A Modular Approach to Tuning Emissive N-Quinolyl Through-Space Charge Transfer States Using sp3-Scaffolds.

Abstract

We have shown that palladium-catalyzed cascade processes provide modular access to rigid quinoline-containing tetracyclic amines. This modular approach enables fine-tuning of the through-space charge transfer (TSCT) state formation between the lone pair localized on the nitrogen atom in the cage moiety and the quinoline moiety by variation of both the intramolecular N-aryl distance and quinoline substitution. Decreasing this N-aryl distance enhances the formation of the TSCT species, giving control over the emission color and photoluminescence quantum yield. Methoxylation of the quinoline unit decreases the propensity of TSCT formation. The development of this structure-activity relationship provides great insight for TSCT formation with an impact on further understanding dimeric, excimeric, and exciplex species. This understanding is crucial for the work underpinning their use in biosensor applications, and the conclusions are of relevance to the broader field of photoluminescence.