2D Semiconducting Polymers Based on Aromatic 1,5‐Diheterocines with Oxygen and Nitrogen

Abstract

AbstractA class of two‐dimensional polymers (2DP) based on aromatic oxygen‐ and nitrogen‐containing 1,5‐diheterocines is proposed. The diheterocines are interconnected via linkages with multiple bonds (─N═N─, ─C≡C─, ─N═CH─, ─CH═CH─) resulting in 30 polymers with 2D π‐conjugated network. According to DFT modeling nine of them are strictly planar species of monoclinic symmetry featuring either direct or indirect electronic transitions with HSE06 energies falling in the range [0.01–1.03] eV. The highest charge carrier velocity and corresponding lowest mass are estimated at 5.79 × 105 m s−1 and 9.45 × 10−3 m0, respectively. In addition to prospective optoelectronic applications, the polymers can be used in separation/filtration technologies. The proof‐of‐principle of N2/O2 separation is presented. Pore sizes of the 2DPs can be varied subject to the size of linkages. This study opens up new avenues for a design of multifunctional 2DPs.