Coumarin-Annelated Regioisomeric Heptahelicenes: Influence of Helicity on Excited-State Properties and Chiroptical Properties

Two regioisomeric pairs of heptahelical mono- and biscoumarins that are differentiated by “inward” and “outward” disposition of the pyran-2-one moiety have been synthesized and investigated to understand the influence of helicity on excited-state and chiroptical properties. A slight variation in the helicities is found to manifest in contrasting excited-state properties of coumarin-annelated heptahelicenes; in addition to the intramolecular charge transfer, structural relaxation in the excited state is shown from theoretical calculations to cause decrease in the fluorescence quantum yield for a system with higher helicity. The optically pure enantiomers of heptahelical coumarins exhibit helicity-dependent chiroptical properties, namely, specific rotations, molar ellipticities, Cotton effects, and anisotropic dissymmetry factors. Theoretical calculations point to factors that are not readily explicable.