A Tetrathiafulvalene-Based Electroactive Covalent Organic Framework

Two‐dimensional covalent organic frameworks (2D COFs) provide a unique platform for the molecular design of electronic and optoelectronic materials. Here, the synthesis and characterization of an electroactive COF containing the well‐known tetrathiafulvalene (TTF) unit is reported. The TTF‐COF crystallizes into 2D sheets with an eclipsed AA stacking motif, and shows high thermal stability and permanent porosity. The presence of TTF units endows the TTF‐COF with electron‐donating ability, which is characterized by cyclic voltammetry. In addition, the open frameworks of TTF‐COF are amenable to doping with electron acceptors (e.g., iodine), and the conductivity of TTF‐COF bulk samples can be improved by doping. Our results open up a reliable route for the preparation of well‐ordered conjugated TTF polymers, which hold great potential for applications in fields from molecular electronics to energy storage. An electroactive COF: A two‐dimensional covalent organic framework (COF) containing well‐known tetrathiafulvalene (TTF) units is synthesized (see figure). The presence of TTF units endows the TTF‐COF with electron‐donating ability, and the open frameworks of TTF‐COF are amenable to doping with electron acceptors (e.g., iodine). In addition, the conductivity of TTF‐COF bulk samples can be improved by doping.