Computational screening of organic semiconductors: exploring side-group functionalisation and assembly to optimise charge transport in chiral molecules
File(s)acs.cgd.1c00473.pdf (4.24 MB)
Published version
Author(s)
Type
Journal Article
Abstract
Molecular materials are challenging to design as their packing arrangement and hence properties are subject to subtle variations in the interplay of soft intermolecular interactions that are difficult to predict. The rational design of new molecular materials with tailored properties is currently hampered by the lack of knowledge of how a candidate molecule will pack in space and how we can control the polymorphs we can experimentally obtain. Here, we develop a simplified approach to aid the material design process, by the development of a screening process that is used to test 1344 helicene molecules that have potential as organic electronic materials. Our approach bridges the gap between single molecule design, molecular assembly, and the resulting charge-carrier mobilities. We find that fluorination significantly improves electron transport in the molecular material by up to 200%; the reference [6]helicene packing showed a mobility of 0.30 cm2 V-1 s-1, fluorination increased the mobility to up to 0.96 and 0.97 (13-fluoro[6]H and 4,13-difluoro[6]H), assuming an outer reorganisation energy of 0.30 eV. Side groups containing triple bonds largely lead to improved transfer integrals. We validate our screening approach through the use of crystal structure prediction to confirm the presence of favourable packing motifs to maximize charge mobility.
Date Issued
2021-09-01
Date Acceptance
2021-05-25
Citation
Crystal Growth and Design, 2021, 21, pp.5036-5049
ISSN
1528-7483
Publisher
ACP Publications
Start Page
5036
End Page
5049
Journal / Book Title
Crystal Growth and Design
Volume
21
Copyright Statement
© 2021 The Authors. Published by American Chemical Society. This work is published under CC BY-NC-ND license.
Sponsor
The Royal Society
Commission of the European Communities
The Royal Society
The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Identifier
https://pubs.acs.org/doi/10.1021/acs.cgd.1c00473
Grant Number
UF120469
758370
RGF\EA\180057
URF\R\180012
EP/J014958/1
EP/J003840/1
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Crystallography
Materials Science, Multidisciplinary
Chemistry
Materials Science
CRYSTAL-STRUCTURE PREDICTION
HARTREE-FOCK
ENERGY
MOBILITY
FLUORINATION
LANDSCAPES
MOLECULES
PERFORMANCE
ENERGETICS
HELICENES
Inorganic & Nuclear Chemistry
0302 Inorganic Chemistry
0306 Physical Chemistry (incl. Structural)
0912 Materials Engineering
Publication Status
Published
Date Publish Online
2021-08-08