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 C 2 + C 2 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 (C 60 ) into the 1D channels via donor-acceptor interaction. Compared to the pristine COF, the electrical conductivity of C 60 @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 cm 2 V -1 s -1 . The improvement in electrical performance stems from the strong donor-acceptor interaction between perylene and C 60 . These results provide insights into the rational construction of conductive COFs through donor-acceptor interaction and demonstrate their great potential in related application fields.