Possible NLO response and electrical/charge transfer capabilities of natural anthraquinones as p-type organic semiconductors: a DFT approach.

Context: Organic semiconductors (OSCs) have attracted a great deal of interest in recent days. There are various types of OSCs, among which small molecules have various inherent benefits. Further research is needed to advance this new kind of material because the field is still developing, and the current focus is on creating small molecules that exist naturally for OSCs. OSCs with nonlinear optical (NLO) characteristics offer a significant advantage over others. Thus, this study theoretically investigates naturally occurring anthraquinones such as chrysophanol and rhein as potential OSCs, as well as their NLO properties. The calculated properties include the ionization potential (IP), electron affinity (EA), and bandgap (E). The FMO energy levels together with the E, IP (8.17-8.53 eV), and EA (1.87-2.44 eV) suggest the semiconductor nature of the studied compounds. The calculated values of reorganization energy (λ) and transfer integrals (V) suggest the p-type character of both molecules. Rhein has the lowest λ (0.19 eV) and E (3.28 eV) and the highest V, predominantly because of its better p-type character. The polarizability increases due to the presence of an electron-withdrawing substituent, leading to better NLO performance for Rhein, which is supported by its lower LUMO and E values.

Methods: The studied molecules were optimized with the DFT/B3LYP-GD3/6-31+G(d,p) method using Gaussian 16 software. The crystal structure was simulated with Materials Studio 7.0, and the V values were calculated with the ADF package. The CDD and DOS plots were obtained with the Multiwfn 3.8 program.