A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp2‐Hybridized Graphitic Polymer

<p>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 &pi;-conjugated porous organic polymer (3D p-POP) using catalyst-free Diels&minus;Alder cycloaddition polymerization followed by acid-promoted aromatization. With a&nbsp;surface area of 801 m²&nbsp;g^-1 , full conjugation throughout the carbon&nbsp;backbone, and an electrical conductivity of 6(2) x&nbsp;10^&ndash;4&nbsp;S cm^&ndash;1&nbsp;upon treatment with I₂&nbsp;vapor, the 3D p-POP represents the first member of a new class of permanently porous 3D organic semiconductors.</p>