Theoretical Investigation of Charge Transport and Optoelectronic Properties of Bowl-Shaped Dicyclopenta[ghi,pqr]perylene Derivatives

We designed a series of 24 bowl-shaped dicyclopenta[ghi,pqr]perylene (DCPP) derivatives with an aim to establish their charge transport and optoelectronic properties in relation to some structural modifications. The descriptors such as bowl-to-bowl inversion barrier, aromaticity, frontier molecular orbitals, ionization energies, and electron affinities (EAs) were predicted and analyzed in this report. We have found that extended π-conjugation and electron-withdrawing groups in the DCPP derivatives result in fairly high EAs (>3.0 eV) and narrow band gaps (1.35–1.66 eV), which promote the air-stable charge injection. By modeling the crystal structures, we find that the compounds are mostly arranged in bowl-in-bowl columnar packing, which is suitable for facilitating the intermolecular charge transport in the crystal. As a result, the p-type, n-type, and even ambipolar behavior of these bowl-shaped DCPP derivatives was anticipated through the systematic screening of the operational conditions. In particular, DCPP-12 (μh/μe = 4.90 × 10–3/2.50 × 10–3 cm2 V–1 s–1) and DCPP-TES-12 (μh/μe = 1.04 × 10–2/1.22 × 10–2 cm2 V–1 s–1) satisfy all the criteria for ambipolar organic semiconductors. Furthermore, the high linear and nonlinear optical activities of the DCPP derivatives pave their way toward organic-based optoelectronic applications.