Helitwistacenes-Combining Lateral and Longitudinal Helicity Results in Solvent-Induced Inversion of Circularly Polarized Light

Helicity is expressed differently in ortho- and para-fused acenes-helicenes and twistacenes, respectively. While the extent of helicity is constant in helicenes, it can be tuned in twistacenes, and the handedness of flexible twistacenes is often determined by more rigid helicenes. Here, we combine helicenes with rigid twistacenes consisting of a tunable degree of twisting, forming helitwistacenes. While the X-ray structures reveal that the connection does not affect the helicity of each moiety, their electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) spectra are strongly affected by the helicity of the twistacene unit, resulting in solvent-induced sign inversion. ROESY NMR and TD-DFT calculations support this observation, which is explained by differences in the relative orientation of the helicene and twistacene moieties. Combining helicenes with twistacenes, in which the extent of twisting can be tuned, has led to the new family of helitwistacenes. The combination of lateral and longitudinal helicity results in polarity-induced and twisting-induced sign inversion of both the electronic circular dichroism and circularly polarized luminescence signals. This sign inversion could be explained by differences in the relative orientation of the helicene and twistacene moieties. image