Semi‐perfluoroalkylated perylene diimides for conjugated polymers with high molecular weight and high electron mobility

Perylene diimides (PDIs) and their derivatives are excellent semiconductors, while conjugated polymers based on PDIs have limited applications because of their low electron mobility (μ_e) derived from low molecular weight. The reported maximum number‐average molecular weight (M_n) of related polymers is only 21 kDa because PDIs have very poor solubility due to strong π–π stacking of their big planar conjugated cores. Herein, it is found that suitable semi‐perfluoroalkyl groups could enhance the solubility of PDIs significantly, and a series of semi‐perfluoroalkyl modified conjugated polymers with high molecular weight and electron mobility were synthesized. The maximum M_n reaches 94.8 kDa [P(4C_F8C_H‐PDI‐T2)_HW]. In their space‐charge‐limited current (SCLC) devices, all polymers exhibit typical characters of electron transporting semiconductors, and the highest μ_e is up to 8.40 × 10⁻³ cm² V⁻¹ s⁻¹ [P(4C_F8C_H‐PDI‐T2)_HW], which is similar as that of widely used electron transporting semiconductor PC₆₁BM (6.41 × 10⁻³ cm² V⁻¹ s⁻¹). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 116–124