# Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach

## Abstract

Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integralmore »

- Authors:

- Departamento de Química Física y Analítica, Universidad de Jaén, Campus Las Lagunillas, E23071 Jaén (Spain)
- Instituto de Energía Solar and Departamento TFB, E.T.S.I. Telecomunicación, Universidad Politécnica de Madrid, Ciudad Universitaria, Madrid 28040 (Spain)

- Publication Date:

- OSTI Identifier:
- 22678974

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 5; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHARGE TRANSPORT; DENSITY FUNCTIONAL METHOD; ELECTRON BEAM INJECTION; ELECTRON TRANSFER; ENERGY LEVELS; EXPERIMENTAL DATA; LIQUID CRYSTALS; PERYLENE

### Citation Formats

```
Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, and García, Gregorio.
```*Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach*. United States: N. p., 2016.
Web. doi:10.1063/1.4960051.

```
Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, & García, Gregorio.
```*Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach*. United States. doi:10.1063/1.4960051.

```
Navarro, Amparo, E-mail: anavarro@ujaen.es, Fernández-Liencres, M. Paz, Peña-Ruiz, Tomás, Granadino-Roldán, José M., Fernández-Gómez, Manuel, and García, Gregorio. Sun .
"Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach". United States.
doi:10.1063/1.4960051.
```

```
@article{osti_22678974,
```

title = {Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach},

author = {Navarro, Amparo, E-mail: anavarro@ujaen.es and Fernández-Liencres, M. Paz and Peña-Ruiz, Tomás and Granadino-Roldán, José M. and Fernández-Gómez, Manuel and García, Gregorio},

abstractNote = {Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.},

doi = {10.1063/1.4960051},

journal = {Journal of Chemical Physics},

number = 5,

volume = 145,

place = {United States},

year = {Sun Aug 07 00:00:00 EDT 2016},

month = {Sun Aug 07 00:00:00 EDT 2016}

}