π-Extended Corannulene-Based Nanographenes: Selective Formation of Negative Curvature

Abstract

A geometrically selective bottom-up synthesis of curved nanographenes is described. The synthetic methodology used involves the extension of the π-system of positively curved corannulene by a [4+2] cycloaddition reaction followed by cyclodehydrogenation (Scholl oxidation). By selecting the conditions for the Scholl oxidation, the formation of a sevenmembered ring that also confers negative curvature to the resulting nanographene can be activated, offering two topologically distinct, curved nanographenes from a common precursor. Additionally, the structure−property relationship in these new nanographenes is explored via theoretical, electrochemical, photophysical, Raman, and X-ray crystallographic studies.