Julolidine based red emitting ESIPT/AIE active material showing luminescence beyond excimer emission: An "on-off" emission response to Cu.

A new julolidine-fluorene based excited state intramolecular proton transfer (ESIPT)/aggregate induced emission (AIE) active Schiff-base (JDF) has been synthesized and evaluated for its photophysical properties in solution and aggregated/solid states. The correlation between the emission behavior and the solid state crystal packing structure revealed the interplay of ESIPT coupled excimer reaction occurring in the solid state, which is one of the rare examples reported so far. For a comprehensive comparison, we synthesized a non-ESIPT methyl derivative (JDF-Me) of JDF capable of showing excimer emission only in the solid state. Further, JDF exhibits normal as well as keto emission in solution, upon addition of water, its poor solvent, that promotes aggregation, the fluorescence emission shows the preponderance of the excimer band in the low energy region. It was also interesting to note that in the solid state (thin films), JDF shows emission beyond the excimer emission, which is wavelength dependent. This is attributed to the formation of diverse clusters leading to the extended delocalization beyond excimers, and represents a clustering-triggered emission ascribing bright red color to the solid JDF. Such mélange of emission characteristics of JDF are responsible for the multicolor emission covering a broad range of electromagnetic spectrum, which is demonstrated by the confocal microscopy images of the JDF recorded in different states. Further, in its aggregated state, JDF recognized Cu ions, selectively, manifested in the form of emission quenching via the interaction of Cu ions with the oxygen and nitrogen atoms of JDF inhibiting the excimer formation.