This review highlights recent developments concerning stabilization strategies of large (hetero-)acenes and discusses the resulting impact on the aromatic system.

Research on materials facilitating efficient singlet fission (SF) is driven by a possible reduction of thermalization losses in organic photovoltaic devices. Intramolecular SF (iSF) is in this context of special interest, as the targeted modification of either chromophores or linkers enables gradual variations of molecular properties. In this combined synthetic, spectroscopic, and computational work, we present and investigate nine novel spiro-linked azaarene dimers, which undergo efficient iSF with triplet yields up to 199%. Additional molecular braces enhance the rigidity of these tailor-made dimers (TMDs), resulting in great agreement between crystal structures and predicted optimal geometries for iSF in solution. Regardless of the employed chromophores and linkages, the dynamics of all nine TMDs are perfectly described by a unified kinetic model. Most notably, an increase in the orbital overlap of the π-systems by decreasing the twist angle between the two chromophores does not only increase the rate of formation of the correlated triplet pair but also further promotes its decorrelation. This new structure–function relationship represents a promising strategy toward TMDs with high triplet lifetimes to be utilized in optoelectronic devices.

A doubly alkylene bridged 6,13‐diphenylpentacene and analogously bridged azapentacenes were prepared; they are persistent. The doubly bridged azapentacenes display superior photochemical, oxidative and thermal stabilities compared to azapentacenes protected by bis(TIPS‐ethynyl)‐substituents—clipping an azaacene into a large ring is a viable complement in stabilization.

The synthesis of five spiro‐linked azaacene dimers is reported and their properties are compared to that of their monomers. Dimerization quenches emission of the longer (≥(hetero)tetracenes) derivatives and furnishes amorphous thin‐films, the absorption is not affected. The larger derivatives were tested as acceptors in bulk‐heterojunction photovoltaic devices with a maximum power conversion efficiency of up to 1.6 %.

The synthesis, property evaluation,a nd single crystal X-ray structures of four 5,7,12,14-tetrafunctionalized diazapentacenes are presented. The synthesis of these compounds either starts from tetrabromo-N,N-dihydrodiazapentacene or from ad iazapentacene tetraketone.P dcatalyzed coupling or addition of al ithiuma cetylide gave the precursors that furnish, after furtherr edox reactions, the diazapentacenes as stable crystalline materials. The performance of the tetraphenyl-substituted compoundas n-channel semiconductor was evaluated in organic field effect transistors.

Ultra‐electron‐deficient azaacenes were synthesized via Buchwald‐Hartwig coupling of ortho‐diaminoarenes with chlorinated mellophanic diimide followed by oxidation of the intermediate N,N’‐dihydro compounds with MnO2 or PbO2. The resulting cata‐annulated bisimide azaacenes have ultrahigh electron affinities with first reduction potentials as low as −0.35 V recorded for a tetraazapentacene. Attempts to prepare a tetrakis(dicarboximide)tetraazaheptacene resulted in the formation of a symmetric butterfly dimer.

The syntheses of new, fourfold alkynylated tetraazaacenoacenes (tetraazaanthracenoanthracene, tetraazatetracenotetracene and tetraazapentacenopentacene) are reported. This novel heteroacenoacene motif exhibits surprisingly strong electronic coupling between its constituting diazaacene units.

An unprecedented, often almost quantitative access to tricyclic aromatic compounds by dual gold catalysis was developed. This synthetic route expands the scope of benzofulvene derivatives through a C(sp )-H bond insertion in easily available starting materials. The insertion takes place with an exclusive chemoselectivity with respect to the competing aromatic C-H positions. A bidirectional synthesis with two competing ortho-aryl C-H bonds in the selectivity-determining step also shows perfect selectivity; this result is explained by a computational investigation of the two conceivable intermediates. The intramolecular competition of two non-equivalent aryl C-H bonds with a benzylic methyl group also showed perfect selectivity.