Chiral Self-assembly Research Articles

Chiral Metal Self-assemblies of Zirconium-Tetrahedra and Their Second Harmonic Generation Activity.

The chirality of metal-organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units for the construction of noncentrosymmetric materials. Herein, by self-assembling the 4,4',4''-nitrilotribenzoic acid (H3NBA) with bis(cyclopentadienyl)-zirconium dichloride (Cp2ZrCl2, Cp = η5-C5H5) in different solvent conditions, we have obtained three hierarchical packing modes of metallo-tetrahedra with distinct spatial symmetry groups (designated as Zr-α, Zr-β, and Zr-γ). Among them, Zr-α employs a simple cubic arrangement and is a common centrosymmetric superstructure, which consists of a pair of equimolar metallo-tetrahedra enantiomers in its unit cell. While Zr-β results in conglomerates with spontaneous resolution without using any resolving agents, giving rise to two enantiopure entities separately (Zr-β-P, Zr-β-M). More importantly, Zr-γ breaks the inversion center of symmetry and crystallizes into a racemic yet non-centrosymmetric superstructure with face-centered cubic packing mode. Based on the non-centrosymmetric nature, the hierarchical superstructure Zr-γ displayed good second harmonic generation activities. This work presents a successful instance wherein the reaction solvent induces the modulation of intermolecular packing mode to afford non-centrosymmetric solid materials, which can greatly promote the development of noncentrosymmetric solid (NCS) materials.

Achiral and chiral ligands synergistically harness chiral self-assembly of inorganics.

Chiral structures and functions are essential natural components in biominerals and biological crystals. Chiral molecules direct inorganics through chiral growth of facets or screw dislocation of crystal clusters. As chirality promoters, they initiate an asymmetric hierarchical self-assembly in a quasi-thermodynamic steady state. However, achieving chiral assembly requires a delicate balance between intricate interactions. This complexity causes the roles of achiral-chiral and inorganic components in crystallization to remain ambiguous. Here, we elucidate a definitive mechanism using an achiral-chiral ligand strategy to assemble inorganics into hierarchical, self-organized superstructures. Achiral ligands cluster inorganic building blocks, while chiral ligands impart chiral rotation. Achiral and chiral ligands can flexibly modulate the chirality of superstructures by fully using their competition in coordination chemistry. This dual-ligand strategy offers a versatile framework for engineering chiroptical nanomaterials tailored to optical devices and metamaterials with optical activities across a broad wavelength range, with applications in imaging, detection, catalysis, and sensing.

Helical Polyallenes: From Controlled Synthesis to Distinct Properties.

Polyallenes with appropriate pendants can form stable helices and exhibit significant optical activity. These helical polyallenes contain reactive double bonds that allow for further functionalization, making them a class of chiral functional materials with broad application prospects. This review article delves into the intricacies of synthesizing well-defined helical polyallenes through controlled synthetic methodologies, including helix-sense selective living polymerization, regioselective and asymmetric living polymerization, and one-pot block copolymerization of allenes with aryl monomers. The systemically outlined characteristics of the resulting helical polyallenes and related copolymers are summarized include their unique chiroptical properties, stimuli-responsiveness, helix-induced chiral self-assembly, and circularly polarized luminescence (CPL). Additionally, current challenges and future perspectives in the research of controlled synthesis, functionalities, and applications of helical polyallenes are discussed in detail.

Chiral Self-Assembly of Twisted Prisms, Cuboids, and Polyhedral Capped Cages with Tartrate Ligands.

Homochiral triangular prisms, cuboid cages, and capped polyhedral cages are successfully synthesized via coordination-driven self-assembly. Typical tartrate ligands demonstrated notable torsional flexibility and variable coordination numbers, allowing for diverse coordination patterns, including saturated chelation and terminal mono-coordination with half-sandwich rhodium and iridium fragments. The ligand lengths, molar ratios, and metal vertices are meticulously designed and fine-tuned to yield chiral cages with entirely distinct architectures. Tartrate ligand exhibits abundant hydrogen bonding interactions and chiral induction capabilities, these supramolecular assemblies are characterized by single-crystal X-ray diffraction, nuclear magnetic resonance, and circular dichroism spectroscopy. An efficient method is developed for constructing chiral structurally versatile cage-like entities, facilitating self-assembly in complicated multi-component systems.

Polymerization-induced Chiral Self-assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures.

In the polymerization-induced chiral self-assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self-assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non-covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non-equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.

Chiral Supramolecular Self-Assembly Catalysts with Enhanced Metal Ion Interaction for Higher Enantioselectivity.

Understanding the interaction between metal ions as catalytic centers and supramolecular scaffolds as chiral substrates plays an important role in developing chiral supramolecular catalysts with high enantioselectivity. Herein, we found that compared with l-norleucine chiral amphiphile (l-NorC16), l-methionine chiral amphiphile (l-MetC16) with the only heteroatom of S site difference in the hydrophilic group can form a similar supramolecular chiral nanoribbon (NR) with the bilayer structure through the self-assembly approach; yet, the interaction between the Cu(II) ion catalytic centers and supramolecular scaffolds is reinforced, favoring the chirality transfer and therefore enhancing their catalytic enantioselectivity of Diels-Alder reaction from 23% [l-NorC16-NR-Cu(II)] to 78% [l-MetC16-NR-Cu(II)]. Our work demonstrates a new strategy from the perspective of strengthening the metal ion-supramolecular scaffold interaction for the preparation of chiral supramolecular catalysts with good catalytic enantioselectivity.

Orientation transitions and chiral assemblies of para-terphenyl molecules on Cd(0001).

The interplay between orientation transition and chiral self-assemblies of para-terphenyl (P3P) molecules on the Cd(0001) surface has been investigated using low temperature scanning tunneling microscopy and density functional theory calculations. Three distinct molecular orientations have been discerned from the self-assembled thin films of P3P. At the low coverage, flat-lying molecules appear in the homochiral domains with the incommensurate registry to the substrate. With the coverage increasing, the incoming molecules are incorporated into the first layer with edge-on orientation and form the self-assembled zigzag chains. The alternative arrangement of zigzag chains with opposite chirality leads to the formation of a c(4 × 2) superstructure, in which the tilted molecules exhibit orientational frustration and fuzzy noises. The analysis of the tunneling spectra reveals that the electronic structure of P3P layers is contingent upon the hybridization between the electronic states of P3P molecules and the Cd(0001) surface. These results provide important insights into the interplay between orientational transition and chiral assembly of P3P molecules on metal substrates.

Configuration space of helical chiral self-assembly of micro/nano-fibers

As undertaking various key functions, helical chiral structures are widely presented in nature. Herein, we develop a general theoretical framework to guide the formation of helical chiral structures through self-assembly of micro/nano-fibers driven by adhesion. By analyzing the spiral contact geometric characteristics of multiple fibers and extending the JKR theory, an analytical model for adhesive contact between helical interfaces is proposed. Further, the complete configuration space of self-assembled fibers depending on the adhesion work, elastic modulus, aspect ratio, and initial helix angle is theoretically obtained. A diversity of helical configurations that far beyond existing experimental findings are predicted, which stems from the existence of multiple energy minimum points on the configuration-energy map. This work reveals the mechanism of adhesion-driven helical chiral structures, and provides theoretical foundation for guiding high-efficient fabrication of helical chiral structures through self-assembly method, which could promote the wide application of chiral structures in fields such as optics, catalysis and drug screening.

Solvent-Mediated Chiral Self-Assembly of Nanosized π-Conjugated Polyhedral Oligomeric Silsesquioxane toward Full Spectrum Luminescence

Solvent-Mediated Chiral Self-Assembly of Nanosized π-Conjugated Polyhedral Oligomeric Silsesquioxane toward Full Spectrum Luminescence

Mechanically Tunable Circularly Polarized Luminescence of Liquid Crystal-Templated Chiral Perovskite Quantum Dots.

Endowing perovskite quantum dots (PQDs) with circularly polarized luminescence (CPL) offers great promise for innovative chiroptical applications, but the existing strategies are inefficient in acquiring stimuli-responsive flexible chiral perovskite films with large, tunable dissymmetry factor (glum) and long-term stability. Here, we report a strategy for the design and synthesis of luminescent cholesteric liquid crystal elastomer (Lumin-CLCE) films with mechanically tunable CPL, which is enabled by liquid crystal-templated chiral self-assembly and in situ covalent cross-linking of judiciously designed photopolymerizable CsPbX3 (X=Cl, Br, I) PQD nanomonomers into the elastic polymer networks. The resulting Lumin-CLCE films showcase circularly polarized structural color in natural light and noticeable CPL with a maximum glum value of up to 1.5 under UV light. The manipulation of CPL intensity and rotation direction is achieved by controlling the self-assembled helicoidal nanostructure and the handedness of soft helices. A significant breakthrough lies in the achievement of a reversible, mechanically tunable perovskite-based CPL switch activated by biaxial stretching, which enables flexible, dynamic anti-counterfeiting labels capable of decrypting preset information in specific polarization states. This work can provide new insights for the development of advanced chiral perovskite materials and their emerging applications in information encryption, flexible 3D displays, and beyond.

Fabrication strategies for chiral self-assembly surface.

Chiral self-assembly is the spontaneous organization of individual building blocks from chiral (bio)molecules to macroscopic objects into ordered superstructures. Chiral self-assembly is ubiquitous in nature, such as DNA and proteins, which formed the foundation of biological structures. In addition to chiral (bio) molecules, chiral ordered superstructures constructed by self-assembly have also attracted much attention. Chiral self-assembly usually refers to the process of forming chiral aggregates in an ordered arrangement under various non-covalent bonding such as H-bond, π-π interactions, van der Waals forces (dipole-dipole, electrostatic effects, etc.), and hydrophobic interactions. Chiral assembly involves the spontaneous process, which followed the minimum energy rule. It is essentially an intermolecular interaction force. Self-assembled chiral materials based on chiral recognition in electrochemistry, chiral catalysis, optical sensing, chiral separation, etc. have a broad application potential with the research development of chiral materials in recent years.

A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence.

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized chiral framework is conducive to directing π-π self-assembly and delivering a strong and persistent CPL signal. Here, perylene diimides (PDIs) are an excellent choice for the organic dye component because, alongside their tunable photophysical and self-assembly properties, functionalization of the PDI's core yields a twisted, chiral π-system, capable of CPL. However, configurationally stable PDI-based macrocycles are rare, and those that are also capable of π-π self-assembly beyond dimers are unprecedented, both of which are advantageous for robust self-assembled chiroptical materials. In this work, we report the first bay-connected bis-PDI macrocycle that is configurationally stable (ΔG⧧ > 155 kJ mol-1). We use this chirally locked macrocycle to uncover new knowledge of chiral PDI self-assembly and to perform new quantitative CPL imaging of the resulting single-crystal materials. As such, we discover that the chirality of a 1,7-disubstituted PDI provides a rational route to designing H-, J- and concomitant H- and J-type self-assembled materials, important arrangements for optimizing (chir)optical and charge/energy transport properties. Indeed, we reveal that CPL is amplified in the single crystals of our chiral macrocycle by quantifying the degree of emitted light circular polarization from such materials for the first time using CPL-Laser Scanning Confocal Microscopy.

Engineering π-Conjugation of Phenylalanine Derivatives for Controllable Chiral Folding and Self-Assemblies.

π-π stacking interaction is an attractive interaction that involves aromatic groups containing π-conjugated domains. It is a promising strategy for stabilizing folded structures with interesting chiroptical properties and manipulating the supramolecular chiral self-assembly process. In this study, we report the engineering of π-conjugated amino acids that utilize π-π stacking interactions to manipulate chiral folding as well as self-assembly evolution. Stepwise conjugation of phenyl, naphthyl, and pyrenyl to N-terminal phenylalanine derivatives witnessed the folding through intramolecular π-interactions in solution phase, which facilitated the formation of chiral geometry and the emergence of chiral optics. Introduction of aromatic domains efficiently lowers the critical aggregation concentration in the aqueous media. Molecular folding enables a special concentration-dependent self-assembly, whereby the supramolecular chirality accomplished inversion with the evolution of helical nanoarchitectures. This work develops a strategy to engineer π-conjugated amino acids with controllable folding behaviors, which also offers implications for the rational design of functional chiral materials.

Pnictogen bonding in imide derivatives for chiral folding and self-assembly.

Pnictogen bonding (PnB) is an attraction interaction that originates from the anisotropic distribution of electron density of pnictogen elements, which however has been rarely found in nitrogen atoms. In this work, for the first time, we unveil the general presence of N-involved PnB in aromatic or aliphatic imide groups and reveal its implications in chiral self-assembly of folding. This long-neglected interaction was consolidated by Cambridge structural database (CSD) searching as well as subsequent computational studies. Though the presence of PnB has limited effects on spectroscopic properties in the solution phase, conformation locking effects are sufficiently expressed in the chiral folding and self-assembly behavior. PnB anchors the chiral conformation to control the emergence and inversion of chiroptical signals, while intramolecular PnB induces the formation of supramolecular tilt chirality. It also enables the chiral folding of imide-containing amino acid or peptide derivatives, which induces the formation of unique secondary structural sequences such as β-sheets. Finally, the effects of PnB in directing folded helical structures were revealed. Examples of cysteine and cystine derivatives containing multiple N⋯O and N⋯S PnBs constitute an α-helix like secondary structure with characteristic circular dichroism. This work discloses the comprehensive existence of imide-involved PnB, illustrates its important role in folding and self-assembly, and sheds light on the rational fabrication of conformation-locked compounds and polymers with controllable chiroptical activities.

Recent advances in circularly polarized luminescence of planar chiral organic compounds.

Circularly polarized luminescence (CPL), as an important chiroptical phenomenon, can not only directly characterize excited-state structural information about chiroptical materials but also has great application prospects in 3D optical displays, information storage, biological probes, CPL lasers and so forth. Recently, chiral organic small molecules with CPL have attracted a lot of research interest because of their excellent luminescence efficiency, clear molecular structures, unique flexibility and easy functionalization. Planar chiral organic compounds make up an important class of chiral organic small molecular materials and often have rigid macrocyclic skeletons, which have important research value in the field of chiral supramolecular chemistry (e.g., chiral self-assembly and chiral host-guest chemistry). Therefore, research into planar chiral organic compounds has become a hotspot for CPL. It is time to summarize the recent developments in CPL-active compounds based on planar chirality. In this feature article, we summarize various types of CPL-active compounds based on planar chirality. Meanwhile, we overview recent research in the field of planar chiral CPL-active compounds in terms of optoelectronic devices, asymmetric catalysis, and chiroptical sensing. Finally, we discuss their future research prospects in the field of CPL-active materials. We hope that this review will be helpful to research work related to planar chiral luminescent materials and promote the development of chiral macrocyclic chemistry.

Angle-resolved optical spectroscopy of photonic cellulose nanocrystal films reveals the influence of additives on the mechanism of kinetic arrest.

Cellulose nanocrystals (CNCs) are rod-like nanoparticles whose chiral self-assembly into photonic films has been promoted as a sustainable source of colouration. Upon drying, an aqueous CNC suspension passes through two regimes: first, a liquid phase, where the CNCs self-organise into a cholesteric liquid crystal, followed by a kinetically-arrested phase, where the helicoidal structure compresses upon loss of solvent, resulting in a solid film with vibrant structural colour. The transition between these two regimes plays an important role in the visual appearance of photonic CNC films, but details on when and how kinetic arrest occurs have remained elusive. In this work, we combine angle-resolved optical spectroscopy of photonic films (approx. 100 vol% CNC) with a model for compressed helicoidal structures to retrieve the suspension conditions during kinetic arrest (approx. 10 vol% CNC). This analysis indicates a shift in the mechanism of kinetic arrest from a glass transition at lower ionic strength to gelation at higher ionic strength, explaining the trends in domain size and film colour. In contrast, neutral additives (glucose, poly(ethylene glycol)) appear to primarily reduce the compression upon drying without affecting cholesteric behaviour, as supported by a general analytical model. These findings deepen our understanding of CNC co-assembly with various commonly-used additives, enabling better control over the production of multifunctional structurally coloured materials.

Multiscale study of the chiral self-assembly of cellulose nanocrystals during the frontal ultrafiltration process.

The structural organization of cellulose nanocrystal (CNC) suspensions at the membrane surface during frontal ultrafiltration has been characterized, for the first time, at the nano- and microscale by in situ small-angle X-ray and light scattering (SAXS and SALS, respectively). During filtration, the particles assembled at the membrane surface and formed the so-called concentration polarization layer (CPL), which contains CNCs arranged in a chiral nematic (cholesteric) helicoidal structure, with the long axis of the CNCs oriented parallel to the membrane surface, and the helical axis of the cholesteric structure oriented perpendicular to the membrane surface. The self-organization of CNCs in the form of oriented cholesteric structures was further characterized by a pitch gradient in the CPL. The structure of the CPL was also investigated upon release of the transmembrane pressure. SAXS data revealed a relaxation process associated with a diffusion of the CNCs from the membrane surface towards the bulk, while SALS measurements revealed a re-organization of the cholesteric phase that was preserved all along the deposit. The preservation of the observed structure after 14 days of continuous filtration followed by air-drying was confirmed using scanning electron microscopy and wide-angle X-ray diffraction, demonstrating the feasibility of the process scale-up.

Selectivity in the chiral self-assembly of nucleobase-arylazopyrazole photoswitches along DNA templates.

The control of supramolecular DNA assembly through external stimuli such as light represents a promising approach to control bioreactions, and modulate hybridization or delivery processes. Here, we report on the design of nucleobase-containing arylazopyrazole photoswitches that undergo chiral organization upon self-assembly along short DNA templates. Chiroptical spectroscopy shows that the specific nucleobases allow selectivity in the resulting supramolecular DNA complexes, and UV light irradiation triggers partial desorption of the arylazopyrazole photoswitches. Molecular modeling studies reveal the differences of binding modes between the two configurations in the templated assembly. Remarkably, our results show that the photoswitching behaviour controls the self-assembly process along DNA, opening the way to potential applications as nano- and biomaterials.

Odd-even effect in chiral side-chain cyanobiphenyl block copolymer assemblies prepared by polymerization-induced chiral self-assembly.

The precise control of the chirality of polymer assemblies is a challenge faced by scientists and has received significant attention in recent years. In this study, we employed the polymerization-induced chiral self-assembly (PICSA) method to create chiral side-chain cyanobiphenyl (CB) block copolymer (BCP) assemblies. The flexible spacers in chiral CB monomers were regulated to exhibit two distinct odd-even effects in the supramolecular asymmetrical arrangement of the CB mesogens inside BCP assemblies. The research results indicated that the liquid crystalline properties of CB mesogens significantly influence the magnitude and sign of their chiroptical properties. These findings have significant implications for the design of polymer assemblies with designable chiroptical functions.

One-pot asymmetric living copolymerization-induced chiral self-assemblies and circularly polarized luminescence.

Controlled synthesis of conjugated block polymers enables the optimization of their self-assembly and may lead to distinct optical properties and functionalities. Herein, we report a direct chain extension of one-handed helical poly(acyl methane) with 1-ethynyl-4-iodo-2,5-bis(octyloxy)benzene, affording well-defined π-conjugated poly(acyl methane)-b-poly(phenylene ethynylene) copolymers. Although the distinct monomers are polymerized via different mechanisms, the one-pot copolymerization follows a living polymerization manner, giving the desired optically active block copolymers with controllable molar mass and low distribution. The block copolymerization induced chiral self-assembly simultaneously due to the one-handed helicity of the poly(acyl methane) block, giving spherical nanoparticles, one-handed helices, and chiral micelles with controlled dimensions regarding the composition of the generated copolymers. Interestingly, the chiral assemblies exhibit clear circularly polarized luminescence with tunable handedness and a high dissymmetric factor.