Co-condensation of metallophthalocyanine with an electron-deficient benzothiadiazole (BTDA) block leads to the formation of a two-dimensional covalent organic framework (2D-NiPc-BTDA COF) that assumes a belt shape and consists of AA stacking of 2D polymer sheets. Integration of BTDA blocks at the edges of a tetragonal metallophthalocyanine COF causes drastic changes in the carrier-transport mode and a switch from a hole-transporting skeleton to an electron-transporting framework. 2D-NiPc-BTDA COF exhibits broad and enhanced absorbance up to 1000 nm, shows panchromatic photoconductivity, is highly sensitive to near-infrared photons, and has excellent electron mobility as high as 0.6 cm(2) V(-1) s(-1).

A donor‐acceptor built‐in covalent organic framework with segregated, periodic, and bicontinuous electron donor‐acceptor ordering is reported. The framework consists of pre‐organized periodic independent pathways for ambipolar electron and hole conduction and constitutes vertically ordered p‐n heterojunctions with a broad D‐A interface for enhanced photoconductivity.

No abstract