TY - JOUR
T1 - Photocatalytic Proton Reduction by a Computationally Identified, Molecular Hydrogen-bonded Framework
AU - Aitchison, Catherine M.
AU - Kane, Christopher M.
AU - Mcmahon, David P.
AU - Spackman, Peter R.
AU - Pulido, Angeles
AU - Wang, Xiaoyan
AU - Wilbraham, Liam
AU - Chen, Linjiang
AU - Clowes, Rob
AU - Zwijnenburg, Martijn A.
AU - Sprick, Reiner Sebastian
AU - Little, Marc A.
AU - Day, Graeme M.
AU - Cooper, Andrew I.
N1 - Funding Information:
The authors gratefully acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/N004884/1), the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC through grant agreement numbers 321156 (ERC-AG-PE5-ROBOT) and 307358 (ERC-stG-2012-ANGLE), and the Leverhulme Research Centre for Functional Materials Design for funding. We thank Diamond Light Source for access to beamlines I19 (CY21726). We thank the Advanced Light Source, supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231, and thank Simon J. Teat for his assistance during this experiment. We acknowledge the use of the IRIDIS High Performance Computing Facility, and associated support services at the University of Southampton, and the ARCHER UK National Supercomputing Service, via our membership of the UK's HEC Materials Chemistry Consortium funded by EPSRC (EP/ L000202, EP/R029431), in the completion of this work. The authors acknowledge the EPSRC UK National Mass Spectrometry Facility at Swansea University. Dr Jan-Gerrit Brandenburg and Prof. Furio Cora are kindly acknowledged for useful discussion.
Publisher Copyright:
This journal is © The Royal Society of Chemistry.
PY - 2020/4/21
Y1 - 2020/4/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85082837272&partnerID=8YFLogxK
U2 - 10.1039/d0ta00219d
DO - 10.1039/d0ta00219d
M3 - Article
AN - SCOPUS:85082837272
SN - 2050-7488
VL - 8
SP - 7158
EP - 7170
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
IS - 15
ER -
