Crystal Engineering in Oligorylenes: The Quest for Optimized Crystal Packing and Enhanced Charge Transport

The crystal structures of organic semiconductors are critical when they are integrated into optoelectronic devices, such as organic field-effect transistors (OFETs). In this study, we introduce a crystal engineering approach that leverages weak, nondirectional dispersion forces and steric effects, working together to govern the molecular packing. We investigated how the substitution at the peri-position affects the crystal structure in a series of oligorylene molecules. Upon elucidation of the crystal structures, we found a distinct difference between symmetrical and unsymmetrical derivatives. The unsymmetrical derivatives are prone to forming a sandwich herringbone (SHB) motif, while symmetrical derivatives exhibit a typical herringbone (HB) motif. In most of the rylene derivatives, substitutions at the peri-position triggered an "end-to-face" orientation within the HB structure, rather than an "edge-to-face" orientation, which occurs more often. Results from the Hirschfeld surface analysis provide evidence that the "end-to-face" orientation promotes C-H-π interactions between terminal methyl groups and the π-core of the molecules. While these C-H<sub>methyl</sub>---π interactions contribute to the overall stability of the packing structure, they remain ineffective in enhancing the charge transport properties. In contrast, a particular derivative, tetramethyl perylene (<b>TMP</b>), exhibits a HB structure with an edge-to-face orientation, promoting both C-H---π and π---π interactions. These interactions are crucial for improving the charge carrier mobility, as evidenced by mobility values. For <b>TMP</b>, we could obtain the mobility value of 0.05 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> in OFETs, whereas a slightly higher mobility of 0.2 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> was observed with Field-Induced Time-Resolved Microwave conductivity (FI-TRMC) technique.

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Publication Details

Journal
Crystal Growth & Design
Published
2025-04-23
DOI
https://doi.org/10.1021/acs.cgd.5c00145
Primary Topic
Crystallography and molecular interactions
Type
article
Field-Weighted Citation Impact
0.00

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article

Crystal Engineering in Oligorylenes: The Quest for Optimized Crystal Packing and Enhanced Charge Transport

Lucia Maini, Christos Gatsios, Martina Volpi, Guillaume Schweicher et al.
Crystal Growth & Design
Crystallography and molecular interactions
article

Crystal Engineering in Oligorylenes: The Quest for Optimized Crystal Packing and Enhanced Charge Transport

Lucia Maini, Christos Gatsios, Martina Volpi, Guillaume Schweicher, Jérôme Cornil, Priya Pandey, Luca Catalano, Shu Seki, Yves Henri Geerts, Peter Erk, Paolo Samorı́, Erika Samoľová, Nemo McIntosh, Petr Brázda, Federico Modesti, Norbert Koch, Caterina Zuffa, Rahul Meena, Nicholas Turetta, Wookjin Choi
article en

Abstract

The crystal structures of organic semiconductors are critical when they are integrated into optoelectronic devices, such as organic field-effect transistors (OFETs). In this study, we introduce a crystal engineering approach that leverages weak, nondirectional dispersion forces and steric effects, working together to govern the molecular packing. We investigated how the substitution at the peri-position affects the crystal structure in a series of oligorylene molecules. Upon elucidation of the crystal structures, we found a distinct difference between symmetrical and unsymmetrical derivatives. The unsymmetrical derivatives are prone to forming a sandwich herringbone (SHB) motif, while symmetrical derivatives exhibit a typical herringbone (HB) motif. In most of the rylene derivatives, substitutions at the peri-position triggered an "end-to-face" orientation within the HB structure, rather than an "edge-to-face" orientation, which occurs more often. Results from the Hirschfeld surface analysis provide evidence that the "end-to-face" orientation promotes C-H-π interactions between terminal methyl groups and the π-core of the molecules. While these C-H<sub>methyl</sub>---π interactions contribute to the overall stability of the packing structure, they remain ineffective in enhancing the charge transport properties. In contrast, a particular derivative, tetramethyl perylene (<b>TMP</b>), exhibits a HB structure with an edge-to-face orientation, promoting both C-H---π and π---π interactions. These interactions are crucial for improving the charge carrier mobility, as evidenced by mobility values. For <b>TMP</b>, we could obtain the mobility value of 0.05 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> in OFETs, whereas a slightly higher mobility of 0.2 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> was observed with Field-Induced Time-Resolved Microwave conductivity (FI-TRMC) technique.

Crystal Growth & DesignVol. 25(9)
University of Modena and Reggio Emilia (IT), Centre National de la Recherche Scientifique (FR), University of Mons (BE), Université Libre de Bruxelles (BE), Czech Academy of Sciences (CZ), Kyoto University (JP), Enercon (Germany) (DE), Humboldt-Universität zu Berlin (DE), Novel (United States) (US), BASF (Germany) (DE), FZU ‒ Institute of Physics of the Academy of Sciences of the Czech Republic (CZ), Walloon Excellence in Lifesciences and Biotechnology (BE), Adler (CA), International Solvay Institutes (BE), University of Rochester (US), Université de Strasbourg (FR), Graduate School USA (US), University of Bologna (IT)
National Science Foundation, European Commission, Fonds De La Recherche Scientifique - FNRS, Fédération Wallonie-Bruxelles, Nederlandse Organisatie voor Wetenschappelijk Onderzoek, Fondation Francqui - Stichting, Engineering and Physical Sciences Research Council, H2020 Marie Skłodowska-Curie Actions
Openalex Percentile: Top 91%
Crystallography and molecular interactions
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