Photocatalytic Proton Reduction by a Computationally Identified, Molecular Hydrogen-Bonded Framework

Aitchison, Catherine ORCID: 0000-0003-1437-8314, Kane, Christopher, McMahon, David P, Spackman, Peter, Wang, xiaoyan, Wilbraham, Liam, Pulido, Angeles, Chen, linjiang, Clowes, Rob, Little, Marc
et al (show 4 more authors) (2020) Photocatalytic Proton Reduction by a Computationally Identified, Molecular Hydrogen-Bonded Framework. Journal of Materials Chemistry A, 2020 (15). 7158 - 7170.

This is the latest version of this item.

[img] Text
Author Accepted Version.pdf - Accepted Version

Download (885kB) | Preview
[img] Text
Photocatalytic.pdf - OA Published Version

Download (3MB) | Preview


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 pi-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.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 24 Jun 2020 10:57
Last Modified: 04 Sep 2022 07:12
DOI: 10.1039/d0ta00219d
Related URLs:

Available Versions of this Item