Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties
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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1052521
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 116, Issue 30; ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
Similar Records
Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings
Thin-Film Deposition and Characterization of a Sn-Deficient Perovskite Derivative Cs2SnI6