Issue 33, 2020

Structure–activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water

Abstract

Most organic semiconductor photocatalysts for solar fuels production are linear polymers or polymeric networks with a broad distribution of molecular weights. Here, we study a series of molecular dibenzo[b,d]thiophene sulfone and fluorene oligomers as well-defined model systems to probe the relationship between photocatalytic activity and structural features such as chain length and planarity. The hydrogen evolution rate was found to vary significantly with bridge head atom, chain length, and backbone twisting. A trimer (S3) of only three repeat units has excellent activity for proton reduction with an EQE of 8.8% at 420 nm, approaching the activity of its polymer analogue and demonstrating that high molar masses are not a prerequisite for good activity. The dynamics of long-lived electrons generated under illumination in the S3 oligomer are very similar to the corresponding polymer, both under transient and quasi-continuous irradiation conditions.

Graphical abstract: Structure–activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water

Supplementary files

Article information

Article type
Edge Article
Submitted
11 May 2020
Accepted
28 Jul 2020
First published
28 Jul 2020
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., 2020,11, 8744-8756

Structure–activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water

C. M. Aitchison, M. Sachs, M. A. Little, L. Wilbraham, N. J. Brownbill, C. M. Kane, F. Blanc, M. A. Zwijnenburg, J. R. Durrant, R. S. Sprick and A. I. Cooper, Chem. Sci., 2020, 11, 8744 DOI: 10.1039/D0SC02675A

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