Excimer formation and evolution of excited state properties in discrete dimeric stacking of an anthracene derivative: a computational investigation.

Herein, density functional theory (DFT) computations were performed to investigate the discrete dimer of a mono-substituted anthracene derivative (2-TA-AN), which exhibited highly efficient pure excimer fluorescence in its crystal form. As a more practical model, its geometry, potential energy curve and excited state property were systematically calculated to better understand the excimer formation process and photophysical properties. The compressed excimer geometry is responsible for the highly efficient excimer emission, arising from the enhanced rigidity that greatly suppresses its non-radiative vibrations. Potential energy curves along three directions reveal the non-uniqueness of excimer formation along the long axis of anthracene, which is in a good agreement with the experimental findings. Upon decreasing the displacement, the intermonomer charge-transfer (CT) component gradually increased towards an approximately equivalent hybridization with the locally-emissive (LE) state of the monomer during the formation of the excimer. The excimer emission wavelength versus intermonomer CT content shows a similar trend along the three directions, revealing a turning point related to the essential transition of the excited state properties from the LE of the monomer to the HLCT of the excimer. The present results will contribute to the better understanding of the structure-property relationships in excimer formation and photophysical properties.