Synthesis and Excited-State Properties of Donor-Acceptor Azahelical Coumarins

A set of three donor-acceptor azahelical coumarins (DA-AHCs), namely, H-AHC, Me-AHC, and Ph-AHC, were rationally designed and synthesized, and their excited-state properties were comprehensively investigated. All three DA-AHCs are shown to display very high fluorosolvatochromic shifts as a result of significant intramolecular charge transfer in their excited states. The para-quinoidal forms of the latter apparently contribute predominantly to large dipole moments in their excited states. By virtue of the fact that these helical systems structurally incorporate a highly fluorescent coumarin dye, they exhibit high quantum yields in both solution and solid states. Indeed, their emission behaviors in the crystalline media are shown to be remarkably correlated with their respective crystal packings. Incisive analyses demonstrate (i) strengthening of hydrogen bonding in the excited state promotes quenching (H-AHC), (ii) efficient crystal packing promotes high emission (Me-AHC) by precluding deactivations via vibrational motions, and (iii) loose crystal packing contributes to excited-state deactivation to account for low quantum yields of emission (Ph-AHC).

Automated summary

A set of donor-acceptor azahelical coumarins (DA-AHCs) with high fluorosolvatochromic shifts and high quantum yields in solution and solid states were designed and synthesized. The excited-state properties of these compounds were investigated, revealing the contribution of intramolecular charge transfer and crystal packing to their emission behaviors. The analysis showed that strengthened hydrogen bonding promoted quenching, efficient crystal packing promoted high emission, and loose crystal packing contributed to excited-state deactivation.