V30 20 C 9.78211 -5.53211 0.0 0 CHG=-1
M  V30 21 C 8.75 -5.975 0.0 0 CHG=-1
M  V30 22 O 6.90187 -6.05711 0.0 0 CHG=1
M  V30 23 O 8.75 -6.975 0.0 0 CHG=1
M  V30 24 O 10.6481 -6.03211 0.0 0 CHG=1
M  V30 25 C 11.5909 -4.96618 0.0 0
M  V30 26 C 12.3319 -4.95736 0.0 0
M  V30 27 F 12.617 -2.25 0.0 0
M  V30 28 P 13.483 -1.75 0.0 0 CHG=-1
M  V30 29 F 14.349 -2.25 0.0 0
M  V30 30 F 13.483 -0.75 0.0 0
M  V30 31 F 14.349 -1.25 0.0 0
M  V30 32 F 12.617 -1.25 0.0 0
M  V30 33 F 13.483 -2.75 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 1 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 2 8 7
M  V30 8 1 3 9
M  V30 9 1 7 1
M  V30 10 2 9 10
M  V30 11 1 10 8
M  V30 12 2 12 11
M  V30 13 1 5 13
M  V30 14 1 11 6
M  V30 15 2 13 14
M  V30 16 1 14 12
M  V30 17 2 2 15
M  V30 18 2 4 16
M  V30 19 10 7 17
M  V30 20 10 17 13
M  V30 21 10 17 18
M  V30 22 10 17 19
M  V30 23 10 17 20
M  V30 24 10 17 21
M  V30 25 3 19 22
M  V30 26 3 21 23
M  V30 27 3 20 24
M  V30 28 3 18 25
M  V30 29 1 25 26
M  V30 30 1 27 28
M  V30 31 1 28 29
M  V30 32 1 28 30
M  V30 33 1 28 31
M  V30 34 1 28 32
M  V30 35 1 28 33
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="[Mn+](~C#O)(~C#O)(~C#O)(~[Br-])1~N2=CC=CC3C=CC4C(C=32)=N~1C=CC=4" inchi="1S/C12H8N2.3CO.BrH.Mn/c1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1;3*1-2;;/h1-8H;;;;1H;/q;;;;;+1/p-1" inchikey="PGQIIBGFONEXSA-UHFFFAOYSA-M" height="200px" width="300px" float="none">
  -INDIGO-03202311252D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 22 25 0 0 0
M  V30 BEGIN ATOM
M  V30 1 Mn 8.825 -5.95 0.0 0 CHG=1
M  V30 2 C 6.77583 -3.41814 0.0 0
M  V30 3 C 8.27456 -4.28287 0.0 0
M  V30 4 C 7.77655 -3.41842 0.0 0
M  V30 5 N 7.77409 -5.14971 0.0 0
M  V30 6 C 6.27336 -4.28844 0.0 0
M  V30 7 C 6.77841 -5.15162 0.0 0
M  V30 8 C 8.27519 -2.55789 0.0 0
M  V30 9 C 9.27305 -2.55853 0.0 0
M  V30 10 C 9.27642 -4.28351 0.0 0
M  V30 11 C 9.77046 -3.41753 0.0 0
M  V30 12 C 10.7644 -3.41305 0.0 0
M  V30 13 C 11.2677 -4.27395 0.0 0
M  V30 14 N 9.78173 -5.14785 0.0 0
M  V30 15 C 10.778 -5.13666 0.0 0
M  V30 16 Br 8.825 -4.95 0.0 0 CHG=-1
M  V30 17 C 7.95897 -6.45 0.0 0
M  V30 18 C 8.825 -6.95 0.0 0
M  V30 19 C 9.69103 -6.45 0.0 0
M  V30 20 O 7.09295 -6.95 0.0 0
M  V30 21 O 8.825 -7.95 0.0 0
M  V30 22 O 10.5571 -6.95 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 4 2
M  V30 2 2 5 3
M  V30 3 1 2 6
M  V30 4 1 3 4
M  V30 5 2 6 7
M  V30 6 1 7 5
M  V30 7 2 9 8
M  V30 8 1 3 10
M  V30 9 1 8 4
M  V30 10 2 10 11
M  V30 11 1 11 9
M  V30 12 2 13 12
M  V30 13 1 10 14
M  V30 14 1 12 11
M  V30 15 2 14 15
M  V30 16 1 15 13
M  V30 17 8 5 1
M  V30 18 8 14 1
M  V30 19 8 1 16
M  V30 20 8 1 17
M  V30 21 8 1 18
M  V30 22 8 1 19
M  V30 23 3 17 20
M  V30 24 3 18 21
M  V30 25 3 19 22
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>{{#moleculelink:|link=ZUZWBGQHMPVNDY-UHFFFAOYSA-M|image=true}}

====Photosensitizer ====
<chemform smiles="" inchi="" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform>

====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}

====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]) and BNAH ({{#moleculelink:|link=CMNUYDSETOTBDE-UHFFFAOYSA-N|image=false|width=300|height=200}}).
====Additives====
In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed.