Proton storage in rechargeable aqueous zinc‐ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H+ insertion/extraction. However, it has not been achieved in organic materials‐based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3‐a:2′,3′‐c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn–HATN batteries experience a H+ uptake/removal behavior with highly reversible structural evolution of HATN. The H+ uptake/removal endows the Zn–HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn–organic batteries and open up new opportunities to construct high‐performance ZIBs.

An efficient methodology for the synthesis of unsymmetrical biheteroaryl molecules has been developed via Pd(II)-catalyzed oxidative C-H/C-H cross-coupling of heteroarenes. An inversion in reactivity and selectivity has been achieved successfully to perform the desired heterocoupling. This process allows the heterocoupling of not only electron-rich N-containing heteroarenes (e.g., xanthines, azoles, and indolizines) but also electron-poor pyridine N-oxides with various thiophenes or furans.

Fishing for complements! There is an alternative to the useful Fischer indole synthesis. The new method utilizes the same retrosynthetic disconnection but is based on a Rh(III) -catalyzed directed CH activation step and a successive coupling with alkynes.

The first highly efficient and scalable cobalt-catalyzed directed C-H functionalization with carbene precursors is presented. This methodology provides a modular route towards a new class of conjugated polycyclic hydrocarbons with tunable emission wavelengths both in solution and in the solid state.

The biheteroaryl structural motif is prevalent in polymers, advanced materials, liquid crystals, ligands, molecules of medicinal interest, and natural products. Many types of synthetic transformations have been known for the construction of heteroaryl-heteroaryl linkages. Coupling reactions provide one of the most efficient ways to achieve these biheterocyclic structures. In this review, four types of coupling reactions are discussed: 1) transition-metal-catalyzed coupling reactions of heteroaryl halides or surrogates with heteroarylmetals; 2) direct inter- and intramolecular heteroarylations of C sp 2-H bonds of heteroarenes with heteroaryl halides or pseudohalides; 3) oxidative C-H/C-H homo- and cross-couplings of two unpreactivated heteroarenes; and 4) transition-metal-catalyzed decarboxylative cross-coupling reactions between haloheteroarenes or heteroarenes and heteroarenecarboxylic acids. The general purpose of this review is to give an exhaustive and clear picture in heteroaryl-heteroaryl bond formation as well as its application in the synthesis of natural products, pharmaceuticals, catalyst ligands, and materials.