Visualization of Multiple-Resonance-Induced Frontier Molecular Orbitals in a Single Multiple-Resonance Thermally Activated Delayed Fluorescence Molecule

Abstract

The spatial distribution and electronic properties of the frontier molecular orbitals (FMOs) in a thermally activated delayed fluorescence (TADF) molecule contribute significantly to the TADF properties, and thus, a detailed understanding and sophisticated control of the FMOs are fundamental to the design of TADF molecules. However, for multiple-resonance (MR)-TADF molecules that achieve spatial separation of FMOs by the MR effect, the distinctive distribution of these molecular orbitals poses significant challenges for conventional computational analysis and ensemble averaging methods to elucidate the FMOs’ separation and the precise mechanism of luminescence. Therefore, the visualization and analysis of electronic states with the specific energy level of a single MR-TADF molecule will provide a deeper understanding of the TADF mechanism. Here, scanning tunneling microscopy/spectroscopy (STM/STS) was used to investigate the electronic states of the DABNA-1 molecule at the atomic scale. FMOs’ visualization and local density of states analysis of the DABNA-1 molecule clearly show that MR-TADF molecules also have well-separated FMOs according to the internal heteroatom arrangement, providing insights that complement existing theoretical prediction methods.