Enantiomer Recognition by the Difference in Adsorption Rates on the Surfaces of Chiral Crystals.

The chirality of biopolymers remains one of the mysteries of Life. For such objects, the phenomenon of supramolecular chirality (SMC) is vital. Enantiomers can be recognized by the adsorption on surfaces with SMC. However, the mechanisms of such chiral recognition are still unknown. In this work, the adsorption kinetics of menthol test enantiomers on the surfaces of γ-glycine and NiSO4•6H2O chiral crystals was studied. It was found that the difference in adsorption was observed in nonequilibrium state more often than in equilibrium. If the enantioselectivity in equilibrium state was observed, the enantioselectivity coefficient α at nonequilibrium conditions was higher. The maximum α in nonequilibrium state was 2.44 for γ-glycine crystals and 2.12 for NiSO4•6H2O crystals. Even if no differences in adsorption were observed under adsorption-desorption equilibrium conditions, a significant enantioselectivity at nonequilibrium conditions was found. This has proved the possibility of chiral recognition on surfaces with SMC by the differences in adsorption rates. Such novel chiral recognition mechanism can provide enhanced enantioselectivity in adsorption, catalysis, chromatographic separation, and chemical sensing.

Circularly Polarized Lasing from Helical Superstructures of Chiral Organic Molecules.

Chiral supramolecular aggregates have the potential to explore circularly polarized lasing with large dissymmetry factors. However, the controllable assembly of chiral superstructures towards deterministic circularly polarized laser emission remains elusive. Here, we design a pair of chiral organic molecules capable of stacking into a pair of definite helical superstructures in microcrystals, which enables circularly polarized lasing with deterministic chirality and high dissymmetry factors. The microcrystals function as optical cavities and gain media simultaneously for laser oscillations, while the supramolecular helices endow the laser emission with strong and opposite chirality. As a result, the microcrystals of two enantiomers allow for circularly polarized laser emission with opposite chirality and high dissymmetry factors up to ~1.0. This work demonstrates the chiral supramolecular assemblies as an excellent platform for high-performance circularly polarized lasers.

Induced Circularly Polarized Luminescence From 0D Quantum Dots by 2D Chiral Nanosheets.

Materials with circularly polarized luminescence (CPL) exhibit great application potential in biological scenes such as cell imaging, optical probes, etc. However, most developed materials are non-aqueous and toxic, which seriously restricts their compatibility with the life systems. Thus, it is necessary to explore a water-based CPL system with high biocompatibility so that to promote the biologic application process. Herein, a facile and efficient route to achieve the CPL properties of a functional aqueous solution is demonstrated by the combination of 0D quantum dots (QDs) and 2D chiral nanosheets. Benefited by the specific absorption ability of nanosheets for left/right-handed CPL, the QDs adsorbed onto the surface of nanosheets through hydrogen bond interactions showed apparent CPL features. In addition, this system has a good extensibility as the CPL property can be effectively regulated by changing the kind of emissive QDs. More importantly, this water-based nano-composite with facile fabrication process (one-step mixing) is suitable for the real applications, which is undoubtedly beneficial for the further progress of functional CPL materials.

Chirality and Curvature on Protein Adsorption and Osteogenesis.

Here we designed enantiomeric lipid-mimetic glutamic acid derivatives (L/D-UG) and investigated their self-assembled chiral nanostructures' interaction with the protein adsorption as well as the osteogenesis. It was found that L or D-UG molecules can self-assemble into vesicle bilayers and two-dimensional (2D) nanocrystals via a kinetic and thermodynamic control, respectively. These chiral vesicles and 2D crystals showed differentiated adsorption of proteins, determined by their curvature and chirality. Specifically, fibronectin constituted by L-amino acids adsorbed preferentially on L-UG 2D crystal in a semi-random pattern and L-2D nanocrystal show as the most effective structures to promote bone regeneration. The controlled vesicle and 2D crystal assemblies with different chirality and curvature helps to clarify their determine roles in protein adsorption and osteogenesis.

Heterochiral π-stacking dimerization of helical secondary structures with emerging supramolecular chirality.

In this work, we report a new type of interface modes between helical secondary structures by noncovalent assembly along the helical axis. The dimerization of helical secondary structures mediated by aromatic π-stacking leads to discrete heterochiral dimeric helical rods consisting of left-handed helix and right-handed helix, which has been demonstrated by single-crystal X-ray diffraction. We conduct chiral induction studies on discrete heterochiral dimers to regulate the preference of the helical sense. Surprisingly, we found a novel supramolecular chirality potentially occurring inside the super-secondary structure of chirality-induced heterochiral helical dimers, rather than the racemization of helical chirality. Furthermore, chirality-induced heterochiral helical dimers can exhibit unique chiral switches when formed or not formed. In order to identify the emerging supramolecular chirality of discrete heterochiral dimeric helix, we covalently synthesized meso-helix structures with opposite helical handedness. The chirality of aromatic chromophore linker was confirmed by chiral induction despite competition from opposite handed helices, which strongly demonstrates the occurrence of emerging supramolecular chirality in heterochiral dimeric helix. This study not only reports the heterochiral π-stacking dimerization of helical secondary structures for the first time, but also discovers novel supramolecular chirality hidden in the structure of noncovalent and even covalent meso-helices.

Supramolecular Chiral Aggregation of Porphyrin Induced by Photo-Generated Triphenylamines Radical Cations.

Here, it is shown that photoirradiation triggered chiral J-aggregates formation of an achiral anionic porphyrin, TPPS (tetrakis(4-sulfonatophenyl) porphyrin), in the presence of chiral triphenylamine (TPA) derivatives. A series of chiral triarylamines linked with aromatic rings is designed through urea or amide bonds. UV-irradiation of self-assembled urea-linked triphenylamine derivatives causes the formation of persistent radical cations in the chlorinated solvents, which subsequently induces the aggregation of TPPS. Transferring chirality of TPA derivatives to achiral TPPS J-aggregates leads to the chiral assemblies with remarkable chiroptical signals. The experimental results demonstrate that, TPA derivatives linked by the urea bond can effectively promote the aggregation of TPPS rather than those with the amide bond although the photo-generated radical cations are both produced. It is suggested that the urea-linked TPA derivatives are more favorable to stable radical cations and thus cause the formation of TPPS chiral J-aggregation. This work may open up an avenue for designing photo-modulated chiral supramolecular assemblies.

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts on-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore. The prochirality recognition of the solvent molecule in the chiral SAMN pores is attributed to the adaptable conformational changes of the chiral chains of the cDBA molecule.

Hypervalent Iodine (III)-Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch.

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge-assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion as biaxial halogen bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial halogen bonding enables chiroptical evolution in solution, allowing for rational control over supramolecular chirality. Leveraging their strong binding affinity, the halogen bonding complexes manifested amorphous properties and deep eutectic behavior in the solid state. Capitalizing on these attributes, this work achieves the successful preparation of supramolecular glasses and deep eutectic solvents. Additionally, halogen bonding appended light irradiation-triggered luminescence through a hydrogen atom transfer process, showing applications in anti-counterfeit and display.

Structural Basis of Cucurbituril-Containing Self-Assembled Supramolecular Chiral Materials.

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.

Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling.

Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a |glum| value up to 0.11. The microcrystals were prepared from highly emissive difluoroboron ß-diketonate (BF2dbk) dyes R-1 or S-1 with chiral binaphthol (BINOL) skeletons. R-1 and S-1 exhibit undetectable CPL signals in solution but manifest intense CPL emission in their chiral microcrystals. The chiral superstructures induced by BINOL skeletons were confirmed by single-crystal XRD analysis. Spectral analysis and theoretical calculations indicate that intermolecular electronic coupling, mediated by the asymmetric stacking in the chiral superstructures, effectively alters excited-state electronic structures and facilitates electron transitions perpendicular to BF2bdk planes. The coupling increases cosθµ,m from 0.05 (monomer) to 0.86 (tetramer) and triggers intense optical activity of BF2bdk. The results demonstrate that optical activity of chromophores within assemblies can be regulated by both orientation and extent of intermolecular electronic couplings.

Dual-Regulation of Supramolecular Chirality in Achiral Side-Chain Azobenzene Liquid-Crystalline Polymers.

Azobenzene (Azo) liquid-crystalline polymers are intriguing due to their unique photo-induced isomerization and supramolecular chirality. However, clarification on multicomponent chiral induction towards Azo polymers remains ambiguous and challenging. Herein, chiral solvents and amines were employed to control the chiroptical activity of achiral Azo polymers. Methyl L-/D-lactate was added as the poor solvent and chiral inducer to achieve the first chiral induction in Azo aggregates. Chiral amines were utilized for the second chiral induction based on the acid-base interactions between the carboxyl groups of polymers and amines. The chiral enhancement and inversion of Azo units could be observed through the synergistic or antagonistic effect between solvents and amines. The impacts of solvent, chemical structures, feed ratio, enantiomeric excess, and temperature on supramolecular chirality were systematically studied. Furthermore, this system displayed the chiroptical switching property and chiral recovery under reversible irradiation.

Vibrational circular dichroism of adenosine crystals.

Adenosine is one of the building blocks of nucleic acids and other biologically important molecules. Spectroscopic methods have been among the most utilized techniques to study adenosine and its derivatives. However, most of them deal with adenosine in solution. Here, we present the first vibrational circular dichroism (VCD) spectroscopic study of adenosine crystals in solid state. Highly regular arrangement of adenosine molecules in a crystal resulted in a strongly enhanced supramolecular VCD signal originating from long-range coupling of vibrations. The data suggested that adenosine crystals, in contrast to guanosine ones, do not imbibe atmospheric water. Relatively large dimensions of the adenosine crystals resulted in scattering and substantial orientational artifacts affecting the spectra. Several strategies for tackling the artifacts have been proposed and tested. Atypical features in IR absorption spectra of crystalline adenosine (e.g., extremely low absorption in mid-IR spectral range) were observed and attributed to refractive properties of adenosine crystals.

Self-Sorting vs Coassembly in Peptide Amphiphile Supramolecular Nanostructures.

The functionality of supramolecular nanostructures can be expanded if systems containing multiple components are designed to either self-sort or mix into coassemblies. This is critical to gain the ability to craft self-assembling materials that integrate functions, and our understanding of this process is in its early stages. In this work, we have utilized three different peptide amphiphiles with the capacity to form ß-sheets within supramolecular nanostructures and found binary systems that self-sort and others that form coassemblies. This was measured using atomic force microscopy to reveal the nanoscale morphology of assemblies and confocal laser scanning microscopy to determine the distribution of fluorescently labeled monomers. We discovered that PA assemblies with opposite supramolecular chirality self-sorted into chemically distinct nanostructures. In contrast, the PA molecules that formed a mixture of right-handed, left-handed, and flat nanostructures on their own were able to coassemble with the other PA molecules. We attribute this phenomenon to the energy barrier associated with changing the handedness of a ß-sheet twist in a coassembly of two different PA molecules. This observation could be useful for designing biomolecular nanostructures with dual bioactivity or interpenetrating networks of PA supramolecular assemblies.

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.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Control of Kinetic Pathways toward Supramolecular Chiral Polymorphs for Tunable Circularly Polarized Luminescence.

An amphiphilic aza-BODIPY dye (S)-1 bearing two chiral hydrophilic side chains with S-stereogenic centers was synthesized. This dye exhibited kinetic-controlled self-assembly pathways and supramolecular chiral polymorphism properties in MeOH/H2O (9/1, v/v) mixed solvent. The (S)-1 monomers first aggregated into a kinetic controlled, off-pathway species Agg. A, which was spontaneously transformed into an on-pathway metastable aggregate (Agg. B) and subsequently into the thermodynamic Agg. C. The three aggregate polymorphs of dye (S)-1 displayed distinct optical properties and nanomorphologies. In particular, chiral J-aggregation characteristics were observed for both Agg. B and Agg. C, such as Davydov-split absorption bands (Agg. B), extremely sharp and intense J-band with large bathochromic shift (Agg. C), non-diminished fluorescence upon aggregation, as well as strong bisignated Cotton effects. Moreover, the AFM and TEM studies revealed that Agg. A had the morphology of nanoparticle while fibril or rod-like helical nanostructures with left-handedness were observed respectively for Agg. B and Agg. C. By controlling the kinetic transformation process from Agg. B to Agg. C, thin films consisting of Agg. B and Agg. C with different ratios were prepared, which displayed tunable CPL with emission maxima at 788-805 nm and g-factors between -4.2×10-2 and -5.1×10-2.

Handedness-Inverted and Stimuli-Responsive Circularly Polarized Luminescent Nano/Micromaterials Through Pathway-Dependent Chiral Supramolecular Polymorphism.

The precise manipulation of supramolecular polymorphs has been widely applied to control the morphologies and functions of self-assemblies, but is rarely utilized for the fabrication of circularly polarized luminescence (CPL) materials with tailored properties. Here, this work reports that an amphiphilic naphthalene-histidine compound (NIHis) readily self-assembled into distinct chiral nanostructures through pathway-dependent supramolecular polymorphism, which shows opposite and multistimuli responsive CPL signals. Specifically, NIHis display assembly-induced CPL from the polymorphic keto tautomer, which become predominant during enol-keto tautomerization shifting controlled by a bulk solvent effect. Interestingly, chiral polymorphs of nanofiber and microbelt with inverted CPL signals can be prepared from the same NIHis monomer in exactly the same solvent compositions and concentrations by only changing the temperature. The tunable CPL performance of the solid microbelts is realized under multi external physical or chemical stimuli including grinding, acid fuming, and heating. In particular, an emission color and CPL on-off switch based on the microbelt polymorph by reversible heating-cooling protocol is developed. This work brings a new approach for developing smart CPL materials via supramolecular polymorphism engineering.

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.

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

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.

Photoisomerization and thermal reconstruction induced supramolecular chirality inversion in nanofiber determined by minority isomer.

Here, amphiphile GCH based on glutamide-cyanostilbene is designed and synthesized, it is found that it can assembly in acetonitrile, and shows circular dichroism signals. After Z-E isomerizaition by UV irradiation, the CD signal of the assembly can be inverted. Unexpectedly, after another heating and cooling process, the circular dichroism signals can be totally inverted even though the E-isomers are in minority. Finally, the molecular dynamics (MD) simulations deeply elucidate the supramolecuar chirality inversion mechanism. This work brings some new insights into the control of chirality inversion, which may provide a perspective for the smart chiroptical materials construction.