Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study
The chemical versatility of organic semiconductors provides nearly unlimited opportunities for tuning their electronic properties. However, despite decades of research, the relationship between molecular structure, molecular packing and charge mobility in these materials remains poorly understood. T...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-08-01
|
| Series: | International Journal of Molecular Sciences |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1422-0067/21/16/5654 |
| _version_ | 1797559812281597952 |
|---|---|
| author | Andrey Sosorev Dmitry Dominskiy Ivan Chernyshov Roman Efremov |
| author_facet | Andrey Sosorev Dmitry Dominskiy Ivan Chernyshov Roman Efremov |
| author_sort | Andrey Sosorev |
| collection | DOAJ |
| description | The chemical versatility of organic semiconductors provides nearly unlimited opportunities for tuning their electronic properties. However, despite decades of research, the relationship between molecular structure, molecular packing and charge mobility in these materials remains poorly understood. This reduces the search for high-mobility organic semiconductors to the inefficient trial-and-error approach. For clarifying the abovementioned relationship, investigations of the effect of small changes in the chemical structure on organic semiconductor properties are particularly important. In this study, we computationally address the impact of the substitution of C-H atom pairs by nitrogen atoms (N-substitution) on the molecular properties, molecular packing and charge mobility of crystalline oligoacenes. We observe that besides decreasing frontier molecular orbital levels, N-substitution dramatically alters molecular electrostatic potential, yielding pronounced electron-rich and electron-deficient areas. These changes in the molecular electrostatic potential strengthen face-to-face and edge-to-edge interactions in the corresponding crystals and result in the crossover from the herringbone packing motif to π-stacking. When the electron-rich and electron-deficient areas are large, sharply defined and, probably, have a certain symmetry, calculated charge mobility increases up to 3–4 cm<sup>2</sup>V<sup>−1</sup>s<sup>−1</sup>. The results obtained highlight the potential of azaacenes for application in organic electronic devices and are expected to facilitate the rational design of organic semiconductors for the steady improvement of organic electronics. |
| first_indexed | 2024-03-10T17:50:34Z |
| format | Article |
| id | doaj.art-19b57c59e4fc4a44a591c6f8e717ac15 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T17:50:34Z |
| publishDate | 2020-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-19b57c59e4fc4a44a591c6f8e717ac152023-11-20T09:20:57ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672020-08-012116565410.3390/ijms21165654Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational StudyAndrey Sosorev0Dmitry Dominskiy1Ivan Chernyshov2Roman Efremov3Department of Structural Biology, Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences, 117997 Moscow, RussiaFaculty of Physics and International Laser Center, Lomonosov Moscow State University, 119991 Moscow, RussiaChemBio Cluster, ITMO University, 191002 Saint Petersburg, RussiaDepartment of Structural Biology, Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences, 117997 Moscow, RussiaThe chemical versatility of organic semiconductors provides nearly unlimited opportunities for tuning their electronic properties. However, despite decades of research, the relationship between molecular structure, molecular packing and charge mobility in these materials remains poorly understood. This reduces the search for high-mobility organic semiconductors to the inefficient trial-and-error approach. For clarifying the abovementioned relationship, investigations of the effect of small changes in the chemical structure on organic semiconductor properties are particularly important. In this study, we computationally address the impact of the substitution of C-H atom pairs by nitrogen atoms (N-substitution) on the molecular properties, molecular packing and charge mobility of crystalline oligoacenes. We observe that besides decreasing frontier molecular orbital levels, N-substitution dramatically alters molecular electrostatic potential, yielding pronounced electron-rich and electron-deficient areas. These changes in the molecular electrostatic potential strengthen face-to-face and edge-to-edge interactions in the corresponding crystals and result in the crossover from the herringbone packing motif to π-stacking. When the electron-rich and electron-deficient areas are large, sharply defined and, probably, have a certain symmetry, calculated charge mobility increases up to 3–4 cm<sup>2</sup>V<sup>−1</sup>s<sup>−1</sup>. The results obtained highlight the potential of azaacenes for application in organic electronic devices and are expected to facilitate the rational design of organic semiconductors for the steady improvement of organic electronics.https://www.mdpi.com/1422-0067/21/16/5654organic electronicsorganic semiconductorsmolecular designcrystal designπ-stackingcharge mobility |
| spellingShingle | Andrey Sosorev Dmitry Dominskiy Ivan Chernyshov Roman Efremov Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study International Journal of Molecular Sciences organic electronics organic semiconductors molecular design crystal design π-stacking charge mobility |
| title | Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study |
| title_full | Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study |
| title_fullStr | Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study |
| title_full_unstemmed | Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study |
| title_short | Tuning of Molecular Electrostatic Potential Enables Efficient Charge Transport in Crystalline Azaacenes: A Computational Study |
| title_sort | tuning of molecular electrostatic potential enables efficient charge transport in crystalline azaacenes a computational study |
| topic | organic electronics organic semiconductors molecular design crystal design π-stacking charge mobility |
| url | https://www.mdpi.com/1422-0067/21/16/5654 |
| work_keys_str_mv | AT andreysosorev tuningofmolecularelectrostaticpotentialenablesefficientchargetransportincrystallineazaacenesacomputationalstudy AT dmitrydominskiy tuningofmolecularelectrostaticpotentialenablesefficientchargetransportincrystallineazaacenesacomputationalstudy AT ivanchernyshov tuningofmolecularelectrostaticpotentialenablesefficientchargetransportincrystallineazaacenesacomputationalstudy AT romanefremov tuningofmolecularelectrostaticpotentialenablesefficientchargetransportincrystallineazaacenesacomputationalstudy |