Four π‐extended phosphoniumfluorene electrolytes (π‐PFEs) are introduced as hole‐blocking layers (HBL) in inverted architecture planar perovskite solar cells with the structure of ITO/PEDOT:PSS/MAPbI3/PCBM/HBL/Ag. The deep‐lying highest occupied molecular orbital energy level of the π‐PFEs effectively blocks holes, decreasing contact recombination. It is demonstrated that the incorporation of π‐PFEs introduces a dipole moment at the PCBM/Ag interface, resulting in significant enhancement of the built‐in potential of the device. This enhancement results in an increase in the open‐circuit voltage of the device by up to 120 mV, when compared to the commonly used bathocuproine HBL. The results are confirmed both experimentally and by numerical simulation. This work demonstrates that interfacial engineering of the transport layer/contact interface by small molecule electrolytes is a promising route to suppress nonradiative recombination in perovskite devices and compensates for a nonideal energetic alignment at the hole‐transport layer/perovskite interface.

Efficient synthetic approaches for the incorporation of nitrogen into polyaromatic compounds (PACs) in different patterns as stabilising moiety for π‐extended systems and modification tool for optoelectronic properties remain a challenge until today. Herein, we developed a new versatile pathway to napthyridine‐based PACs as non‐symmetric and regioisomeric pendant to pyrazine‐based PACs. A combination of a gold‐catalysed synthesis of 2‐aminoquinolines and the development of an in situ desulfonation and condensation of these precursors are the key steps of the protocol. The shape and type of attached functional groups of the PACs can be designed in a late stage of the overall synthetic procedure by the chosen anthranile and backbone of the ynamide introduced in the gold‐catalysed step. Single‐crystal X‐ray diffraction and the investigation of electronic properties of the compounds show the influence of the attached substituents. All naphthyridine‐based PACs show halochromic behaviour implying their use as highly sensitive proton sensor in non‐protic solvents.

The synthesis of aryl amines via the formation of a C−N bond is an essential tool for the preparation of functional materials, active pharmaceutical ingredients and bioactive products. Usually, this chemical connection is only possible by transition metal‐catalyzed reactions, photochemistry or electrochemistry. Here, we report a metal‐free arene C−H amination using hydroxylamine derivatives under benign conditions. A charge transfer interaction between the aminating reagents TsONHR and the arene substrates enables the chemoselective amination of the arene, even in the presence of various functional groups. Oxygen was crucial for an effective conversion and its accelerating role for the electron transfer step was proven experimentally. In addition, this was rationalized by a theoretical study which indicated the involvement of a dioxygen‐bridged complex with a “Sandwich‐like” arrangement of the aromatic starting materials and the aminating agents at the dioxygen molecule.

The gold-catalyzed annulation of diethynyl N-heterocycles for the synthesis of quinoxaline-/phenazine-based pentalenes and the study of their optoelectronic properties are described. The inhibition of the gold catalyst by the nitrogen centers in the substrate and the product could be overcome by increasing the reaction temperature to 130 °C, which usually leads to catalyst decomposition in gold catalysis. At 130 °C, 6,7-di(arylethynyl)quinoxalines in chlorobenzene give the corresponding pentalenes. The annulation of 2,3-di(arylethynyl)quinoxalines requires an even higher temperature under microwave irradiation. The quinoxaline-based pentalenes showed lower LUMO levels compared to the corresponding naphthalene-based pentalenes.

Novel dialkynyl pyridines were synthesized and protected as alkyl salts for dual gold(I)‐catalyzed cycloisomerization. Different alkyl groups and counter ions were screened for the salts, with benzyl and hexafluorophosphate providing the best results. The cyclization led to NMR yields of >95 % being obtained for a number of substrates. Step‐wise hydrogenation of products could be performed in one‐pot by Pd/C, with selective reduction of the double bonds, followed by deprotection of the benzyl group.