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

Abstract

A 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 × 10 5 m s −1 and 9.45 × 10 −3 m 0 , respectively. In addition to prospective optoelectronic applications, the polymers can be used in separation/filtration technologies. The proof-of-principle of N 2 /O 2 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.