Cyclopentadithiophene-Based Organic Semiconductors: Effect of Fluorinated Substituents on Electrochemical and Charge Transport Properties

Thiophene-based semiconductors are often hole conductors that have been converted to electron-transporting materials by incorporation of electron-withdrawing groups at terminal positions, such as fluorinated substituents. This conversion of an otherwise p-type material to n-type material is often attributed to the lowering of the lowest unoccupied molecular orbital (LUMO) energy level due to the increased electron affinity in the molecule. Yet, it is not clear if lowering of LUMO energy level is a sufficient condition for yielding n-type material. Herein, we report small-molecule semiconductors based on cyclopentadithiophene (CPD), which can be orthogonally functionalized at two different positions, which allows us to tune the frontier orbital energy levels. We find that simply lowering the LUMO energy level, without inclusion of fluoro groups, does not result in conversion of the otherwise p-type material to n-type material, whereas incorporation of fluorinated substituents does. This indicates that charge transport behavior is not an exclusive function of the frontier orbital energy levels.