Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction: Difference between revisions
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{{DOI|doi=10.1039/c6sc01913g | {{DOI|doi=10.1039/c6sc01913g}} | ||
===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= | 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=JLRZSCLFGATQEH-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=LKSLWZSWOWNWCR-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. | ||
Line 82: | Line 82: | ||
M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform><chemform smiles=" | </chemform><chemform smiles="CC(C)(C)C1=CC2=N(~[Ru](~Cl)(~Cl)(~C#O)(~C#O)~N3=C2C=C(C(C)(C)C)C=C3)C=C1" inchikey="XUQJAKJUMNDNTK-UHFFFAOYSA-L" inchi="InChI=1S/C18H24N2.2CO.2ClH.Ru/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;2*1-2;;;/h7-12H,1-6H3;;;2*1H;/q;;;;;+2/p-2" float="none" width="200" height="200"> | ||
RDKit 2D | |||
0 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0999 V3000 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS 27 29 0 0 0 | M V30 COUNTS 27 29 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C | M V30 1 C 3.05985 -4.92507 0 0 | ||
M V30 2 C | M V30 2 C 4.79015 -4.92459 0 0 | ||
M V30 3 C | M V30 3 C 3.92664 -4.42497 0 0 | ||
M V30 4 N | M V30 4 N 4.79015 -5.92553 0 0 | ||
M V30 5 C | M V30 5 C 3.05985 -5.93002 0 0 | ||
M V30 6 C | M V30 6 C 3.92882 -6.42503 0 0 | ||
M V30 7 C 6. | M V30 7 C 6.75985 -2.90007 0 0 | ||
M V30 8 C | M V30 8 C 8.49015 -2.89959 0 0 | ||
M V30 9 | M V30 9 C 7.62664 -2.39997 0 0 | ||
M V30 10 C | M V30 10 C 8.49015 -3.90053 0 0 | ||
M V30 11 C | M V30 11 C 6.75985 -3.90502 0 0 | ||
M V30 12 | M V30 12 N 7.62882 -4.40003 0 0 | ||
M V30 13 Ru | M V30 13 Ru 6.85 -6.2 0 0 | ||
M V30 14 | M V30 14 Cl 9.15 -5.55 0 0 | ||
M V30 15 | M V30 15 Cl 5.675 -7.425 0 0 | ||
M V30 16 C | M V30 16 C 7.10882 -7.16593 0 0 | ||
M V30 17 C | M V30 17 C 7.71603 -6.7 0 0 | ||
M V30 18 O | M V30 18 O 7.62671 -8.02303 0 0 | ||
M V30 19 O | M V30 19 O 8.74102 -6.675 0 0 | ||
M V30 20 | M V30 20 C 2.19382 -4.42507 0 0 | ||
M V30 21 | M V30 21 C 2.94382 -3.12603 0 0 | ||
M V30 22 C | M V30 22 C 1.44382 -5.72411 0 0 | ||
M V30 23 C | M V30 23 C 0.89478 -3.67507 0 0 | ||
M V30 24 C | M V30 24 C 7.62664 -1.39997 0 0 | ||
M V30 25 C | M V30 25 C 9.12664 -1.39997 0 0 | ||
M V30 26 C | M V30 26 C 6.12664 -1.39997 0 0 | ||
M V30 27 C | M V30 27 C 7.62664 0.10003 0 0 | ||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
Line 124: | Line 124: | ||
M V30 5 2 5 6 | M V30 5 2 5 6 | ||
M V30 6 1 6 4 | M V30 6 1 6 4 | ||
M V30 7 | M V30 7 2 9 7 | ||
M V30 8 2 10 8 | |||
M V30 | M V30 9 1 7 11 | ||
M V30 | M V30 10 1 8 9 | ||
M V30 | M V30 11 2 11 12 | ||
M V30 | M V30 12 1 12 10 | ||
M V30 | M V30 13 1 2 11 | ||
M V30 14 | M V30 14 8 13 4 | ||
M V30 15 | M V30 15 8 13 12 | ||
M V30 16 | M V30 16 8 13 15 | ||
M V30 17 | M V30 17 8 13 14 | ||
M V30 18 | M V30 18 8 13 16 | ||
M V30 19 | M V30 19 8 13 17 | ||
M V30 20 3 | M V30 20 3 16 18 | ||
M V30 21 3 | M V30 21 3 17 19 | ||
M V30 22 | M V30 22 1 20 21 | ||
M V30 23 | M V30 23 1 20 22 | ||
M V30 24 1 | M V30 24 1 20 23 | ||
M V30 25 1 | M V30 25 1 1 20 | ||
M V30 26 1 | M V30 26 1 24 25 | ||
M V30 27 1 | M V30 27 1 24 26 | ||
M V30 28 1 | M V30 28 1 24 27 | ||
M V30 29 1 | M V30 29 1 9 24 | ||
M V30 END BOND | M V30 END BOND | ||
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.[ | </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- | -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 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS | M V30 COUNTS 37 38 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 | M V30 1 F 11.8253 -4.67831 0.0 0 | ||
M V30 2 | M V30 2 P 12.6827 -4.19071 0.0 0 CHG=-1 VAL=6 | ||
M V30 3 | M V30 3 F 12.6945 -5.18061 0.0 0 | ||
M V30 4 | M V30 4 F 13.5447 -4.67885 0.0 0 | ||
M V30 5 | M V30 5 F 12.6888 -3.2002 0.0 0 | ||
M V30 6 | M V30 6 F 13.541 -3.69224 0.0 0 | ||
M V30 7 | M V30 7 F 11.8296 -3.68535 0.0 0 | ||
M V30 8 C | M V30 8 C 5.27521 -4.13902 0.0 0 | ||
M V30 9 | M V30 9 C 6.98617 -4.13854 0.0 0 | ||
M V30 10 C 6. | M V30 10 C 6.13231 -3.64451 0.0 0 | ||
M V30 11 | M V30 11 N 6.98617 -5.12829 0.0 0 | ||
M V30 12 C 5. | M V30 12 C 5.27521 -5.13273 0.0 0 | ||
M V30 13 C | M V30 13 C 6.13447 -5.62221 0.0 0 | ||
M V30 14 C | M V30 14 C 6.13447 -6.61103 0.0 0 | ||
M V30 15 C | M V30 15 C 6.99136 -8.09195 0.0 0 | ||
M V30 16 C | M V30 16 N 6.99162 -7.10547 0.0 0 | ||
M V30 | M V30 17 C 6.13453 -8.5874 0.0 0 | ||
M V30 | M V30 18 C 5.27422 -7.10846 0.0 0 | ||
M V30 | M V30 19 C 5.28061 -8.09733 0.0 0 | ||
M V30 | M V30 20 C 4.41886 -3.64461 0.0 0 | ||
M V30 | M V30 21 C 3.56252 -3.1502 0.0 0 | ||
M V30 | M V30 22 C 4.42427 -8.59174 0.0 0 | ||
M V30 | M V30 23 C 3.56792 -9.08615 0.0 0 | ||
M V30 | M V30 24 Mn 8.13836 -6.06687 0.0 0 CHG=1 | ||
M V30 | M V30 25 N 8.13836 -5.07805 0.0 0 | ||
M V30 | M V30 26 C 8.9947 -5.57246 0.0 0 CHG=-1 | ||
M V30 | M V30 27 C 8.9947 -6.56128 0.0 0 CHG=-1 | ||
M V30 | M V30 28 C 8.39429 -7.02199 0.0 0 CHG=-1 | ||
M V30 | M V30 29 C 8.13836 -4.08923 0.0 0 | ||
M V30 | M V30 30 C 8.13836 -3.10041 0.0 0 | ||
M V30 | M V30 31 O 9.85105 -5.07805 0.0 0 CHG=1 | ||
M V30 32 O 9.85105 -7.05569 0.0 0 CHG=1 | |||
M V30 33 O 8.65021 -7.97712 0.0 0 CHG=1 | |||
M V30 34 C 4.41886 -2.64461 0.0 0 | |||
M V30 35 C 3.55284 -4.14461 0.0 0 | |||
M V30 36 C 4.42427 -9.59174 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 | M V30 1 1 1 2 | ||
M V30 2 2 | M V30 2 1 2 3 | ||
M V30 3 1 | M V30 3 1 2 4 | ||
M V30 4 1 2 | M V30 4 1 2 5 | ||
M V30 5 2 | M V30 5 1 2 6 | ||
M V30 6 1 | M V30 6 1 2 7 | ||
M V30 7 | M V30 7 2 10 8 | ||
M V30 8 2 9 | M V30 8 2 11 9 | ||
M V30 9 | M V30 9 1 8 12 | ||
M V30 10 1 | M V30 10 1 9 10 | ||
M V30 11 | M V30 11 2 12 13 | ||
M V30 12 | M V30 12 1 13 11 | ||
M V30 13 1 | M V30 13 1 13 14 | ||
M V30 14 | M V30 14 2 16 14 | ||
M V30 15 | M V30 15 2 17 15 | ||
M V30 16 1 | M V30 16 1 14 18 | ||
M V30 17 1 | M V30 17 1 15 16 | ||
M V30 18 | M V30 18 2 18 19 | ||
M V30 19 1 17 | M V30 19 1 19 17 | ||
M V30 20 1 | M V30 20 1 8 20 | ||
M V30 21 1 | M V30 21 1 20 21 | ||
M V30 22 | M V30 22 1 19 22 | ||
M V30 23 | M V30 23 1 22 23 | ||
M V30 24 10 | M V30 24 10 11 24 | ||
M V30 25 10 | M V30 25 10 16 24 | ||
M V30 26 10 | M V30 26 10 24 25 | ||
M V30 27 10 | M V30 27 10 24 26 | ||
M V30 28 | M V30 28 10 24 27 | ||
M V30 29 | M V30 29 10 24 28 | ||
M V30 30 3 | M V30 30 3 25 29 | ||
M V30 31 3 | M V30 31 1 29 30 | ||
M V30 32 3 | M V30 32 3 26 31 | ||
M V30 33 3 27 32 | |||
M V30 34 3 28 33 | |||
M V30 35 1 20 34 | |||
M V30 36 1 20 35 | |||
M V30 37 1 22 36 | |||
M V30 38 1 22 37 | |||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
Line 228: | Line 240: | ||
====Photosensitizer ==== | ====Photosensitizer ==== | ||
<chemform smiles="C1C=C2P(C3C=CC=CC=3)(C3C=CC=CC=3)~[Re+]3(N4=C(C5N3=CC([*])=C([*])C=5)C=C([*])C([*])=C4)(C#O)(C#O)~P(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC(P(C4C=CC=CC=4)(C4C=CC=CC=4)~[Re+]4(N5=C(C6N4=CC([*])=C([*])C=6)C=C([*])C([*])=C5)(C#O)(C#O)~P(C4C=CC=CC=4)(C4C=CC=CC=4)C4C=CC(P(C5C=CC=CC=5)(C5C=CC=CC=5)~[Re+]5(N6=CC([*])=C([*])C=C6C6C=C([*])C([*])=CN=65)(C#O)(C#O)~P(C5C=CC=CC=5)(C5C=CC=CC=5)C=1C=C2)=CC=4)=CC=3" | <chemform smiles="C1C=C2P(C3C=CC=CC=3)(C3C=CC=CC=3)~[Re+]3(N4=C(C5N3=CC([*])=C([*])C=5)C=C([*])C([*])=C4)([C-]#[O+])([C-]#[O+])~P(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC(P(C4C=CC=CC=4)(C4C=CC=CC=4)~[Re+]4(N5=C(C6N4=CC([*])=C([*])C=6)C=C([*])C([*])=C5)([C-]#[O+])([C-]#[O+])~P(C4C=CC=CC=4)(C4C=CC=CC=4)C4C=CC(P(C5C=CC=CC=5)(C5C=CC=CC=5)~[Re+]5(N6=CC([*])=C([*])C=C6C6C=C([*])C([*])=CN=65)([C-]#[O+])([C-]#[O+])~P(C5C=CC=CC=5)(C5C=CC=CC=5)C=1C=C2)=CC=4)=CC=3.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchikey="" inchi="" float="none" width="200" height="200" r1="H,CH3,CH3,H" r2="CH3,H,CH3,OMe"> | ||
-INDIGO- | -INDIGO-02262410222D | ||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS | M V30 COUNTS 180 201 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C | M V30 1 C 6.35983 -3.83559 0.0 0 | ||
M V30 2 C | M V30 2 C 7.69328 -4.60497 0.0 0 | ||
M V30 3 C | M V30 3 C 7.25019 -3.83585 0.0 0 | ||
M V30 4 C | M V30 4 C 7.248 -5.37622 0.0 0 | ||
M V30 5 C | M V30 5 C 5.91276 -4.60993 0.0 0 | ||
M V30 6 C | M V30 6 C 6.36212 -5.37792 0.0 0 | ||
M V30 7 C | M V30 7 C 9.11694 -9.62574 0.0 0 | ||
M V30 8 C | M V30 8 C 9.11651 -8.08625 0.0 0 | ||
M V30 9 C | M V30 9 C 8.67199 -8.85454 0.0 0 | ||
M V30 10 C | M V30 10 C 10.0071 -8.08625 0.0 0 | ||
M V30 11 C | M V30 11 C 10.0111 -9.62574 0.0 0 | ||
M V30 12 C | M V30 12 C 10.4515 -8.8526 0.0 0 | ||
M V30 13 C 11. | M V30 13 C 11.7872 -3.79111 0.0 0 | ||
M V30 14 C | M V30 14 C 13.1206 -4.56048 0.0 0 | ||
M V30 15 C 12. | M V30 15 C 12.6775 -3.79137 0.0 0 | ||
M V30 16 C 12. | M V30 16 C 12.6753 -5.33173 0.0 0 | ||
M V30 17 C | M V30 17 C 11.3401 -4.56545 0.0 0 | ||
M V30 18 C 11. | M V30 18 C 11.7894 -5.33344 0.0 0 | ||
M V30 19 P | M V30 19 P 7.69505 -3.06532 0.0 0 | ||
M V30 20 P | M V30 20 P 11.3423 -3.02058 0.0 0 | ||
M V30 21 P | M V30 21 P 5.91725 -6.14844 0.0 0 | ||
M V30 22 P | M V30 22 P 7.78226 -8.85454 0.0 0 | ||
M V30 23 P | M V30 23 P 11.3412 -8.8526 0.0 0 | ||
M V30 24 P | M V30 24 P 13.1202 -6.10226 0.0 0 | ||
M V30 25 Re | M V30 25 Re 12.2309 -7.49758 0.0 0 CHG=1 | ||
M V30 26 Re | M V30 26 Re 6.91477 -7.54207 0.0 0 CHG=1 | ||
M V30 27 Re | M V30 27 Re 9.49497 -3.04895 0.0 0 CHG=1 | ||
M V30 28 C | M V30 28 C 11.3412 -7.49758 0.0 0 CHG=-1 | ||
M V30 29 C 11. | M V30 29 C 11.786 -6.72705 0.0 0 CHG=-1 | ||
M V30 30 C | M V30 30 C 9.05011 -3.81948 0.0 0 CHG=-1 | ||
M V30 31 C 9. | M V30 31 C 9.93984 -3.81948 0.0 0 CHG=-1 | ||
M V30 32 C | M V30 32 C 7.80449 -7.54207 0.0 0 CHG=-1 | ||
M V30 33 C | M V30 33 C 7.35963 -6.77154 0.0 0 CHG=-1 | ||
M V30 34 O | M V30 34 O 7.80449 -6.00102 0.0 0 CHG=1 | ||
M V30 35 O | M V30 35 O 8.69422 -7.54207 0.0 0 CHG=1 | ||
M V30 36 O | M V30 36 O 10.4514 -7.49758 0.0 0 CHG=1 | ||
M V30 37 O | M V30 37 O 11.3412 -5.95653 0.0 0 CHG=1 | ||
M V30 38 O | M V30 38 O 8.60525 -4.59 0.0 0 CHG=1 | ||
M V30 39 O | M V30 39 O 10.3847 -4.59 0.0 0 CHG=1 | ||
M V30 40 C 13. | M V30 40 C 13.7493 -5.47313 0.0 0 | ||
M V30 41 C 14. | M V30 41 C 14.1464 -3.98571 0.0 0 | ||
M V30 42 C 13. | M V30 42 C 13.5186 -4.61319 0.0 0 | ||
M V30 43 C 15. | M V30 43 C 15.0067 -4.21563 0.0 0 | ||
M V30 44 C 14. | M V30 44 C 14.6131 -5.70396 0.0 0 | ||
M V30 45 C 15. | M V30 45 C 15.2382 -5.07073 0.0 0 | ||
M V30 46 C 13. | M V30 46 C 13.8907 -6.54712 0.0 0 | ||
M V30 47 C 15. | M V30 47 C 15.4302 -6.54565 0.0 0 | ||
M V30 48 C 14. | M V30 48 C 14.6616 -6.10165 0.0 0 | ||
M V30 49 C 15. | M V30 49 C 15.4308 -7.43622 0.0 0 | ||
M V30 50 C 13. | M V30 50 C 13.8913 -7.44124 0.0 0 | ||
M V30 51 C 14. | M V30 51 C 14.6647 -7.88115 0.0 0 | ||
M V30 52 C | M V30 52 C 12.2017 -2.7903 0.0 0 | ||
M V30 53 C 13. | M V30 53 C 13.2892 -1.70068 0.0 0 | ||
M V30 54 C 12. | M V30 54 C 12.4318 -1.93019 0.0 0 | ||
M V30 55 C 13. | M V30 55 C 13.9194 -2.32998 0.0 0 | ||
M V30 56 C 12. | M V30 56 C 12.8344 -3.42212 0.0 0 | ||
M V30 57 C 13. | M V30 57 C 13.6923 -3.18628 0.0 0 | ||
M V30 58 C | M V30 58 C 11.3423 -2.13085 0.0 0 | ||
M V30 59 C 10. | M V30 59 C 10.5713 -0.798349 0.0 0 | ||
M V30 60 C 10. | M V30 60 C 10.571 -1.68597 0.0 0 | ||
M V30 61 C | M V30 61 C 11.3422 -0.352549 0.0 0 | ||
M V30 62 C | M V30 62 C 12.1163 -1.68328 0.0 0 | ||
M V30 63 C | M V30 63 C 12.1106 -0.793501 0.0 0 | ||
M V30 64 C | M V30 64 C 6.83565 -2.83505 0.0 0 | ||
M V30 65 C | M V30 65 C 5.34899 -3.23491 0.0 0 | ||
M V30 66 C | M V30 66 C 6.2063 -3.46486 0.0 0 | ||
M V30 67 C | M V30 67 C 5.11792 -2.37484 0.0 0 | ||
M V30 68 C | M V30 68 C 6.60365 -1.97154 0.0 0 | ||
M V30 69 C | M V30 69 C 5.7427 -1.7468 0.0 0 | ||
M V30 70 C | M V30 70 C 7.69505 -2.1756 0.0 0 | ||
M V30 71 C | M V30 71 C 6.92404 -0.843091 0.0 0 | ||
M V30 72 C | M V30 72 C 6.92381 -1.73071 0.0 0 | ||
M V30 73 C | M V30 73 C 7.69499 -0.397292 0.0 0 | ||
M V30 74 C | M V30 74 C 8.46908 -1.72801 0.0 0 | ||
M V30 75 C | M V30 75 C 8.46334 -0.838244 0.0 0 | ||
M V30 76 C | M V30 76 C 11.111 -9.71202 0.0 0 | ||
M V30 77 C 11. | M V30 77 C 11.5108 -11.1987 0.0 0 | ||
M V30 78 C 11. | M V30 78 C 11.7407 -10.3413 0.0 0 | ||
M V30 79 C 10. | M V30 79 C 10.6507 -11.4297 0.0 0 | ||
M V30 80 C | M V30 80 C 10.2474 -9.94397 0.0 0 | ||
M V30 81 C | M V30 81 C 10.0227 -10.805 0.0 0 | ||
M V30 82 C | M V30 82 C 12.1117 -9.29746 0.0 0 | ||
M V30 83 C 13. | M V30 83 C 13.6512 -9.29599 0.0 0 | ||
M V30 84 C 12. | M V30 84 C 12.8827 -8.85198 0.0 0 | ||
M V30 85 C 13. | M V30 85 C 13.6519 -10.1866 0.0 0 | ||
M V30 86 C | M V30 86 C 12.1124 -10.1916 0.0 0 | ||
M V30 87 C 12. | M V30 87 C 12.8858 -10.6315 0.0 0 | ||
M V30 88 C | M V30 88 C 8.01254 -9.71397 0.0 0 | ||
M V30 89 C | M V30 89 C 9.10216 -10.8015 0.0 0 | ||
M V30 90 C 8. | M V30 90 C 8.87265 -9.94406 0.0 0 | ||
M V30 91 C | M V30 91 C 8.47286 -11.4317 0.0 0 | ||
M V30 92 C | M V30 92 C 7.38072 -10.3466 0.0 0 | ||
M V30 93 C | M V30 93 C 7.61656 -11.2046 0.0 0 | ||
M V30 94 C | M V30 94 C 7.01173 -9.2994 0.0 0 | ||
M V30 95 C | M V30 95 C 6.24326 -10.6333 0.0 0 | ||
M V30 96 C | M V30 96 C 7.01207 -10.1898 0.0 0 | ||
M V30 97 C | M V30 97 C 5.47171 -10.1886 0.0 0 | ||
M V30 98 C | M V30 98 C 6.2371 -8.85285 0.0 0 | ||
M V30 99 C | M V30 99 C 5.46941 -9.30273 0.0 0 | ||
M V30 100 C | M V30 100 C 5.28812 -5.51931 0.0 0 | ||
M V30 101 C | M V30 101 C 3.8007 -5.12228 0.0 0 | ||
M V30 102 C | M V30 102 C 4.42819 -5.75009 0.0 0 | ||
M V30 103 C | M V30 103 C 4.03063 -4.26191 0.0 0 | ||
M V30 104 C | M V30 104 C 5.51896 -4.6555 0.0 0 | ||
M V30 105 C | M V30 105 C 4.88573 -4.0304 0.0 0 | ||
M V30 106 C | M V30 106 C 5.14672 -6.59331 0.0 0 | ||
M V30 107 C | M V30 107 C 4.37825 -7.92728 0.0 0 | ||
M V30 108 C | M V30 108 C 5.14707 -7.48367 0.0 0 | ||
M V30 109 C | M V30 109 C 3.6067 -7.48252 0.0 0 | ||
M V30 110 C | M V30 110 C 4.37209 -6.14676 0.0 0 | ||
M V30 111 C | M V30 111 C 3.6044 -6.59663 0.0 0 | ||
M V30 112 C | M V30 112 C 15.9538 -7.84068 0.0 0 | ||
M V30 113 C 17. | M V30 113 C 17.2873 -8.61006 0.0 0 | ||
M V30 114 C | M V30 114 C 16.8442 -7.84094 0.0 0 | ||
M V30 115 C | M V30 115 C 16.842 -9.38131 0.0 0 | ||
M V30 116 N 15. | M V30 116 N 15.5068 -8.61502 0.0 0 | ||
M V30 117 C | M V30 117 C 15.9561 -9.38302 0.0 0 | ||
M V30 118 C 15. | M V30 118 C 15.5112 -10.1535 0.0 0 | ||
M V30 119 C 15. | M V30 119 C 15.5127 -11.693 0.0 0 | ||
M V30 120 C | M V30 120 C 15.9567 -10.9244 0.0 0 | ||
M V30 121 C 14. | M V30 121 C 14.6221 -11.6936 0.0 0 | ||
M V30 122 N 14. | M V30 122 N 14.6171 -10.1541 0.0 0 | ||
M V30 123 C 14. | M V30 123 C 14.1772 -10.9276 0.0 0 | ||
M V30 124 R# | M V30 124 R# 15.9576 -12.4636 0.0 0 RGROUPS=(1 1) | ||
M V30 125 R# 18. | M V30 125 R# 18.177 -8.61006 0.0 0 RGROUPS=(1 1) | ||
M V30 126 C | M V30 126 C 7.63909 0.0146492 0.0 0 | ||
M V30 127 C | M V30 127 C 7.63865 1.55414 0.0 0 | ||
M V30 128 C | M V30 128 C 7.19412 0.785853 0.0 0 | ||
M V30 129 C | M V30 129 C 8.52921 1.55414 0.0 0 | ||
M V30 130 N | M V30 130 N 8.53321 0.0146492 0.0 0 | ||
M V30 131 C 8. | M V30 131 C 8.97363 0.787792 0.0 0 | ||
M V30 132 C 9. | M V30 132 C 9.86335 0.787792 0.0 0 | ||
M V30 133 C | M V30 133 C 11.1959 1.55881 0.0 0 | ||
M V30 134 C | M V30 134 C 10.3082 1.55904 0.0 0 | ||
M V30 135 C 11. | M V30 135 C 11.6417 0.787854 0.0 0 | ||
M V30 136 N | M V30 136 N 10.3109 0.0137595 0.0 0 | ||
M V30 137 C | M V30 137 C 11.2008 0.0195098 0.0 0 | ||
M V30 138 R# 11. | M V30 138 R# 11.6407 2.32933 0.0 0 RGROUPS=(1 1) | ||
M V30 139 R# | M V30 139 R# 7.19379 2.32467 0.0 0 RGROUPS=(1 1) | ||
M V30 140 C | M V30 140 C 4.8284 -10.9379 0.0 0 | ||
M V30 141 C | M V30 141 C 3.49538 -11.708 0.0 0 | ||
M V30 142 C | M V30 142 C 4.38299 -11.7088 0.0 0 | ||
M V30 143 C | M V30 143 C 3.05009 -10.9367 0.0 0 | ||
M V30 144 N | M V30 144 N 4.38134 -10.1636 0.0 0 | ||
M V30 145 C | M V30 145 C 3.49156 -10.1687 0.0 0 | ||
M V30 146 C | M V30 146 C 3.0467 -9.39818 0.0 0 | ||
M V30 147 C | M V30 147 C 1.71272 -8.6297 0.0 0 | ||
M V30 148 C | M V30 148 C 2.15633 -9.39851 0.0 0 | ||
M V30 149 C | M V30 149 C 2.15749 -7.85815 0.0 0 | ||
M V30 150 N | M V30 150 N 3.49324 -8.62354 0.0 0 | ||
M V30 151 C | M V30 151 C 3.04337 -7.85585 0.0 0 | ||
M V30 152 R# | M V30 152 R# 0.822997 -8.6297 0.0 0 RGROUPS=(1 1) | ||
M V30 153 R# | M V30 153 R# 3.05051 -12.4785 0.0 0 RGROUPS=(1 1) | ||
M V30 154 R# | M V30 154 R# 4.82786 -12.4793 0.0 0 RGROUPS=(1 2) | ||
M V30 155 R# | M V30 155 R# 1.71137 -7.08835 0.0 0 RGROUPS=(1 2) | ||
M V30 156 R# 14. | M V30 156 R# 14.1785 -12.4648 0.0 0 RGROUPS=(1 2) | ||
M V30 157 R# 17. | M V30 157 R# 17.2895 -7.07069 0.0 0 RGROUPS=(1 2) | ||
M V30 158 R# | M V30 158 R# 6.3044 0.786395 0.0 0 RGROUPS=(1 2) | ||
M V30 159 R# 12. | M V30 159 R# 12.5314 0.789322 0.0 0 RGROUPS=(1 2) | ||
M V30 160 P 16.625 -2.225 0.0 0 CHG=-1 | |||
M V30 161 F 16.125 -1.35897 0.0 0 | |||
M V30 162 F 16.125 -3.09103 0.0 0 | |||
M V30 163 F 17.625 -2.225 0.0 0 | |||
M V30 164 F 17.125 -1.35897 0.0 0 | |||
M V30 165 F 17.125 -3.09103 0.0 0 | |||
M V30 166 F 15.625 -2.225 0.0 0 | |||
M V30 167 P 2.775 -2.375 0.0 0 CHG=-1 | |||
M V30 168 F 2.275 -1.50897 0.0 0 | |||
M V30 169 F 2.275 -3.24103 0.0 0 | |||
M V30 170 F 3.775 -2.375 0.0 0 | |||
M V30 171 F 3.275 -1.50897 0.0 0 | |||
M V30 172 F 3.275 -3.24103 0.0 0 | |||
M V30 173 F 1.775 -2.375 0.0 0 | |||
M V30 174 P 9.55 -13.35 0.0 0 CHG=-1 | |||
M V30 175 F 9.05 -12.484 0.0 0 | |||
M V30 176 F 9.05 -14.216 0.0 0 | |||
M V30 177 F 10.55 -13.35 0.0 0 | |||
M V30 178 F 10.05 -12.484 0.0 0 | |||
M V30 179 F 10.05 -14.216 0.0 0 | |||
M V30 180 F 8.55 -13.35 0.0 0 | |||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
Line 579: | Line 612: | ||
M V30 182 1 128 158 | M V30 182 1 128 158 | ||
M V30 183 1 135 159 | M V30 183 1 135 159 | ||
M V30 184 1 160 161 | |||
M V30 185 1 160 162 | |||
M V30 186 1 160 163 | |||
M V30 187 1 160 164 | |||
M V30 188 1 160 165 | |||
M V30 189 1 160 166 | |||
M V30 190 1 167 168 | |||
M V30 191 1 167 169 | |||
M V30 192 1 167 170 | |||
M V30 193 1 167 171 | |||
M V30 194 1 167 172 | |||
M V30 195 1 167 173 | |||
M V30 196 1 174 175 | |||
M V30 197 1 174 176 | |||
M V30 198 1 174 177 | |||
M V30 199 1 174 178 | |||
M V30 200 1 174 179 | |||
M V30 201 1 174 180 | |||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
Line 590: | Line 641: | ||
==== Additives==== | ==== Additives==== | ||
In this study, no additives were tested. | In this study, no additives were tested. | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]][[Category:Publication]] |
Latest revision as of 13:46, 3 May 2024
Abstract[edit | edit source]
Summary[edit | edit source]
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 100877. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex [Re(bpy)(CO)3(MeCN)][PF6] and photosensitizer 100878. 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[edit | edit source]
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[edit | edit source]
Content of the published article in detail[edit | edit source]
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[edit | edit source]
[Re(bpy)(CO)3(MeCN)][PF6] Ru(dtBubpy)(CO)2Cl2 [Mn(dtBubpy)(CO)3(MeCN)][PF6]
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
cat | cat conc [µM] | PS | PS conc [mM] | solvent A | . | . | λexc [nm] | . | TON CO | . | . | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.05 | 0.05 | 436 | 27 | |||||||||
2. | 0.05 | 0.05 | 436 | 98 | |||||||||
3. | 0.05 | 0.05 | 436 | 22 | |||||||||
4. | 0.05 | 0.05 | 436 | 71 | |||||||||
5. | 0.05 | 436 | 6 | ||||||||||
6. | 0.05 | 436 | 8 | ||||||||||
7. | 0.05 | 0.05 | 436 | 20 | |||||||||
8. | 0.05 | 0.05 | 436 | 32 | |||||||||
9. | 0.05 | 0.05 | 436 | 11 | |||||||||
10. | 0.05 | 0.05 | 436 | 48 |
cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | λexc [nm] | . | TON CO | TON H2 | TON HCOOH | . | . | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.05 | 0.05 | 436 | 20 | 72 | 290 | |||||||||||
2. | 0.05 | 0.05 | 0.03 | 436 | 16 | 49 | 280 | ||||||||||
3. | 0.05 | 0.05 | 436 | 32 | 85 | ||||||||||||
4. | 0.05 | 0.05 | 0.03 | 436 | 80 | 60 |
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEOA (100507).
Additives[edit | edit source]
In this study, no additives were tested.