Access to Functionalized Pyrenes, Peropyrenes, Terropyrenes, and Quarterropyrenes via Reductive Aromatization

Herein we report a versatile concept for the synthesis of fourfold functionalized, soluble pyrenes, peropyrenes, terropyrenes, and quarterropyrenes. They were obtained by a modular stepwise approach towards the rylene scaffold via Suzuki–Miyaura cross coupling, oxidative cyclodehydrogenation in the presence of caesium hydroxide under air, and finally zinc‐mediated reductive silylation. The silylated reaction products were characterized by X‐ray crystallography. The first example of a synthesized and crystallized quarterropyrene is presented and its oxidation reaction investigated. The functionalized ropyrenes were systematically characterized by means of UV/Vis–NIR and photoluminescence spectroscopy showing a bathochromic shift of 80 nm per naphthalene unit and a nearly linear increase of the extinction coefficients. Cyclic voltammograms and DFT calculations identify them as electron‐rich dyes and show a narrowing of the electrochemically determined HOMO–LUMO gap and lower oxidation potentials for the higher homologues.