New N-heterocyclic fluorophores are sought-after compounds for organic electronic devices. Here, we report on a straightforward synthesis to access meta/para-dipyrrolobenzenes and para-dipyrrolopyrazines in high yields using a bidirectional gold-catalyzed cyclization strategy. The versatility of our reaction protocol was showcased by preparing dipyrroloarenes with different substituents, various functional groups, and in a multitude of substitution patterns. Furthermore, we showed that the dipyrroloarenes can be post-modified by N-alkylation to improve the solubility or bromination to yield precursors for further derivatization via cross-coupling. Investigation of the photophysical properties of themostly unprecedenteddipyrroloarenes identified strong blue emitters such as the diphenyl metadipyrrolobenzene with a quantum yield of 98%. Moreover, we showed that changes in the solvent polarity or interactions with Lewis acids such as borane can be used to fine-tune the photophysical properties of the fluorophores.

New N-heterocyclic compounds for organic functional materials and their efficient syntheses are highly demanded. A surprising entropy-induced selectivity switch in the gold-catalyzed intramolecular hydroarylation of 2-ethynyl N-aryl indoles was found and its exploitation led to straightforward syntheses of indolo[1,2-a]quinolines. Experimental and computational mechanistic investigations gave insight into this uncommon selectivity phenomenon and into the special reactivity of the indolo[1,2-a]quinolines. The high functional group tolerance of this methodology enabled access to a diverse scope with high yields. In addition, bidirectional approaches, post-functionalization reactions, and π-extension of the core structure were feasible. An indepth study of the photophysical properties explored the structure-effect relationship for different derivatives and revealed a high potential of these compounds for future applications as functional materials.

The transition-metal-catalyzed cyclization of bissilylethynylated N,N'-dihydrotetraazapentacene (TIPS-TAP-H 2 ) into bissilylated cyclopenta[fg,qr]pentacenes is reported. Depending on the catalyst either none, one or two silyl groups migrate and change their positions in the formed five-membered rings. The optoelectronic properties are quite similar, whereas the packing motifs differ dramatically. Control experiments and quantum chemical calculations were performed to investigate the mechanism of the reaction and the selectivity of the silyl shift.

Brominated pentannulated dihydrotetraazapentacenes were prepared by gold-or palladium-catalyzed 5-endodig cyclization of TIPS-ethynylated dihydrotetraazaacenes (TIPS = triisopropylsilyl). Post-functionalization was demon-strated by Sonogashira alkynylation and Rosenmund-von Braun cyanation. Calculations predict these species to act as n-type semiconductors, which was verified for two derivates through characterization in organic field-effect transistors.

Our recently developed gold‐catalyzed synthesis of indolo[1,2‐a]quinolines was successfully expanded towards bidirectional approaches, enabling access to two heptacyclic structural motifs. In the case of benzobispyrido[1,2‐a]indoles, previously inaccessible modifications of the only known representative were made possible. In addition, the synthesis of a new class of nitrogen‐containing heptacycles – namely benzobispyrrolo[1,2‐a]quinolines – was achieved by applying alkynylated benzodipyrrole derivatives as starting materials. All new compounds alongside with their corresponding precursors were fully characterized and their properties were investigated by X‐ray crystallography, photophysical measurements and computational methods. The study revealed important structure‐effect relationships between the solid‐state structures and the observed photophysical properties, e. g. aggregation‐induced emission and solid‐state fluorescence.