Issue 15, 2020

Photocatalytic proton reduction by a computationally identified, molecular hydrogen-bonded framework

Abstract

We show that a hydrogen-bonded framework, TBAP-α, with extended π-stacked pyrene columns has a sacrificial photocatalytic hydrogen production rate of up to 3108 μmol g−1 h−1. This is the highest activity reported for a molecular organic crystal. By comparison, a chemically-identical but amorphous sample of TBAP was 20–200 times less active, depending on the reaction conditions, showing unambiguously that crystal packing in molecular crystals can dictate photocatalytic activity. Crystal structure prediction (CSP) was used to predict the solid-state structure of TBAP and other functionalised, conformationally-flexible pyrene derivatives. Specifically, we show that energy–structure–function (ESF) maps can be used to identify molecules such as TBAP that are likely to form extended π-stacked columns in the solid state. This opens up a methodology for the a priori computational design of molecular organic photocatalysts and other energy-relevant materials, such as organic electronics.

Graphical abstract: Photocatalytic proton reduction by a computationally identified, molecular hydrogen-bonded framework

Supplementary files

Article information

Article type
Paper
Submitted
06 Phe 2020
Accepted
14 Ube 2020
First published
20 Ube 2020
This article is Open Access
Creative Commons BY license

J. Mater. Chem. A, 2020,8, 7158-7170

Photocatalytic proton reduction by a computationally identified, molecular hydrogen-bonded framework

C. M. Aitchison, C. M. Kane, D. P. McMahon, P. R. Spackman, A. Pulido, X. Wang, L. Wilbraham, L. Chen, R. Clowes, M. A. Zwijnenburg, R. S. Sprick, M. A. Little, G. M. Day and A. I. Cooper, J. Mater. Chem. A, 2020, 8, 7158 DOI: 10.1039/D0TA00219D

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