Highly Conductive Covalent–Organic Framework Films

Abstract Chemically inert organic networks exhibiting electrical conductivity comparable to metals can advance organic electronics, catalysis, and energy storage systems. Covalent–organic frameworks (COFs) have emerged as promising materials for those applications due to their high crystallinity, porosity, and tunable functionality. However, their low conductivity has limited their practical utilization. In this study, copper‐coordinated‐fluorinated‐phthalocyanine and 2,3,6,7‐tetrahydroxy‐9,10‐anthraquinone‐based COF (CuPc‐AQ‐COF) films with ultrahigh conductivity are developed. The COF films exhibit an electrical conductivity of 1.53 × 10 3 S m −1 and a Hall mobility of 6.02 × 10 2 cm 2 V −1 s −1 at 298 K, reaching the level of metals. The films are constructed by linking phthalocyanines and anthraquinones through vapor‐assisted synthesis. The high conductivity properties of the films are attributed to the molecular design of the CuPc‐AQ‐COFs and the generation of high‐quality crystals via the vapor‐assisted method. Density functional theory analysis reveals that an efficient donor–acceptor system between the copper‐coordinated phthalocyanines and anthraquinones significantly promotes charge transfer. Overall, the CuPc‐AQ‐COF films set new records of COF conductivity and mobility and represent a significant step forward in the development of COFs for electronic, catalytic, and electrochemical applications.