New Photosensitizers Based on Heteroleptic Cu(I) Complexes and CO2 Photocatalytic Reduction with (Ni(II)(cyclam))Cl2

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DOI 10.1002/chem.202001279
Authors Lisa‐Lou Gracia, Luisa Luci, Cecilia Bruschi, Letizia Sambri, Patrick Weis, Olaf Fuhr, Claudia Bizzarri,
Submitted 16.07.2020
Published online 16.07.2020
Licenses http://creativecommons.org/licenses/by-nc/4.0/,
Subjects General Chemistry, Catalysis, Organic Chemistry
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Abstract

Summary

A photochemical reduction of CO2 was shown using the nickel catalyst Ni(cyclam)Cl2 and the copper-based photosensitizers 100906, 100907, 100908 and100909. Turnover numbers (TONs) of 8.1 for CO were reached in acetonitrile/TEOA for complex 100908 after 4 hours. Employing the other synthesized photosensitizers 100906, 100907 or 100909, TONs of 4.3 to 4.9 were obtained. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below).

Advances and special progress

The first example of Cu(I)-based photosensitizers used for photocatalytic CO2 reduction in combination with Ni(cyclam)Cl2 was successfully reported, demonstrating the usability of a fully noble-metal free CO2 reduction system. The TONs are consistent with previously reported results on noble-metal based photosensitizers.

Additional remarks

The developed heteroleptic photosensitizer complexes showed a high stability in acetonitrile and no ligand release or formation of the homoleptic complexes was detected in UV/Vis stability studies.

Content of the published article in detail

The article contains results for the reduction of CO2 to CO under visible-light catalysis using a nickel complex as catalyst and copper-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/TEOA with photosensitizer 100908.

Catalysts

Ni(cyclam)Cl2

Photosensitizers

100906 100907 100908 100909

Investigations

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A....λexc [nm].TON CO.
1.

Ni(cyclam)Cl2

0.1

Molecule:100906

1

BIH

0.02

MeCN

420 nm (4 x 8 W)4.3
2.

Ni(cyclam)Cl2

0.1

Molecule:100907

1

BIH

0.02

MeCN

420 nm (4 x 8 W)4.9
3.

Ni(cyclam)Cl2

0.1

Molecule:100908

1

BIH

0.02

MeCN

420 nm (4 x 8 W)8.1
4.

Ni(cyclam)Cl2

0.1

Molecule:100909

1

BIH

0.02

MeCN

420 nm (4 x 8 W)4.6
5.

Ni(cyclam)Cl2

0.1

Molecule:100906

1

BIH

0.01

MeCN

420 nm (4 x 8 W)2.6
6.

Ni(cyclam)Cl2

0.1

Molecule:100907

1

BIH

0.01

MeCN

420 nm (4 x 8 W)3.5
7.

Ni(cyclam)Cl2

0.1

Molecule:100908

1

BIH

0.01

MeCN

420 nm (4 x 8 W)5.0
8.

Ni(cyclam)Cl2

0.1

Molecule:100909

1

BIH

0.01

MeCN

420 nm (4 x 8 W)1.8
9.

Ni(cyclam)Cl2

0.1

Molecule:100906

1

BIH

0.01

MeCN

420 nm (4 x 8 W)2.8
10.


Molecule:100908

1

BIH

0.01

MeCN

420 nm (4 x 8 W)
11.

Ni(cyclam)Cl2

0.1

Molecule:100908

1

BIH

0.01

MeCN

420 nm (4 x 8 W)
12.

Ni(cyclam)Cl2

0.1

Molecule:100908

1


MeCN

420 nm (4 x 8 W)
13.

Ni(cyclam)Cl2

0.1

Molecule:100908

1

BIH

0.01

MeCN

420 nm (4 x 8 W)
14.

Ni(cyclam)Cl2

0.1


BIH

0.01

MeCN

420 nm (4 x 8 W)
15.

Ni(cyclam)Cl2

0.1

Molecule:100906

1

BIH

0.01

MeCN

dark
16.

[Cu(ACN)4][BF4]

0.1

Molecule:100906

1

BIH

0.01

MeCN

420 nm (4 x 8 W)
17.

Ni(cyclam)Cl2

0.1

Molecule:100906

1

BIH

0.02

MeCN

420 nm (4 x 8 W)7.3
18.

Ni(cyclam)Cl2

0.1

Molecule:100907

1

BIH

0.02

MeCN

420 nm (4 x 8 W)6.5

Sacrificial Electron Donor

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

Additives

In this study, TEOA was used as a proton donor. For one experiment, N(Me)3 was employed instead. The catalyst [Cu(ACN)4][BF4] was used for a control experiment.

Investigations