A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp2‐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. Here, we report 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. With a surface area of 801 m² g^-1 , full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2) x 10^–4 S cm^–1 upon treatment with I₂ vapor, the 3D p-POP represents the first member of a new class of permanently porous 3D organic semiconductors.