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Macrocycle‐based host–guest complexation offers an intriguing protocol in producing chiroptical materials, while the bulky size and dynamic exchange between hosts and guests hinders the ordered aggregation to afford the long‐range chiral arrangement. It remains great challenges in assembling cucurbit[n]urils (CB[n]s) included complexes to induce supramolecular chirality ascribed to the excellent water solubility and flexible packing. Herein, we unveiled the structural basis on the formation of chiroptical coassemblies from CB[n] (n=6, 7) complexes. Perylene diimides (PDIs) with cationic chiral pendants formed complexes in the aqueous media, which selectively showed chiroptical properties. Chlorination at the bay position, increasing alkyl length of cationic chiral pendants or reducing the number of polyaromatic rings would hinder the chiral aggregation. In a comprehensive manner, CB[6] favors ordered aggregation into one‐dimensional fibrous nanoarchitectures that greatly facilitates the supramolecular chirality. In contrast, CB[7] with larger cavity and water solubility shrinks the ordered arrangement of complexes, reducing the formation possibility of supramolecular chiral nanoarchitectures. This work suggests the great potential of CB[6] in the preparation and manipulation of supramolecular chiral assemblies, shedding light on the macrocycle‐based functional chiroptical materials. [ABSTRACT FROM AUTHOR]

Dynamic chemistry utilizing both covalent and noncovalent bonds provides valid protocols in manipulating properties of self‐assemblies and functions. Here we employ dynamic chemistry to realize multiple‐route control over supramolecular chirality up to five states. N‐protected fluorinated phenylalanine in the carboxylate state self‐assembled into achiral nanoparticles ascribed to the amphiphilicity. Protonation promoted one‐dimensional growth into helices with shrunk hydrophilicity, which in the presence of disulfide pyridine undergo chirality inversion promoted by the hydrogen bonding‐directed coassembly. Further interacting with the water‐soluble reductant cleavages the disulfide bond to initiate the rearrangement of coassemblies with a chirality inversion as well. Finally, by tuning the pH environments, aromatic nucleophilic substitution reaction between reduced products and perfluorinated phenylalanine occurs, giving distinct chiral nanoarchitectures with emerged luminescence and circularly polarized luminescence. We thus realized a particular five‐state control by combining dynamic chemistry at one chiral compound, which greatly enriches the toolbox in fabricating responsive chiroptical materials. [ABSTRACT FROM AUTHOR]

Hydrogels behave as potential candidates to investigate circularly polarized light (CP)‐matter interaction, which however suffer from small sensitivity towards circular polarization. Here we report a general protocol to build hydrogels from π‐conjugated amino acids with coassembled charge‐transfer (CT) complexes, covering a wide scope of donors and acceptors, which were incorporated into stable hydrogel matrices. CT complexes formed block coassemblies with gelators, induced the emergence of macroscopic chiral helices, where efficient chirality transfer occurs to realize tunable Cotton effects from visible light to NIR‐I region depending on the structures of CT pairs. The hybrid hydrogels showed tunable photothermal performances with excellent heating‐cooling cycling durability. Circularly polarized NIR light selectively triggered gel‐solution phase transition at different timescales. Left‐ and right‐CP illumination generates up to 2.5 folds difference in gel collapse time that allows for direct discrimination by naked eyes. [ABSTRACT FROM AUTHOR]

The halogen bond is the attractive interaction between the electrophilic region of a halogen atom and the nucleophilic region of another molecular entity, emerging as a favorable manner to manipulate supramolecular chirality in self‐assemblies. Engineering halogen bonded helical structures remains a challenge due to its sensitivity to solvent polarity and competitive forces like hydrogen bonds. Herein, we report a X⋅⋅⋅X (X=Cl, Br, I) type weak halogen bond that induces the formation and evolution of supramolecular helical structures both in solid and solution state. The π‐conjugated phenylalanine derivatives with F, Cl, Br and I substitution self‐assembled into 21 helical packing driven by hydrogen bond and halogen bond, respectively. The specific molecular geometries of π‐conjugated amino acids gave rise to multiple noncovalent forces to stabilize the X⋅⋅⋅X halogen bond with small bond energies ranging from −0.69 to −1.49 kcal mol−1. Halogen bond induced an opposite helicity compared to the fluorinated species, accompanied by the inversed circularly polarized luminescence. [ABSTRACT FROM AUTHOR]

Deep understanding of structure–property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self‐assembled π‐conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N‐terminus, which afforded 21 and 31 symmetry supramolecular tilt chirality in solid‐states. Helical assemblies enabled diversified Cotton effects and CPL performances, which were in accordance with the tilted chirality between anthracene segments. Such correlation shows fine universality, whereby the chiroptical prediction could be realized. Furthermore, on top of charge‐transfer complexation, manipulation of CPL emission colors and handedness were realized. [ABSTRACT FROM AUTHOR]