Fully Conjugated Tetraoxa[8]circulene-Based Porous Semiconducting Polymers

Tetraoxa[8]circulenes (TOCs) are a class of hetero[8]circulenes featuring a planar cyclooctatetraene core with a mixed aromatic/antiaromatic motif that governs their electronic properties. Polymeric TOCs (pTOCs) have been the subject of several computational simulations because they are predicted to be low-band-gap semiconductors, but they have not been available synthetically yet. Here, we report the first example of pTOCs, a new family of porous semiconductors, synthesized under ionothermal conditions through the intermolecular cyclization of 1,4,5,8-anthracene tetrone. pTOCs are porous, with surface areas up to 1656 m2 g−1, and exhibit light-switchable and tunable semiconducting properties.