An efficient strategy for improving carrier transport performance – Introducing fluorine into aryl substituted tetracene

Abstract Why does the fluorination of just one phenyl in 5,11-diphenyltetracene ( PPT ) bring about so tremendous change of the charge carrier mobility? Herein, we carried out density functional theory (DFT) to provide insight into this remarkable difference by investigating their geometries, electronic structures, reorganization energies, transfer integrals, intermolecular interactions and band structures. The improved charge mobility from PPT to FPPT (5-(perfluorophenyl)-11-phenyltetracene) can be attributed to favorable molecular packing due to the increase of π–π interaction which is confirmed by Hirshfeld surfaces analysis. Furthermore, we calculated charge mobilities of novel compound 4,11-diphenyltetracene ( PPT′ ) and its fluorinated derivative 4-(perfluorophenyl)-11-phenyltetracene ( FPPT′ ), on the basis of the predicted packing motifs. The largest charge mobility of FPPT′ (2.49 cm 2 /V s) exhibits one-fold higher than PPT′ (1.07 cm 2 /V s) due to dense packing structures, which further confirms our finding that fluorination may be an effective means to improve the carrier mobility. This work paves the way towards the development of a computational protocol that could be implemented not only for rationalizing synthetic efforts but also for design of high-performance organic transport materials.