Rylene and Rylene Diimides: Comparison of Theoretical and Experimental Results and Prediction for High-Rylene Derivatives.

Low rylene (R) and rylene diimides (RD) are important organic semiconductors and dyes. High R and RD with larger conjugated cores show different properties compared with their low counterparts. Herein, absorption spectra, frontier molecular orbitals, band gaps, inner-sphere reorganization energy (λi), ionization potential, electron affinity, and atomic charge population of 20 rylene compounds were calculated by the density functional theory method. The theoretical results agree well with experimental ones. We predict some unusual properties of some high rylene derivatives that are unknown compounds due to synthetic difficulties. The lowest unoccupied molecular orbital energy levels of RD compounds change slightly, from -3.61 to -3.79 eV, which makes them strong electron acceptors. The band gaps narrow with the size increase of conjugated cores, which makes high rylene derivatives near-infrared dyes. The rising highest occupied molecular orbital energy levels of high rylene derivatives makes them unstable in the air. The λi falls with the size increase of the conjugated core, and the size of RD-4 or R-4 is big enough for the small λi to favor charge transport. The charge population analysis indicates R and RD have different charge distribution under the effect of electron-withdrawing imide groups, which contributes to distinct properties.