Herein we report the facile reductive O-triflylation and O-silylation of naphthalene diimide as a scalable one-step approach. The resulting highly reactive 1,3,6,8-tetratriflato-2,7-diazapyrene was prepared at the 3 gram scale and serves as a versatile platform for further functionalizations via Sonogashira cross coupling or nucleophilic aromatic substitution by piperidine or iodide leading to tetrasubstituted diazapyrenes with tunable optoelectronic properties. Fine tuning is demonstrated by means of absorption and emission maxima varying within a range of more than 100 nm. The different diazapyrenes are characterized by means of XRD diffraction, UV-Vis and photoluminescence spectroscopy as well as cyclic voltammetry and TD-DFT calculations. The applicability of so far unaccessible tetra-1-alkynyl diazapyrenes for organic molecular beam epitaxy (OMBE) is demonstrated by characterization of a sub-monolayer on Cu(111) using scanning tunneling microscopy (STM).

We report a new high-yield synthesis of so far not accessible tetraphenylphosphonium methylcarbonate Ph₄P[OCO₂Me] via solvothermal fluoride-induced demethylation and MeF elimination at Me₂CO₃ (DMC) by Ph₄P–F, structurally characterized as λ⁵-fluorophosphoran by XRD. The synthetic value of Ph₄P[OCO₂Me] key compound for preparing nearly all kinds of other Ph₄P[anion] salts with perfectly crystallizing (not symmetry frustrated) cation is demonstrated by examples beyond ionic liquid research: a complete set of silylchalcogenide salts Ph₄P[ESiMe₃] (E = S, Se, and Te) including the first example of a structurally characterized non-coordinating, naked [Te–SiMe₃]⁻ anion is presented. With this set of soft Lewis bases and metal organic Lewis acids [Cp₃La] at hand, a comprehensive series of crystalline 1 : 1 lanthanate complexes Ph₄P[Cp₃La–ESiMe₃] has been prepared. Their structural features and trends such as complexation induced Si–E bond elongation and a pronounced trend in La–E–Si bond angle contraction with E = S < Se < Te are discussed. Heteronuclear ¹H, ¹³C, ²⁹Si, and ¹³⁹La NMR studies provide a set of ¹³⁹La NMR shifts for homologs of heavy chalcogen–lanthanum complexes.

A set of four tetraalkynyl rylene and diaza-rylene (L) templated clusters of the type [LCo ₈ (CO) ₂₄ ] was synthesized and fully characterized. Their solid state pyrolysis led to carbon nanoparticles of different shapes depending on the C : N and C : Co ratio.