A Three-Dimensional Porous Organic Semiconductor Based on Fully sp -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  g , full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10  S cm upon treatment with I vapor, the 3D p-POP is the first member of a new class of permanently porous 3D organic semiconductors.