A comparative investigation on excimer fluorescence toward its bright future

Must excimers quench fluorescence? This study aims to clarify the misconception that excimers are defective species with weak fluorescence. For this purpose, we utilized a rigid xanthene template to connect anthracene units for constructing an inter-excimer and an intra-excimer. Their photophysical properties were systematically investigated in solution and crystal forms, representing dynamic and static environments, respectively. In solutions, the inter- and intra-excimers exhibited low fluorescence efficiencies due to the limited formation and ease of dissociation of the excimers. In crystals, the inter- and intra-excimers both demonstrated a significant increase in fluorescence efficiency, which was ascribed to the greatly suppressed non-radiation for the static excimer in a rigid environment. Furthermore, the efficiency of the inter-excimer was higher than that of the intra-excimer, which arose from the more stable excited state for more effective non-radiative suppression. Therefore, it was concluded that the probability and stability of excimer formation are the key factors for improving excimer fluorescence efficiency. Overall, their fluorescence efficiencies can be ranked as follows: dynamic inter-excimer < dynamic intra-excimer < static intra-excimer < static inter-excimer, which is subjected to environmental rigidity and excimer stability. This work will provide a comprehensive understanding of excimers and propose a novel design strategy to achieve high-efficiency fluorescent materials for innovative organic photo-functional applications.