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Use of abiotic chemical systems for understanding higher order superstructures is challenging. Here we report a ring‐in‐ring(s) system comprising a hydrogen‐bonded macrocycle and cyclobis(paraquat‐o‐phenylene) tetracation (o‐Box) or cyclobis(paraquat‐p‐phenylene) tetracation (CBPQT4+, p‐Box) that assembles to construct discrete higher order structures with adaptive conformation. As indicated by mass spectrometry, computational modeling, NMR spectroscopy, and single‐crystal X‐ray diffraction analysis, this ring‐in‐ring(s) system features the box‐directed aggregation of multiple macrocycles, leading to generation of several stable species such as H4G (1 a/o‐Box) and H5G (1 a/o‐Box). Remarkably, a dimeric shish‐kebab‐like ring‐in‐rings superstructure H7G2 (1 a/o‐Box) or H8G2 (1 a/p‐Box) is formed from the coaxial stacking of two ring‐in‐rings units. The formation of such unique dimeric superstructures is attributed to the large π‐surface of this 2D planar macrocycle and the conformational variation of both host and guest. [ABSTRACT FROM AUTHOR]

The anode‐cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V‐based AZIBs, Al2(SO4)3 is proposed as decent electrolyte additive to manipulate OH−‐mediated cross‐communication between Zn anode and NaV3O8 ⋅ 1.5H2O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH− accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH− toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH−‐mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates. [ABSTRACT FROM AUTHOR]