Negatively Curved Nanographene with Heptagonal and [5]Helicene Units

Negatively curved nanographene (NG) 4, having two heptagons and a [5]helicene, was unexpectedly obtained by aryl rearrangement and stepwise cyclodehydrogenations. X-ray crystallography confirmed the saddle-shaped structures of intermediate 3 and NG 4. The favorability of rearrangement over helicene formation following radical cation or arenium cation mechanisms is supported by theoretical calculations. NG 4 demonstrates a reversible mechanochromic color change and solid-state emission, presumably benefiting from its loose crystal packing. After resolution by chiral high-perfomance liquid chromatography, the circular dichroism spectra of enantiomers 4-(P) and 4-(M) were measured and showed moderate Cotton effects at 350 nm (vertical bar Delta epsilon vertical bar = 148 M-1 cm(-1)).