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Abstract Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl2bpy2 catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies. The solvent and ligand were found to be essential for the generation of catalytic active Co(I) species, among which acetonitrile and bipyridine ligand are resistant to the disproportionation events of Co(I). Investigations, based on Quick-X-Ray Absorption Fine Structure (Q-XAFS) spectroscopy, Electron Paramagnetic Resonance (EPR), IR allied with DFT calculations, allow comprehensive mechanistic insights that establish the structural information of the catalytic active cobalt species along with the whole catalytic Co(I)/Co(III) cycle. Moreover, the acetonitrile and bipyridine system can be further extended to the acylation, allylation, and benzylation of aryl zinc reagents, which present a broad substrate scope with a catalytic amount of Co salt. Overall, this work provides a basic mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions.

Defect-assisted nonradiative recombination and carrier aggregation at the interface hinder the potential of perovskites as emitter for light-emitting diodes. Here, Fang et al. achieve an external quantum efficiency of 24.1% by combining multidimensional perovskite with cascade conduction bands.

Enriching the chemical space of polycyclic heterocycles is of high value in chemical biology. Here, the authors report an electrooxidative protocol for the regioselective dearomative annulation of indoles and benzofurans under undivided cell conditions and obtain five- to eight-membered fused heterocycles.

Oxidative C–H/N–H cross-coupling is a convenient method to construct C–N bonds, however this is rarely achieved in a sustainable manner. Here, the authors show an oxidant-free electrochemical C–H/N–H cross-coupling between electron-rich arenes and diarylamines to afford triarylamines with exclusive para-selectivity.

Non-viral vectors are important for transfection but can be limited in the uptake, protection and release of ssDNA. Here, the authors report on the design of metal-organic-framework vectors with precisely controlled pore geometry and demonstrate the vector in the transfection of immune cells.