Dedicated to Professor Klaus Müllen on the occasion of his 75th birthdayBN-heteroarenes, which employ both boron and nitrogen in aromatic hydrocarbons, have gained great attention in the fields of organic chemistry and materials science. Nevertheless, the extensive studies on BN-heteroarenes are largely limited to 1,2-azaborine-based compounds with B-N covalent bonds, whereas 1,3-and 1,4-BN-heteroarenes are relatively rare due to their greater challenge in the synthesis. Recently, significant progresses have been achieved in the synthesis and applications of BN-heteroarenes featuring 1,4-azaborines, especially driven by their significant potential as multiresonant thermally activated delayed fluorescence (MR-TADF) materials. Therefore, it is timely to review these advances from the chemistry perspective. This review summarizes the synthetic methods and recent achievements of 1,4-azaborine-based BN-heteroarenes and discusses their unique properties and potential applications of this emerging class of materials, highlighting the value of 1,4-BN-heteroarenes beyond MR-TADF materials. It is hoped that this review would stimulate the conversation and cooperation between chemists who are interested in azaborine chemistry and materials scientists working in the fields of organic optoelectronics, metal catalysis, and carbon-based nanoscience etc.

The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom‐up fabrication based on molecular precursors. This approach offers a unique platform for all‐carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5‐atom wide armchair GNRs (5‐AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5‐AGNRs are obtained via on‐surface synthesis under ultrahigh vacuum conditions from Br‐ and I‐substituted precursors. It is shown that the use of I‐substituted precursors and the optimization of the initial precursor coverage quintupled the average 5‐AGNR length. This significant length increase allowed the integration of 5‐AGNRs into devices and the realization of the first field‐effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub‐nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B−N bonds (BN‐PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high‐mobility organic semiconductors based on existing BN‐PAHs through a “periphery engineering” strategy. Tetraphenyl‐ and diphenyl‐substituted BN‐anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized. DPBNA exhibits the highest hole mobility of 1.3 cm2 V−1 s−1 in organic field‐effect transistors, significantly outperforming TPBNA and all the reported BN‐PAHs. Remarkably, this is the first BN‐PAH with mobility over 1 cm2 V−1 s−1, which is a benchmark value for practical applications as compared with amorphous silicon. Furthermore, high‐performance phototransistors based on DPBNA are also demonstrated, implying the high potential of BN‐PAHs for optoelectronic applications when the “periphery engineering” strategy is implemented.

A simple and versatile method for macrocyclizing unprotected native peptides with a wide range of easily accessible diiodo and triiodoarene reagents via the palladium-catalyzed multiple S-arylation of cysteine residues is developed. Iodoarenes with different arene and heteroarene cores can be incorporated into peptide macrocycles of varied ring sizes and amino acid compositions with high efficiency and selectivity under mild conditions.

Based on a combination of the CALYPSO method for crystal structure prediction and first-principles calculations, we explore the crystal structures of VH2 under the pressure range of 0−300 GPa. The cubic Fm-3m phase with regular VH8 cubes is predicted to transform into orthorhombic Pnma structure with fascinating distorted VH9 tetrakaidecahedrons at 47.36 GPa. Both the Fm-3m phase at 0 GPa and the Pnma phase at 100 GPa are mechanically and dynamically stable, as verified with the calculations of elastic constants and phonon dispersions, respectively. Moreover, the calculated electronic band structure and density of states indicate both stable phases are metallic. Remarkably, the analyses of the Poisson’s ratio, electron localization function (ELF) and Bader charge substantiate that both stable phases are ionic crystals on account of effective charges transferring from V atom to H. On the basis of the microscopic hardness model, the Fm-3m and Pnma crystals of VH2 are potentially incompressible and hard materials with the hardness values of 17.83 and 17.68 GPa, respectively.