Synthesis, crystal structure and photophysical properties of pyrene-helicene hybrids.

Abstract

Synthesis of helically chiral aromatics resulting from fusion of pyrene and [4]- or [5]helicene has been accomplished using photoredox catalysis employing a Cu-based sensitizer as the key step. Photocyclisation experiments for the synthesis of the target compounds were carried out in batch and using continuous flow strategies. The solid-state structures, UV/Vis absorption spectra and fluorescence spectra of the pyrene-helicene hybrids were investigated and compared to that of the parent [5]helicene to discern the effects of merging a pyrene moiety within a helicene skeleton. The studies demonstrated that pyrene-helicene hybrids adopt co-planar or stacked arrangements in the solid state, in contrast to the solid-state structure of the parent [5]helicene. The UV/Vis and fluorescence spectra of the pyrene-helicene hybrids exhibited strong red-shifts when compared to the parent [5]helicene. DFT calculations suggest that the strategy of extending the π surface in the y axis of the helicenes increased their HOMO levels while also decreasing their LUMO levels, resulting in significantly reduced band gaps.