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

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

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.

2050-7488
7158-7170
Aitchison, Catherine
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Kane, Christopher
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Mcmahon, David P.
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Spackman, Peter
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Pulido, Angeles
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Wang, Xiaoyan
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Wilbraham, Liam
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Chen, Linjiang
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Clowes, Rob
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Zwijnenburg, Martijn
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Sprick, Reiner Sebastian
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Little, Marc A.
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Day, Graeme M.
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Cooper, Andrew I.
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Aitchison, Catherine
d59849c7-8ffa-4afa-a34b-e2777aba23a3
Kane, Christopher
934222c0-d761-4f34-802f-358b0a2f6d2b
Mcmahon, David P.
026a4184-d048-4a12-964e-5c6d9da81c68
Spackman, Peter
0b8d8f08-0b3b-45ce-8607-dafa10f28afe
Pulido, Angeles
cdc804ed-2c64-4f41-85f9-b8fadc2940b6
Wang, Xiaoyan
42b11c69-2876-47e0-9422-8b3595592aec
Wilbraham, Liam
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Chen, Linjiang
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Clowes, Rob
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Zwijnenburg, Martijn
aca065ed-5cc7-4dc0-b6f0-efb961d0a810
Sprick, Reiner Sebastian
c04c0344-840f-41a9-a3d7-4e297a4aafbd
Little, Marc A.
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Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Cooper, Andrew I.
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Aitchison, Catherine, Kane, Christopher, Mcmahon, David P., Spackman, Peter, Pulido, Angeles, Wang, Xiaoyan, Wilbraham, Liam, Chen, Linjiang, Clowes, Rob, Zwijnenburg, Martijn, Sprick, Reiner Sebastian, Little, Marc A., Day, Graeme M. and Cooper, Andrew I. (2020) Photocatalytic proton reduction by a computationally identified, molecular hydrogen-bonded framework. Journal of Materials Chemistry A, 8 (15), 7158-7170. (doi:10.1039/D0TA00219D).

Record type: Article

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.

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TA-ART-01-2020-000219_Manuscript_Revised - Accepted Manuscript
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Accepted/In Press date: 14 March 2020
e-pub ahead of print date: 20 March 2020
Published date: 21 April 2020

Identifiers

Local EPrints ID: 438872
URI: http://eprints.soton.ac.uk/id/eprint/438872
ISSN: 2050-7488
PURE UUID: e0643ed6-ced0-4ed0-9d30-e741bddbd522
ORCID for Angeles Pulido: ORCID iD orcid.org/0000-0002-7596-7262
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 26 Mar 2020 17:30
Last modified: 23 Jul 2022 04:51

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Contributors

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

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