Lewis Acid–Base Chemistry of 7-Azaisoindigo-Based Organic Semiconductors

5 years ago

Lewis Acid–Base Chemistry of 7-Azaisoindigo-Based Organic Semiconductors

Timothy L. Kelly, Kyle M. Fransishyn, Nicholas M. Randell

Low-band-gap organic semiconductors are important in a variety of organic electronics applications, such as organic photovoltaic devices, photodetectors, and field effect transistors. Building on our previous work, which introduced 7-azaisoindigo as an electron-deficient building block for the synthesis of donor–acceptor organic semiconductors, we demonstrate how Lewis acids can be used to further tune the energies of the frontier molecular orbitals. Coordination of a Lewis acid to the pyridinic nitrogen of 7-azaisoindigo greatly diminishes the electron density in the azaisoindigo π-system, resulting in a substantial reduction in the lowest unoccupied molecular orbital (LUMO) energy. This results in a smaller highest occupied molecular orbital–LUMO gap and shifts the lowest-energy electronic transition well into the near-infrared region. Both H⁺ and BF₃ are shown to coordinate to azaisoindigo and affect the energy of the S₀ → S₁ transition. A combination of time-dependent density functional theory and UV/vis and ¹H NMR spectroscopic titrations reveal that when two azaisoindigo groups are present and high concentrations of acid are used, both pyridinic nitrogens bind Lewis acids. Importantly, we demonstrate that this acid–base chemistry can be carried out at the solid–vapor interface by exposing thin films of aza-substituted organic semiconductors to vapor-phase BF₃·Et₂O. This suggests the possibility of using the BF₃-bound 7-azaisoindigo-based semiconductors as n-type materials in various organic electronic applications.

Publisher URL: http://dx.doi.org/10.1021/acsami.7b06335

DOI: 10.1021/acsami.7b06335