A computational exploration of the crystal energy and charge-carrier mobility landscapes of the chiral [6]helicene molecule

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Title: A computational exploration of the crystal energy and charge-carrier mobility landscapes of the chiral [6]helicene molecule
Author(s): Rice, B
LeBlanc, LM
Otero-de-la-Roza, A
Fuchter, MJ
Johnson, ER
Nelson, J
Jelfs, KE
Item Type: Journal Article
Abstract: The potential of a given π-conjugated organic molecule in an organic semiconductor device is highly dependent on molecular packing, as it strongly influences the charge-carrier mobility of the material. Such solid-state packing is sensitive to subtle differences in their intermolecular interactions and is challenging to predict. Chirality of the organic molecule adds an additional element of complexity to intuitive packing prediction. Here we use crystal structure prediction to explore the lattice-energy landscape of a potential chiral organic semiconductor, [6]helicene. We reproduce the experimentally observed enantiopure crystal structure and explain the absence of an experimentally observed racemate structure. By exploring how the hole and electron-mobility varies across the energy–structure–function landscape for [6]helicene, we find that an energetically favourable and frequently occurring packing motif is particularly promising for electron-mobility, with a highest calculated mobility of 2.9 cm2 V−1 s−1 (assuming a reorganization energy of 0.46 eV). We also calculate relatively high hole-mobility in some structures, with a highest calculated mobility of 2.0 cm2 V−1 s−1 found for chains of helicenes packed in a herringbone fashion. Neither the energetically favourable nor high charge-carrier mobility packing motifs are intuitively obvious, and this demonstrates the utility of our approach to computationally explore the energy–structure–function landscape for organic semiconductors. Our work demonstrates a route for the use of computational simulations to aid in the design of new molecules for organic electronics, through the a priori prediction of their likely solid-state form and properties.
Publication Date: 5-Jan-2018
Date of Acceptance: 27-Dec-2017
URI: http://hdl.handle.net/10044/1/55823
DOI: https://dx.doi.org/10.1039/c7nr08890f
ISSN: 2040-3364
Publisher: Royal Society of Chemistry
Start Page: 1865
End Page: 1876
Journal / Book Title: Nanoscale
Volume: 10
Copyright Statement: © The Royal Society of Chemistry 2018
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Commission of the European Communities
Funder's Grant Number: EP/L014580/1
UF120469
EP/M017257/1
EP/P000525/1
EP/P005543/1
742708
Keywords: 10 Technology
02 Physical Sciences
03 Chemical Sciences
Nanoscience & Nanotechnology
Publication Status: Published
Embargo Date: 2019-01-05
Appears in Collections:Physics
Chemistry
Experimental Solid State
Centre for Environmental Policy
Faculty of Natural Sciences



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