Diastereoselective Supramolecular Encapsulation and Chirality Transfer Between Cholesteryl Binaphthyl Conjugates and Polyaromatic Hydrocarbon.

Diastereoselective effect plays an important role in the synthesis of chiral complexes and macrocyclic compounds, while its function in selective coassembly and chirality transfer has yet to be unveiled. In this work, two pairs of diastereomers containing R/S- binaphthyl and homochiral cholesteryl domains are synthesized, which provide multiple sites to encapsulate polyaromatic hydrocarbon through π-π and CH-π interactions. X-ray structures and computational studies suggest the binaphthol derivatives feature CH-π folding into butterfly-like open geometry, while binaphthylenediamine derivatives adopt closed geometry supported by van der Waals between cholesteryl domains. Driven by solvophobic forces, the building units self-assemble into vesicles and nanofibers in the aqueous and methanol phases, respectively. Binaphthol derivatives selectively encapsulate pyrene by naphthalene domains in the vesicle phase, while binaphthylenediamine derivatives encapsulate pyrene by cholesteryl domains in the nanofiber phase. Density functional theory-based calculations and circular dichroism spectra evidence the closed geometry of binaphthylenediamine derivatives facilitates a clamp-type host to increase the affinity toward pyrene in spite of the strong solvation competition. This work unveils the diastereoselectivity in the chiral coassembly, deepening the understanding of the precise synthesis of functional chiroptical complexes.

Hypervalent Iodine(III) Mediated Halogen Bonded Supramolecular Chiral System with Cholesteryl Naphthalimides.

Halogen bonding acknowledged as a noteworthy weak interaction, has gained growing recognition in the field of supramolecular chemistry. In this study, we selected structurally rigid diaryliodonium ions (I(III)) with two biaxial σ-holes as halogen-bond donors, to bind with three chiral acceptor molecules bearing cholesteryl and naphthalimides with distinct geometries. The abundant carbonyl oxygen atoms in side-arm substituents function as multiple acceptors for halogen bonding. The self-aggregation of chiral acceptor molecules demonstrates adaptiveness to solvent media, evidenced by the inversion of the Cotton effect and the morphological evolution from spherical to rod-like nanoarchitectures in different solvent systems. The distinct geometries of the acceptor molecules conferred various binding modes with I(III). The introduction of I(III) as a halogen-bond donor regulates the aggregation of the donors, achieving amplification of chiroptical signals and inheriting solvent responsiveness from the self-aggregated assembly. This study successfully utilized rational structural design and multimodal control strategies to achieve regulation of supramolecular chirality.

Ultrasensitive Solvatochirochromism of Single Benzene Chromophores.

Solvents influence the structure, aggregation and folding behaviors of solvatochromic compounds. Ultrasensitive solvent mediated chiroptical response is conducive to the fabrication of molecular platform for sensing and recognition, which however, remains great challenges in conceptual or applicable design. Here we report a cysteine-based single benzene chromophore system that shows ultrasensitivity to solvents. Compared to the ratiometrically responsive systems, the chiroptical activities could be triggered or inverted depending on the substituents of chiral entities with an ultralow solvent volume fraction (<1 vol %). One drop of dipolar solvents shall significantly induce the emergence or inversion of chiroptical signals in bulky phases. Based on the experimental and computational studies, the ultrasensitivity is contributed to the intimate interplay between solvents and chiral compounds that anchors the specific chiral conformation. It illustrates that structurally simple organic compounds without aggregation or folding behaviors possess pronounced solvatochiroptical properties, which sheds light on the next-generation of chiroptical sensors and switches.

Thermal Chiroptical Switch Based on an Ultrahigh Temperature-Initiated Macrocycle Gel Platform.

Responsive chiral optical materials have gained considerable interests from the fields of sensing, display, and optical devices. Materials that are capable of changing chiral optics under harsh conditions such as strong basic/acidic or ultrahigh temperature provides thoughts for the design of materials working at special environments, which however, are still underdeveloped. Here, a proof-of-concept design of organogel is reported that acts as matrices for thermal chiroptical switch with critical working temperature above 100 °C. The reversible solution-to-gel transition of the specific ß-cyclodextrin/dimethyl formide/LiCl system is initialized at about 130 °C, when the luminophores with aggregation-induced-emission property shall be lighted up with transferred chirality from inherent chiral ß-cyclodextrin. It allows for the controlled emergence of circularly polarized luminescence. This delicate design enables successful fabrication of ultrahigh temperature thermal chiroptical switch.

Chiral Superlattices Self-Assembled from Post-Modified Metal-Organic Polyhedra.

Metal-organic polyhedra (MOPs) are inherently porous, discrete, and solvent-dispersive, and directing them into chiral superlattices through direct self-assembly remains a considerable challenge due to their nanoscale size and structural complexity. In this work, we illustrate a postmodification protocol to covalently conjugate a chiral cholesteryl pendant to MOPs. Postmodification retained the coordination cores and allowed for reaction-induced self-assembly in loosely packed nanosized columns without supramolecular chirality. Solvent-processed bottom-up self-assembly in aqueous media facilitated the well-defined packing into twisted superlattices with a 5 nm lattice parameter. Experimental and computational results validated the role of intercholesteryl forces in spinning the nanosized MOPs, which achieved the chirality transfer to supramolecular scale with chiral optics. This work establishes a novel protocol in rational design of MOP-based chiroptical materials for potential applications of enantioselective adsorption, catalysis, and separation.

Multiple-State Control over Supramolecular Chirality through Dynamic Chemistry Mediated Molecular Engineering.

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.

Halogen Interaction Effects on Chiral Self-Assemblies on Cyclodipeptide Scaffolds Across Hierarchy.

How halogenation affects protein or peptide folding and self-assembly hierarchically? This study tries to answer this question by using the halogen bonding mediated self-assemblies on cyclodipeptide scaffolds. Single-functionalized cyclodipeptides (Cyclo-GX) based on para-halogenated phenylalanine in the solid state form homochiral helical nanotubes via consecutive X···O bonds (X = Cl, Br, and I) independent of halogen kinds. In contrast, double-functionalized cyclodipeptides (Cyclo-XX) feature versatile self-assembly architectures depending on the para-substituents (X = H, F, Cl, Br, and I), affording nanotubular, lamellar, and triple helical nanotubular architectures. Cyclo-BrBr exclusively adopts intramolecular Type-IV X···X interaction that alters the molecular folding and packing, which also gives rise to opposite chirality at molecular folding (secondary structure), stacking (tertiary structure), and self-assembled nanohelices (quarternary structure) at macroscopic scale. It unveils how halogenation impacts on the self-assembly and chirality at hierarchical levels in specific peptides. Clusteroluminescence is found for the cyclodipeptides, achieving high quantum yield up to 71%, whereby circularly polarized luminescence is realized with tunable handedness by controlling halogen substituents.

Chiral Polymer Dots Show Unexpected Versatility of Highly Ordered Self-Assembly into Chiroptical Liquid Crystals, Ultra-Thin Films, and Long-Ribbons.

Compared to the organic counterparts, chiral self-assembly of nanomaterials shows persistency to kinetic factors such as solvent environments, and consequently, dynamic modulation of self-assembly and functions remains major challenge. Here, it is shown that alkylated, chiral polymer dots (c-PDs) give highly ordered self-assemblies with amplified chirality adaptive to solvent environments, and one-to-many hierarchical aggregation can be realized. The c-PDs tended to self-assemble into nanohelices with cubic packing in the solid state, which, thanks to the thermo-responsiveness, transformed into thermic liquid crystals upon heating. Cotton effects and circularly polarized luminescence evidenced the chirality transfer from central chirality to supramolecular chirality. At the air-water interface, the c-PDs are self-assembled into monolayers, which further stack into multiple layers with chirality transfer and highly ordered packing. In addition, undergoing a good/poor solvent exchange, the c-PDs afforded ultra-long microribbons up to a length scale of millimeters, which are constituted by the bilayer lamellar stacking. The versatile chiral self-assembly modalities with long-range ordered packing arrays of carbonized c-PDs via solvent strategy are realized. This feature is comparable to the organic species, although the c-PDs have no atomic precise structures. This work would surely expand the applications of quantum dot ordered self-assembly with adaptiveness to kinetic factors.

Hydrogen Bonded Foldamers with Axial Chirality: Chiroptical Properties and Applications.

Folding phenomenon refers to the formation of a specific conformation widely featured by the intramolecular interactions, which broadly exist in biomacromolecules, and are closely related to their structures and functions. A variety of oligomeric folded molecules have been designed and synthesized, namely "foldamer", exhibiting potentials in pharmaceutical and catalysis. Molecular folding is a promising strategy to transfer chirality from substituents to the whole skeleton, when chirality transfer, amplification, evolution, and other behaviors could be achieved. Investigating chirality using foldamer model deepens the understanding of the structure-function correlation in biomacromolecules and expands the molecular toolbox towards chiroptical and asymmetrical chemistry. Substitutes with abundant hydrogen bonding sites conjugated to a rotatable aryl group afford a parallel ß-sheet-like conformation, which enables the emergence and manipulation of axial chirality. This concept aims to give a brief introduction and summary of the hydrogen bonded foldamers with anchored axial chirality, by taking some recent cases as examples. Design principles, control over axial chirality and applications are also reviewed.

Charge-Transfer Complex Doped Photothermal Hydrogels for Discriminating Circularly Polarized Near-Infrared Light.

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.

Arene-Perfluoroarene Force Driven Sublimation-Removable Chiral Coassemblies.

Multiple constituent coassembly is an emerging strategy to manipulate supramolecular chirality and chiroptical properties such as circularly polarized luminescence (CPL). However, the second or third constituent could not be removed from pristine self-assembly. Here we developed a constitute-removable chiral coassembly using sublimation that could realize coassembly with tunable supramolecular chirality, luminescence and CPL properties. Octafluoronapthalene (OFN) with small sublimation enthalpy formed coassemblies with perylene-conjugated peptoids via arene-perfluoroarene (AP) interaction that induced the emergence of macroscopic chirality and hypsochromic luminescence from yellow to green. Coassembly with OFN accelerated one-dimensional growth and induced the emergence of macroscopic chirality and CPL. Despite the stability at ambient conditions, vacuum-treatment triggered fast sublimation of OFN, which behaved as a sacrificial template. Physical removal of OFN retained the helical nanoarchitectures as well as the basic features of Cotton effects and CPL activities. X-ray diffraction suggested the back-fill consolidation occurred on the molecular voids by OFN removal that slightly varied the templated molecular arrangements. Sublimation of perfluorinated building units is green and efficient and non-destructive, which is potentially applicable in constructing template-directed chiroptical materials and devices.

Biogenetic Chiral Deep Eutectic Solvents that Produce Self-Assembled Chiroptical Materials.

Deep eutectic solvents (DESs) show particular properties compared to ionic liquids and other traditional organic solvents. Controlled synthesis of chiral materials in DESs is unprecedented due to the complex interplays between DESs and solutes. In this work, all bio-derived chiral DESs were prepared using choline chloride or cyclodextrin as hydrogen bonding acceptors and natural chiral acids as donors, which performed as chiral matrices for the rational synthesis of chiroptical materials by taking advantage of the efficient chirality transfer between the DESs and solutes. In a very selective manner, building units with molecular pockets could facilitate strong binding affinity towards chiral acid components of DESs disregarding the presence of competitive hydrogen bonding acceptors. Chirality transfer from DESs to nanoassemblies leads to chirality amplification in the presence of minimal amounts of entrapped chiral acids, thanks to the spontaneous symmetry breaking of solutes during aggregation. This work utilizes chiral DESs to control supramolecular chirality, and illustrates the structural basis for the fabrication of DES-based chiral materials.

Four-Component Ugi Reaction for Optical Chirality Sensing and Surface Nanoengineering of Chiral Self-Assemblies.

Using green chemistry to control chirality at hierarchical levels as well as chiroptical activities endows with new opportunities to the development of multiple functions. Here, the four-component Ugi reaction is introduced for the general and precise optical chirality sensing of amines as well as the surface nanoengineering of chiral soft self-assemblies. To overcome the relatively weak Cotton effects, direct synthesis of a folded peptide structure on a rotatable ferrocene core with axial chirality was accomplished from chiral amine, 1,1'-ferrocenyl dicarboxylic acid, formaldehyde and isocyanide. Enhanced Cotton effects benefiting from the folded structure allow for the precise and quantitative sensing of natural and synthetic chiral amines covering alkyl, aromatic amines and amino acid derivatives. In addition, aqueous reaction enables the modification of amine-bearing dye to microfibers self-assembled from π-conjugated amino acids. Surface dye-modification via Ugi reaction barely changes the pristine morphology, showing non-invasive properties in contrast to dye staining, which is applicable in soft nano/microarchitectures from self-assembly. This work which combines the four-component Ugi reaction to enable precise ee% detection and surface nanoengineering of soft chiral assemblies sheds light on the advanced application of green chemistry to chirality science.

Co-Assembly of Chiral Amines and a Four-Armed Cyano-Substituted Luminophore through Hydrogen Bonds for Potential Development of Smart Chiroptical Materials.

Chirality transfer from chiral molecules to assemblies is of vital importance to the design of functional chiral materials. In this work, selective co-assembly behaviors between chiral molecules and an achiral luminophore, potentially driven by the intermolecular salt-bridge type hydrogen bonds are reported. Cyano-substituted tetrakis(arylthio)benzene carboxylic acid (TA) served as the luminophore and hydrogen bond donors, which underwent co-assembly with different chiral amines. It was found that structures of chiral amines affect the chirality transfer and the properties of co-assemblies due to effects on hydrogen bonds and stacking pattern. Only in specific co-assemblies, the chiroptical properties occurred at both ground state and excited states based on the emerged Cotton effects and circularly polarized luminescence (CPL) signals, revealing that the chirality was successfully transferred from molecular level to supramolecular level. In addition, accurate quantitative examination of chiral amines was realized by circular dichroism (CD) spectra. This work demonstrates the characteristic chirality response and transfer through co-assembly, providing a potential method to develop smart chiroptical materials.

X⋠⋠⋠X Halogen Bond-Induced Supramolecular Helices.

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.

Transpositional Circularly Polarized Luminescence from Transient Charge-Transfer Coassembly.

Charge-transfer (CT) complexation between electron-rich and deficient aromatics has been widely applied in functional optical and photovoltaic materials. The selective complexation and spontaneous disassociation behavior of a dynamic charge-transfer coassembly possess potential in designing smart and dynamic luminescent materials, which however have not been addressed so far. In this work, the transient charge-transfer driven coassembly between π-conjugated amino acids and tetracyanobenzene, showing dynamic luminescent transition and circularly polarized luminescence (CPL) evolution property, is illustrated. Transient coassembly behaviors are independent to the diverse binding sites covering fluorene, naphthalene, and anthracene, attributed to the intramolecular CH…π interaction. Incorporation of fluorescent dyes enables a transient light harvesting process with hyperchromic CPL properties. Spontaneous green-to-red CPL transition hydrogels are also fabricated by embedding a competitive CT donor. Using a polymeric matrix treated by organic solvents, charge-transfer coassembly is immobilized with diverse circularly polarized luminescence. Such sensitive complexation shows applications in moisture-responsive luminescent materials and multiple luminescent color evolutions are realized.

Polyhedral Oligosilsesquioxanes in Functional Chiral Nanoassemblies.

Incorporation of giant molecular nanoparticles with atomic precision into chiral nanoassemblies facilitates the fabrication of functional ordered phases with supramolecular chirality, which remains mysterious. Reported here is the first example of polyhedral oligosilsesquioxane (POSS) derivatives that self-assemble into well-defined chiral nanoassemblies. POSSs were covalently conjugated to N-terminal aromatic amino acids, which self-assembled into nanohelices and twists with explicit handedness tuned by solvent polarity. Chiral nanoassemblies showed active chiroptical responses including Cotton effects and circularly polarized luminescence. The chiral systems can bind guest molecules by charge-transfer interactions, whereby self-assembled structures, chiroptical activities, and luminescent colors were further modulated. The unique coassembly systems were applied for instant information encryption and storage with multiple luminescent displays. This work offers a new protocol for the design of functional chiral materials of POSS by molecular self-assembly.

Multi-Modal Chiral Superstructures in Self-Assembled Anthracene-Terminal Amino Acids with Predictable and Adjustable Chiroptical Activities and Color Evolution.

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.

Modular Molecular Self-Assembly for Diversified Chiroptical Systems.

Bottom-up multicomponent molecular self-assembly is an efficient approach to fabricate and manipulate chiral nanostructures and their chiroptical activities such as the Cotton effect and circular polarized luminescence (CPL). However, the integrated coassembly suffers from spontaneous and inherent systematic pathway complexity with low yield and poor fidelity. Consequently, a rational design of chiral self-assembled systems with more than two components remains a significant challenge. Herein, a modularized, ternary molecular self-assembly strategy that generates chiroptically active materials at diverse hierarchical levels is reported. N-terminated aromatic amino acids appended with binding sites for charge transfer and multiple hydrogen bonds undergo the evolution of supramolecular chirality with unique handedness and luminescent color, generating abundant CPL emission with high luminescence dissymmetry factor values in precisely controlled modalities. Ternary coassembly facilitates high-water-content hydrogel formation constituted by super-helical nanostructures, demonstrating a helix to toroid topological transition. This discovery would shed light on developing complicated multicomponent systems in mimicking biological coassembly events.

Chiroptical Helices of N-Terminal Aryl Amino Acids through Orthogonal Noncovalent Interactions.

In the solid state, amino acids (alanine and phenylglycine) with appended pyrene segments self-assembled into α-helix-like structures by asymmetrical H-bonds between carboxylic acid and amide segments, further inducing supramolecular tilted chirality of the achiral pyrenes. These structures bind melamine and electron-deficient units through H-bond and charge-transfer interactions, respectively. Charge-transfer interactions enhance the dissymmetry g-factor of absorption (gabs ; up to 1.4×10-2 ) with an extended Cotton effect active region (from 250 to 600 nm). Incorporating melamine inverts the handedness of circularly polarized luminescence and boosts the dissymmetry g-factor (glum ). Melamine also induces macroscopic chirality at the nanoscale, whereby the 2D lamellar structures are transformed into 1D helices at the nanoscale, leading to giant tubular structures at the microscale.