Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties
Abstract
Modulation of organic semiconductor band gap, electron affinities (EA), ionization potentials (IP), and reorganization energies (λ) associated with charge transfer is critical for its applications. We report here that trifluoromethylation not only increases both IP and EA significantly as expected but also narrows the HOMO–LUMO band gaps and increases considerably the air-stability of arene-based n-type organic semiconductors. The increased air-stability results from relatively high EA energies and a change in oxidation mechanism. Calculated EAs and IPs show that trifluoromethylated arenes are excellent candidates for n-type semiconductor materials; though a moderate increase of inner-sphere reorganization energy (λi) associated with charge transfer is the penalty for the improved performance of the trifluoromethylated compounds. However, since λi decreases as the π conjugation increases, a rational design to produce air-stable n-type semiconductor materials with reasonably small λi is simply to prepare trifluoromethylated arenes with extended π conjugation. Finally, we found that structural isomerization can fine-tune the optoelectronic and electronic transfer properties of the corresponding aromatics.
- Authors:
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1052521
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 116; Journal Issue: 30; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- Environmental Molecular Sciences Laboratory
Citation Formats
Sun, Haoran, Putta, Anjaneyulu, and Billion, Michael. Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties. United States: N. p., 2012.
Web. doi:10.1021/jp301718j.
Sun, Haoran, Putta, Anjaneyulu, & Billion, Michael. Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties. United States. https://doi.org/10.1021/jp301718j
Sun, Haoran, Putta, Anjaneyulu, and Billion, Michael. 2012.
"Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties". United States. https://doi.org/10.1021/jp301718j.
@article{osti_1052521,
title = {Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties},
author = {Sun, Haoran and Putta, Anjaneyulu and Billion, Michael},
abstractNote = {Modulation of organic semiconductor band gap, electron affinities (EA), ionization potentials (IP), and reorganization energies (λ) associated with charge transfer is critical for its applications. We report here that trifluoromethylation not only increases both IP and EA significantly as expected but also narrows the HOMO–LUMO band gaps and increases considerably the air-stability of arene-based n-type organic semiconductors. The increased air-stability results from relatively high EA energies and a change in oxidation mechanism. Calculated EAs and IPs show that trifluoromethylated arenes are excellent candidates for n-type semiconductor materials; though a moderate increase of inner-sphere reorganization energy (λi) associated with charge transfer is the penalty for the improved performance of the trifluoromethylated compounds. However, since λi decreases as the π conjugation increases, a rational design to produce air-stable n-type semiconductor materials with reasonably small λi is simply to prepare trifluoromethylated arenes with extended π conjugation. Finally, we found that structural isomerization can fine-tune the optoelectronic and electronic transfer properties of the corresponding aromatics.},
doi = {10.1021/jp301718j},
url = {https://www.osti.gov/biblio/1052521},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 30,
volume = 116,
place = {United States},
year = {Thu Aug 02 00:00:00 EDT 2012},
month = {Thu Aug 02 00:00:00 EDT 2012}
}