Discrete Macrocycles with Fixed Chirality and Two Distinct Sides: Dipole-Dependent Chiroptical Response.

Control of symmetry is fundamental in molecular design with aimed properties. Herein we report a set of chiroptical C -symmetric molecules with variable dipolar structures based on a rim-differentiated cylindrical macrocycle, pillar[5]arene. Incorporation of electron-withdrawing ester groups formed an explicit two-sided structure, leading to increase in response wavelength and luminescence efficiency. On the other hand, chiroptical measurement of separated enantiomers revealed that such a dipolar character diminished dissymmetry of the electronic transitions. By suppressing the dipole, the dissymmetry factor for luminescence was enhanced from 0.4×10 to 5.1×10 in a less dipolar methoxy-substituted molecule, which was larger than reported pillar[5]arene derivatives without C -symmetry around one order of magnitude.