A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp(2)‐Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Now, the synthesis of a three‐dimensional π‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels–Alder cycloaddition polymerization followed by acid‐promoted aromatization is presented. With a surface area of 801 m(2) g(−1), full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10(−4) S cm(−1) upon treatment with I(2) vapor, the 3D p‐POP is the first member of a new class of permanently porous 3D organic semiconductors.