Abstract
A novel doubly cyclopentannulated carbazole which is accessible through a successive π-expansion of di(1-naphthylamine) is disclosed. The carbazole moiety is generated in the final step through intramolecular oxidative coupling. The π-expansion of carbazole resulted in strongly altered optoelectronic and electrochemical properties. The solid-state structure features an interesting packing motif with alternating face-to-face π⋅⋅⋅π and edge-to-face C-H⋅⋅⋅π interactions. The experimental findings were corroborated by theoretical calculations.