Issue 33, 2023

Significance of the connecting position between Zn(ii) porphyrin and Re(i) bipyridine tricarbonyl complex units in dyads for room-temperature phosphorescence and photocatalytic CO2 reduction: unexpected enhancement by triethanolamine in catalytic activity

Abstract

We synthesized three new dyads composed of a Zn porphyrin and fac-Re(bpy)(CO)3Br (bpy = 2,2′-bipyridine) units, ZnP-nBpy[double bond, length as m-dash]ReBr (n = 4, 5, and 6), in which the porphyrin is directly connected at the meso-position through the 4-, 5-, or 6-position of the bpy. We investigated the relationships between the connecting positions and the photophysical properties as well as catalytic activity in the CO2 reduction reaction. The dyad connected through the 6-position, ZnP-6Bpy[double bond, length as m-dash]ReBr, showed obvious phosphorescence with a lifetime of 280 μs at room temperature, in N,N-dimethylacetamide (DMA), whereas the other two dyads showed almost no phosphorescence under the same conditions. The photocatalytic CO2 reduction reactions in DMA using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as the electron donor and the three dyads ZnP-nBpy[double bond, length as m-dash]ReBr selectively produced CO with similar initial rates, but the durabilities were low. The addition of triethanolamine (TEOA) suppressed the decomposition of dyads, improving their durabilities and reaction efficiencies. In particular, ZnP-5Bpy[double bond, length as m-dash]ReBr was remarkably improved—it gave the highest durability and reaction efficiency among the three dyads; the reaction quantum yield reached 24%. The reason for this significant activity is no accumulation of electrons on the Zn porphyrin in ZnP-5Bpy[double bond, length as m-dash]ReBr, which would be caused by dual interactions of TEOA with the Re and Zn ions in the dyad. As the highest catalytic activity was observed in ZnP-5Bpy[double bond, length as m-dash]ReBr among the three dyads, which had no room-temperature phosphorescence (RTP), the catalytic activities and RTP properties are considered independent, but they are greatly influenced by the connecting positions on the bpy ligand in ZnP-nBpy[double bond, length as m-dash]ReBr.

Graphical abstract: Significance of the connecting position between Zn(ii) porphyrin and Re(i) bipyridine tricarbonyl complex units in dyads for room-temperature phosphorescence and photocatalytic CO2 reduction: unexpected enhancement by triethanolamine in catalytic activity

Supplementary files

Transparent peer review

To support increased transparency, we offer authors the option to publish the peer review history alongside their article.

View this article’s peer review history

Article information

Article type
Edge Article
Submitted
12 mai 2023
Accepted
14 jul 2023
First published
18 jul 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 8743-8765

Significance of the connecting position between Zn(II) porphyrin and Re(I) bipyridine tricarbonyl complex units in dyads for room-temperature phosphorescence and photocatalytic CO2 reduction: unexpected enhancement by triethanolamine in catalytic activity

Y. Kuramochi, Y. Suzuki, S. Asai, T. Suzuki, H. Iwama, M. S. Asano and A. Satake, Chem. Sci., 2023, 14, 8743 DOI: 10.1039/D3SC02430J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements