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The development of efficient and selective organic synthetic approaches for complex molecules has garnered significant attention due to the need for precise control over molecular structures and functions. Rotaxanes, a type of mechanically interlocked molecules (MIMs), have shown promising applications in various fields including sensing, catalysis, and material science. However, the highly selective synthesis of oligo[n]rotaxanes (mostly n≥3) through controlling host‐guest complexation and supramolecular threading assembly process still remains an ongoing challenge. In particular, the utilization of two‐dimensional (2D) macrocycles with structural shape‐persistency for the synthesis of oligo[n]rotaxanes is rare. In this concept, research on cooperatively threaded host‐guest complexation with hydrogen‐bonded (H‐bonded) aramide macrocycles and selective synthetic protocols of oligo[n]rotaxanes has been summarized. The high efficiency and selectivity in synthesis are ascribed to the synergistic interplay of multiple non‐covalent bonding interactions such as hydrogen bonding and intermolecular π–π stacking of macrocycles within the unique supramolecular structure of threaded host‐guest complexes. This review focuses on the latest progress in the concepts, synthesis, and properties of H‐bonded aramide macrocycle‐based oligorotaxanes, and presents an in‐depth outlook on challenges in this emerging field. [ABSTRACT FROM AUTHOR]

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]