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

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.