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

Catherine M. Aitchison; Christopher M. Kane; David P. McMahon; Peter R. Spackman; Angeles Pulido; Xiaoyan Wang; Liam Wilbraham; Linjiang Chen; Rob Clowes; Martijn A. Zwijnenburg; Reiner Sebastian Sprick; Marc A. Little; Graeme M. Day; Andrew I. Cooper

doi:10.1039/D0TA00219D

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

Catherine M. Aitchison,

‡^a Christopher M. Kane,‡^a David P. McMahon,‡^b Peter R. Spackman,^bc Angeles Pulido,

^b Xiaoyan Wang,^a Liam Wilbraham,^d Linjiang Chen,

^ac Rob Clowes,^a Martijn A. Zwijnenburg,

^d Reiner Sebastian Sprick,

^a Marc A. Little,

^a Graeme M. Day

*^b and Andrew I. Cooper

*^ac

Author affiliations

* Corresponding authors

^a Department of Chemistry and Materials Innovation Factory, University of Liverpool, Liverpool L7 3NY, UK
E-mail: aicooper@liverpool.ac.uk

^b Computational Systems Chemistry, School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK
E-mail: g.m.day@soton.ac.uk

^c Leverhulme Research Centre for Functional Materials Design, University of Liverpool, Liverpool L7 3NY, UK

^d Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK

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.

This article is part of the themed collections: Celebrating our 2021 Prizewinners and Journal of Materials Chemistry A HOT Papers

Journal of Materials Chemistry A

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

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

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