BN-Embedded Cycloarenes: One-Pot Borylation Synthesis, Photoelectric Properties, and Application in Perovskite Solar Cells.

Incorporating heteroatoms, such as nitrogen, oxygen, and/or sulfur atoms, into cycloarenes can effectively regulate their molecular geometries and (opto)electronic properties. However, the rarity of cycloarenes and heterocycloarenes limits the further exploitation of their applications. Herein, we designed and synthesized the first examples of boron and nitrogen (BN)-doped cycloarenes ( and ) via one-pot intramolecular electrophilic borylation of imine-based macrocycles. adopts a bowl-shaped conformation, while possesses a planar geometry. Accordingly, the solubility of was significantly improved by replacing two hexagons in with two N-pentagons, due to the creation of distortions away from planarity. Various experiments and theoretical calculations were carried out for heterocycloarenes and , demonstrating that the incorporated BN bonds diminish the aromaticity of 1,2-azaborine units and their adjacent benzenoid rings but preserve the dominant aromatic properties of pristine kekulene. Importantly, when two additional electron-rich nitrogen atoms were introduced, the highest occupied molecular orbital energy level of was elaborately lifted compared with that of . As a result, the energy-level alignment of with the work function of the anode and the perovskite layer was suitable. Therefore, for the first time, heterocycloarene () was explored as a hole-transporting layer in inverted perovskite solar cell devices, in which the power conversion efficiency reached 14.4%.