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 5 2020
Accepted
28 7 2020
First published
28 7 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

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