Pushing the Limits of Acene Chemistry: The Recent Surge of Large Acenes

Acenes, consisting of linearly fused benzene rings, are an important fundamental class of organic compounds with various applications. Hexacene is the largest acene that was synthesized and isolated in the 20th century. The next largest member of the acene family, heptacene, was observed in 2007 and since then significant progress in preparing acenes has been reported. Significantly larger acenes, up to undecacene, could be studied by means of low‐temperature matrix isolation spectroscopy with in situ photolytic generation, and up to dodecacene by means of on‐surface synthesis employing innovative precursors and highly defined crystalline metal surfaces under ultrahigh vacuum conditions. The review summarizes recent experimental and theoretical advances in the area of acenes that give a significantly deeper insight into the fundamental properties and nature of the electronic structure of this fascinating class of organic compounds.