Structures, Chiroptical Properties, and Unexpectedly Facile Helical Inversion of Highly Elongated Anthracene-Fused Expanded Helicenes

Chemistry. 2024 Dec 12:e202404348. doi: 10.1002/chem.202404348. Online ahead of print.

Abstract

Helical fused anthracenes were elongated by fusing additional aromatic units at both ends to yield novel expanded helicenes. Compounds [5]HA2N and [7]HA consisting of 19 and 21 benzene rings, respectively, were synthesized by fourfold cycloisomerization of the corresponding terminal alkyne precursors. The helical structures were confirmed by X-ray crystallographic analysis, where the aromatic frameworks stacked effectively with the helical turn numbers exceeding two. The enantiomers of the two compounds were resolved by chiral HPLC. Whereas [5]HA2N readily underwent enantiomerization at room temperature at the barrier to enantiomerization of 91 kJ mol-1, the barrier was enhanced to 99 kJ mol-1 for the long analog [7]HA. The enantiomers of [7]HA exhibited strong responses in the circular dichroism (CD) and circularly polarized luminescence (CPL) spectra, as scaled by dissymmetry factors |gabs| = 0.034 and |glum| = 0.012. Theoretical calculations by the r2SCAN-3c method suggested stepwise mechanisms for the enantiomerization via helical inversion with acceptable barrier heights. The unexpectedly flexible nature of the aromatic frameworks of [5]HA2N and [7]HA was discussed on the basis of the proposed mechanism.

Keywords: arene; circular dichroism; circularly polarized luminescence; helicene; inversion mechanism.