Rational Construction of Electrically Conductive Covalent Organic Frameworks through Encapsulating Fullerene via Donor–Acceptor Interaction

Abstract A new kind of perylene‐based 2D covalent organic framework (COF) is designed and synthesized based on the C2 + C2 topological diagram. The perylene‐based COF is constructed via the condensation reaction using 2,5,8,11‐tetrakis((4‐formylphenyl) perylene (TFPPer) and 2,5,8,11‐tetrakis(4‐aminophenyl) perylene (TAPPer) as building blocks. The resulting TFPPer‐TAPPer‐COF features high crystallinity, excellent stability, intrinsic porosity, and an electron‐rich skeleton. Significantly, the electrical performance of the COF can be enhanced through the encapsulation of fullerene (C60) into the 1D channels via donor–acceptor interaction. Compared to the pristine COF, the electrical conductivity of C60@TFPPer‐TAPPer‐COF can be greatly increased from 8.98 × 10−8 to 1.59 × 10−5 S cm−1, meanwhile the carrier mobility rises from 1.04 × 10−3 to 4.23 × 10−2 cm2 V−1 s−1. The improvement in electrical performance stems from the strong donor–acceptor interaction between perylene and C60. These results provide insights into the rational construction of conductive COFs through donor–acceptor interaction and demonstrate their great potential in related application fields.