Supramolecular chirality is involved not only in biological events such as gene communication, replication, and enzyme catalysis but also in artificial self-assembly systems and aggregated materials. The precise control of supramolecular chirality, and especially supramolecular chirality inversion (SMCI), would deepen the understanding of chiral transfer and regulation in both living systems and artificial self-assembly systems, providing efficient ways to construct advanced chiral materials with an optimum assembly pathway necessary for various functions. In this review, the fundamental principles of SMCI are comprehensively summarized, with a focus on the helical assemblies having opposite handedness or chiroptical properties of the compositions. Thereafter, various SMCI strategies that have been developed for chiral nanostructures and assembled materials are systematically reviewed, and the promising applications of SMCI, including chiroptical switches, chiral recognition, enantiomeric separation, asymmetric catalysis, chiral optoelectronic materials, chiral spin filters, and biomedical uses, are highlighted accordingly. Finally, the scientific challenges and future perspectives for assembling materials with SMCI are also discussed.

Self-assembled stereomutation with supramolecular chirality inversion.

Memorable full-color circularly polarized luminescence from chiral co-assembled polymer films enabled by multipath transfer

Macroscopic regulation of chiral supramolecular nanostructures in liquid-crystalline block copolymers is of great significance in photonics and nanotechnology. Although fabricating helical phase structures via chiral doping and microphase separation has been widely reported, the chiral memory and self-recovery capacity of asymmetric phase structures are the major challenge and still deeply rely on the presence of chiral additives. Herein, we demonstrate the first controllable chiral microphase separation in an achiral amphiphilic block copolymer consisting of poly(ethylene oxide) and azobenzene (Azo) groups. Chirality can be transferred to the fabricated helical nanostructures by doping with chiral additives (tartaric acid, TA). After the removal of the chiral additives and then performing cross-linking, the formed helical nanostructures will completely dispense with the chiral source. The supramolecular chirality and the micron-scale phase structure can be maintained under UV irradiation and heating-cooling treatment, enabling a reversible “on–off” chiroptical switch feature. This work is expected to avoid the tedious synthesis and expensive raw materials and shows a great application prospect in chiral separation and so on.

/pdf/self-recovery-of-chiral-microphase-separation-in-an-achiral-45zgoesk.pdf

Self-recovery of chiral microphase separation in an achiral diblock copolymer system

Preparation of chiral polymers: precise chirality transfer from natural species to achiral artificial polymers

Chirality, an inherent characteristic observed throughout nature, plays a pivotal role across a wide range of scales, from subatomic to galactic, and holds significance in myriad scientific fields, including chemistry, biology, and nanotechnology. Since the discovery of molecular chirality in 1848, there have been monumental advances, especially in the realm of chiral macromolecules and chiral supramolecular assemblies. This progress, primarily propelled by innovations in polymer science and supramolecular chemistry, has opened up numerous applications, spanning enantioselective sensing, catalysis, optics, and biomedicine. Both chiral macromolecules, synthesized either from chiral or achiral components, and chiral supramolecular assemblies, often manifest enhanced chiroptical responses and other intriguing chiral-related characteristics. However, challenges remain, particularly in precisely characterizing and understanding the governing factors and dynamics of these complex systems, as well as in synthesizing novel chiral macromolecules and chiral supramolecular assemblies that can efficiently interact with circularly polarized light. This review offers a comprehensive overview of the most recent advances in the synthesis, properties, characterization, and applications of chiral macromolecules and chiral supramolecular assemblies. In addition, it provides an insightful perspective on the current challenges and the future direction of research in this rapidly evolving field. 

Chiral Macromolecules and Supramolecular Assemblies: Synthesis, Properties and Applications

Circularly polarized luminescence (CPL) plays a pivotal role in cutting-edge display and information technologies. Currently achieving precise color control and dynamic signal regulation in CPL still remains challenging due to the elusory relationship between fluorescence and chirality. Inspired by the natural mechanisms governing color formation and chiral interaction, we proposed an addition-subtraction principle theory to address this issue. Three fluorene-based polymers synthesized by Suzuki polycondensation with different electron-deficient monomers exhibit similar structures and UV-vis absorption, but distinct fluorescence emissions due to intramolecular charge transfer. Based on this, precise-color CPL-active films are obtained through quantitative supramolecular co-assembly directed by addition principle. Particularly, an ideal white-emitting CPL film (CIE coordinates: (0.33, 0.33)) is facilely fabricated with a high quantum yield of 80.8% and a dissymmetry factor (glum) of 1.4 × 10-2. Structural analysis reveals that the ordered stacking orientation favors higher glum. Furthermore, to address the dynamically regulated challenge, the comparable subtraction principle is proposed, involving a contactless chiral communication between excited and ground states. The representative system consisting of as-prepared fluorene-based polymers and chirality-selective absorption azobenzene (Azo)-containing polymers is constructed, achieving CPL weakening, reversal, and enhancement. Finally, a switchable quick response code is realized based on trans-cis isomerization of Azo moiety.

Precise Modulation of Circularly Polarized Luminescence via Polymer Chiral Co-assembly and Contactless Dynamic Chiral Communication.

The evolution of hierarchical chirality at macromolecular and supramolecular levels in biological systems is ubiquitous; however, achieving precise control over transitions between them in polymer systems is still challenging. Here, we reported multiple chiroptical transitions and inversion phenomena in side-chain azobenzene (Azo) polymers, PAzo-l/d-m (m = 3, 6, 7, 8, 9, and 10, where m is the total number of atoms from the chiral stereocenter to the Azo unit), with different distances from the chiral stereocenter to the Azo unit. In the case of m = 3, an unexpected macromolecular-to-supramolecular chirality transition and inversion occurred in situ when the Azo-polymer underwent from a macromolecular-dissolved state to a supramolecular-aggregated state. To our surprise, an exciton-coupling induced multiple chiroptical inversion was observed upon the heating-assisted reassembly treatment, which was demonstrated to be driven by H- to J-aggregation transition. Furthermore, the odd–even effect was first established to regulate the supramolecular helical orientations (left- or right-handedness) in side-chain Azo-polymer assemblies.

https://pubs.rsc.org/en/content/articlepdf/2022/sc/d2sc05255e

Unexpected chirality transition and inversion mediated by dissolution–aggregation and the odd–even effect

The construction of chiral superstructures through self-assembly of non-chiral polymers usually relies on the interplay of multiple non-covalent bonds, which is significantly limited by the memory ability of induced chirality. Although the introduction of covalent crosslinking can undoubtedly enhance the stability of chiral superstructures, the concurrent strong constraining effect hinders the application of chirality-smart materials. To address this issue, we have made the first attempt at the reversible fixation of supramolecular chirality by introducing dynamic covalent crosslinking into the chiral self-assembly of side-chain polymers. After chiral induction, the reversible [2 + 2] cycloaddition reaction of cinnamate group in polymer chains can be further controlled by light to manipulate inter-chain crosslinking and decrosslinking. Based on this photo-programmable and dynamic chiral fixation strategy, a novel pattern-embedded storage mechanism of chiral polymeric materials was established for the first time.

Simultaneous Chiral Fixation and Chiral Regulation Endowed by Dynamic Covalent Bonds.

Building Permanently Optically Active Particles from Absolutely Achiral Polymer

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