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Comprehensive Summary: The 21st century has witnessed a continuous evolution in the development of boron‐stereogenic chemistry. Since the 1990s, various innovations for the synthesis of tetracoordinate boron‐stereogenic compounds, which exhibited great potential applications, have been demonstrated by synthetic chemists. This paper reviews the significant progress and recent advances towards the assembly of enantioenriched boron‐stereogenic compounds, and hopes to shed light on new perspectives and inspire further research in this emerging field. [ABSTRACT FROM AUTHOR]

Various fascinating optical characteristics in organisms encourage scientists to develop biomimetic synthesis strategies and mimic their unique microstructure. Inspired by the Chameleon's skin with tunable color and superior flexibility, this work designs the evaporated‐induced self‐assembly technique to synthesize the chiral photonic crystal film. Ultrasonic‐intensified and additive‐assisted techniques synergistically optimize the film properties, on the aspects of optic and mechanic. The film shows considerable rigidity and superior flexibility, which can undergo multiple mechanical deformations. Without destroying the chiral nematic structure, the ultimate strain approaches 50%, which exceeds most cellulose‐derived film materials. It also integrates excellent optical performance. The film color can cover the total visible region by tuning the photonic bandgap and has angle‐dependent properties. It can make the response to humidity and solvents, and chromaticity variation reflects the degree of stimulation. Importantly, this structural‐dependent color change is reversible. Lastly, the photonic crystal materials with excellent mechanics and unique optics have been applied in the security. The anti‐counterfeiting material design contains photonic crystal ink, repeatable writing paper, information‐hiding film, and color‐changing labels, with the features of environmentally friendly, economical, non‐destructive, and convenient for authentication. [ABSTRACT FROM AUTHOR]

An elliptical chiral split‐ring‐resonator‐based bilayer thin metasurface is introduced in this paper. The proposed metasurface realizes strong electromagnetic (EM) activity with asymmetric transmission in the K‐band of the microwave regime. The efficiency is more than 80% over a range of frequencies from 18.6 to 20.8 GHz. Angular stability up to 60° makes the structure robust for practical applications. The structure also exhibits a negative refractive index for circularly polarized wave due to the strong chirality factor. Polarization azimuth rotation angle of 90° and ellipticity of 0° reveal the pure EM/optical activity. Furthermore, the simulation and measured results also affirmed orthogonal pure linear polarization transformation. The proposed chiral metasurface finds applications in radar and satellite belonging to K‐band. [ABSTRACT FROM AUTHOR]

Front cover: In establishing the left‐right axis of the body in Drosophila, a torsion‐like deformation of the cell occurs (cell chirality). Two myosin Is, Myo1D and Myo1C, are thought to be involved in this process, producing right‐handed and left‐handed cell chirality, respectively. A paper published in the May issue of this journal (Utsunomiya et al. (2024) Genes Cells 29: 380‐396, DOI: 10.1111/gtc.13110) reported that when these myosin Is were expressed in macrophages to observe their interactions with the membrane at the single‐molecule level, Myo1D exhibited mobility consistent with free diffusion, whereas Myo1C showed notably lower mobility. This picture, depicting two vortices in a strait, aptly illustrates their differences. Compared to the fast currents that produce the right‐handed vortex in the back, the currents of the left‐handed vortex in the foreground are docile. Designed by TRAIS Co., Ltd. (Kobe, Japan). [ABSTRACT FROM AUTHOR]

Protein misfolding and amyloid formation are implicated in the protein dysfunction, but the underlying mechanism remains to be clarified due to the lack of effective tools for detecting the transient intermediates. Sum frequency generation vibrational spectroscopy (SFG‐VS) has emerged as a powerful tool for identifying the structure and dynamics of proteins at the interfaces. In this review, we summarize recent SFG‐VS studies on the structure and dynamics of membrane‐bound proteins during misfolding processes. This paper first introduces the methods for determining the secondary structure of interfacial proteins: combining chiral and achiral spectra of amide A and amide I bands and combining amide I, amide II, and amide III spectral features. To demonstrate the ability of SFG‐VS in investigating the interfacial protein misfolding and amyloid formation, studies on the interactions between different peptides/proteins (islet amyloid polypeptide, amyloid β, prion protein, fused in sarcoma protein, hen egg‐white lysozyme, fusing fusion peptide, class I hydrophobin SC3 and class II hydrophobin HFBI) and surfaces such as lipid membranes are discussed. These molecular‐level studies revealed that SFG‐VS can provide a unique understanding of the mechanism of interfacial protein misfolding and amyloid formation in real time, in situ and without any exogenous labeling. [ABSTRACT FROM AUTHOR]

Chiroptical response, demonstrating chiral interaction between optical vortex and chiral structure, plays an important role in variety of fields like optics and material science. However, the flexibility and efficiency of chiral structure fabrication are limited due to mask requirement and a point‐by‐point constructing strategy. In this paper, a novel chiral lithography method is proposed that utilizes optical vortex phase beam shaping to achieve chiral structure processing with high efficiency and flexibility. By programming topological charges of the vortex phase, chiral structures with adjustable appearance, rotation, and chirality can be produced using femtosecond laser single pulse exposure. Transmittance measurements of fabricated chiral structures array confirm a 66% helical dichroism that is predicted by simulation. Moreover, with the aid of convolutional neural networks (CNN), an accuracy of 98% in Orbital Angular Momentum (OAM) recognition can be achieved. This chiral lithography method provides an alternative for chiral structure fabrication and holds promise in the development of chiral optics, optical communications, and next‐generation optical devices. [ABSTRACT FROM AUTHOR]

In this paper, an ultra‐wideband chirality selective metastructure absorber is proposed that enables differential absorption and reflection of circularly polarized waves in the terahertz (THz) range. The structure achieves circular dichroism (CD) by using asymmetrically split metal rings as fundamental meta‐atoms. Most critically, the high impedance surface and air‐resonant cavities are inserted separately in the meta‐atoms and dielectric substrate to enhance CD and broaden the bandwidth of absorption. The metastructure absorber can achieve more than 90% absorption of right circularly polarized waves at 0.675–1.244 THz, and it can maintain more than 90% reflection of left circularly polarized waves at 0.607–1.229 THz without changing the direction of rotation. Besides, its CD can reach more than 80% at 0.687–1.213 THz with a relative bandwidth of 55.3%. Spin‐selective absorption, which is closely related to breaking chiral symmetry, is investigated through power loss distribution, wide‐angle incidence, and scan parameter optimization. The proposed strategy is further validated in the THz band, and the polarization selection and manipulation techniques can be applied to chiral sensing/radio‐thermometry, circular polarization detectors/lasers, and molecular spectroscopy. [ABSTRACT FROM AUTHOR]

Recently, the application of magnetic fields to chiral chemical systems has been rewarding. In a forward‐looking 1986 paper, 'Chiral Metals?', Wallis, Karrer, and Jack D. Dunitz forecast 'that the limitation to proper symmetry elements in a chiral conductor could be associated with the emergence of new properties, those connected with interactions between applied electric and magnetic fields and their internal counterparts.' This was a prescient remark, but it has become manifest in ways that would not have been foreseen in its details by the authors. Here are reviewed the development of chiral conductors broadly imagined by Dunitz and coworkers, based on enantiopure tetrathiafulvalene derivatives that restrict space groups to those that have only symmetry operations of the first kind, as well as the new emergent properties associated with the transport of electrons when magnetic fields are applied to chiral crystals among other systems. These include electrical magnetochiral anisotropy (eMChA), inverse electrical magnetochiral anisotropy (ieMChA), helimagnetism and chirality induced spin selectivity (CISS). The conclusion discussing the circumstances under which achiral TTF crystals becomes chiral, only seems to introduce an oxymoron. [ABSTRACT FROM AUTHOR]

The recently discovered ferroelectric nematic (NF) liquid crystals (LCs) with over 0.04 C m−2 ferroelectric polarization and 104 relative dielectric constants, coupled with sub‐millisecond switching, offer potential applications in high‐power super capacitors and low voltage driven fast electro‐optical devices. This paper presents electrical, optical, and electro‐optical studies of a ferroelectric nematic LC material doped with commercially available chiral dopants. While the NF phase of the undoped LC is only monotropic, the chiral NF phase is enantiotropic, indicating a chirality induced stabilization of the polar nematic order. Compared to undoped NF material, a remarkable improvement of the electro‐optical switching time is demonstrated in the chiral doped materials. The color of the chiral mixtures that exhibit a selective reflection of visible light in the chiral NF phase, can be reversibly tuned by 0.02–0.1 V µm−1 in‐plane electric fields, which are much smaller than typically required in full‐color cholesteric LC displays and do not require complicated driving scheme. The fast switchable reflection color at low fields has potential applications for LC displays without backlight, smart windows, shutters, and e‐papers. [ABSTRACT FROM AUTHOR]

Fundamental studies of the interaction of chiral light with chiral matter are important for the development of techniques that allow handedness‐selective optical detection of chiral organic molecules. One approach to achieve this goal is the creation of a Fabry–Pérot cavity that supports eigenmodes with a desired electromagnetic handedness. This paper theoretically studies chiral Fabry–Pérot cavities with mirrors comprising 1D photonic crystal slabs made of van der Waals As2S3, a material with one of the highest known in‐plane anisotropies. By utilizing the anisotropy provided by As2S3, Fabry–Pérot cavities with constitutional and configurational chiralities are designed. It is demonstrated that in cavities with constitutional chirality, electromagnetic modes of left or right handedness exist due to the chirality of both mirrors, often referred to as handedness preserving mirrors in the literature. At the same time, cavities with configurational chirality support modes of both handednesses due to the chiral morphology of the entire structure, set by the twist angle between the optical axes of the upper and lower non‐chiral anisotropic mirrors. The developed chiral Fabry–Pérot cavities can be tuned to any distance between the mirrors by properly twisting them, making such systems a prospective platform for the coupling of chiral light with chiral matter. [ABSTRACT FROM AUTHOR]

The use of hierarchically structured materials as catalysts has been finding increasing application in the past years. For these catalytic systems, not only the nano‐scale matters: a high degree of order across multiple length scales, along with its control and analytical assessment, is of paramount importance to obtain innovative properties that can find application in catalysis. Most reviews dealing with hierarchically structured materials are concerned with the "bottom‐up" transfer of structural information along the different length scales, with special emphasis on the transmission of chirality. Due to their mesoscale size together with their complex behaviour, these systems are often susceptible to feel the effects of macroscopic forces, that can exert a "top‐down" control of their catalytic properties, so that an external stimulus, acting at the level of the supramolecular architecture of the catalyst, can ultimately determine the outcome of the catalyzed reaction at the molecular level. We review in this paper some recent reports that deal with the experimental implementation of this concept, either by using a mechanical force in a full range direct transmission to the reaction coordinate, or by means of a stepwise relay transmission from the macroscopic level (purely supramolecular chirality) to the nanoscopic one. We focus in this review on these multi‐length scale communication control effects, identifying the different mechanisms that are affecting the catalytic activity. [ABSTRACT FROM AUTHOR]

This paper presents an all‐dielectric chiral metasurface composed of an array of two‐layer distorted square structures with nanoholes. This metasurface can simultaneously generate dual‐band opposite chiral responses, which can be attributed to the bound states in the continuum (BICs) and the distorted chiral structure. By combining the BICs with chirality, a dual‐band chiral nonlinear metasurface and a chiral‐sensing method are proposed. The simulated results show that the third harmonic generation (THG) conversion efficiency can reach the order of 10−4 for two peaks with a peak‐pump intensity of approximately 5.3 GW cm−2 in the near‐infrared region. Moreover, the third‐harmonic circular dichroism for each peak can reach up to 0.99 and ‐0.94, respectively. Furthermore, it is theoretically demonstrated that this metasurface can be used for chiral sensing with high sensitivities. These results provide new insights for linear and nonlinear spin‐dependent applications. [ABSTRACT FROM AUTHOR]

The reaction of trans‐[Pt(DMSO)2MeCl] with 2‐alkylsubstituted pyridines pyR affords a series of complexes of the type [Pt(pyR)(DMSO)MeCl]. These complexes are rare examples of organometallic square‐planar complexes having four different ligands. Of the three possible geometric isomers, only the trans(N,S)‐[Pt(pyR)(DMSO)MeCl] was observed in solution and isolated in the solid state. However, the lack of chirality typical to square planar geometry can be resolved in several ways one of which is described in this paper. 1H NMR studies reveal diastereotopicity of the DMSO methyls, as well as the CH2 protons in the ethyl‐ and neopentyl‐pyridine complexes and the methyls in the isopropyl‐pyridine derivative. This observation can be ascribed to restricted rotations around the Pt−N bond, thus resulting in the presence of planar chirality for these complexes. Additionally, large downfield shifts in the 1H NMR spectra of the α C−H protons in the pyridine substituents suggested the presence of Pt⋯H−C interactions, confirmed via single crystal X‐ray studies in the case of the isopropyl complex [Pt(pyip)(DMSO)MeCl] (4), which shows an apical Pt⋯H interaction with a short 2.585 Å distance. DFT calculations shed light into the stability of these complexes and the influence of the pyridine‐substituent on their chiral configuration. [ABSTRACT FROM AUTHOR]

Carbon‐based nanomaterials have catalyzed breakthroughs across various scientific and engineering disciplines. The key to unlocking a new generation of tailor‐made nanomaterials based on single‐walled carbon nanotubes (SWCNTs) lies in the precise sorting of raw material into individual chiralities, each possessing unique properties. This can be achieved using conjugated polymer extraction (CPE), but to a very limited extent since the process generates only a few chirality‐enriched suspensions. Therefore, it is imperative to comprehend the mechanism of the wrapping of SWCNTs by polymers to unleash CPE's full potential. However, the lack of a diverse palette of chirality‐selective polymers with varying macromolecular parameters has hindered a comprehensive understanding of how the nature of the polymer affects the performance and selectivity of SWCNT isolation. To address this gap, multiple batches of such polymers are synthesized to elucidate the impact of molecular weight and dispersity on the purity and concentrations of the generated SWCNT suspensions. The obtained results explain the inconsistent outcomes reported in the literature, greatly improving the application potential of this promising SWCNT sorting approach. Concomitantly, the discovered significant influence of the macromolecular characteristics of conjugated polymers on the SWCNT isolation efficacy sheds considerable insight into the unresolved mechanism of this sorting technique. [ABSTRACT FROM AUTHOR]

Helical architectures with controllable helical sense bias have recently attracted considerable interest for mimicking biological helices and developing novel chiral materials. Coordination polymers (CPs), composed of metal ion nodes and organic linkers, are intriguing systems showing tunable structures and functions. However, CPs with helical morphologies have rarely been explored so far. Particularly, chirality inversion through external stimulus has not been achieved in helical CPs. In this work, we carried out an in‐depth investigation on the self‐assembly of 1D gadolinium(III) phosphonate CPs using GdX3 (X=Cl, Br, I) and Gd(RSO3) (R=CH3, C6H5, CF3) as metal sources and R‐(1‐phenylethylamino)methyl phosphonic acid (R‐pempH2) as ligand. Superhelices were formed by precise control of the interchain interactions through different intercalated anions. Furthermore, the twisting direction of superhelices could be controlled by synergistic effect of anions and pH. This study may provide a new route to fabricate helical nanostructures of CPs with a desirable chiral sense and help understand the inner mechanism of the self‐assembly process of macroscopic helical structures of molecular systems. [ABSTRACT FROM AUTHOR]

In spite of the many resolution techniques available to separate enantiomers, diastereomeric resolution still remains the most widely used technique in industry. However, drawbacks of this technique are the limited yield of the desired enantiomer and the expensive enantiopure resolving agent that is required. We show here for the first time that a combination of diastereomeric resolution with Viedma ripening using a racemic resolving agent can also provide a single stereoisomer when using an excess of the racemic resolving agent, without the need for the resolving agent to racemize. The requirements of this process are, like for an enantiomeric system, that the compound crystallizes as a racemic conglomerate and that at least one chiral center in the target molecule is racemizable. In addition, owing to the presence of the racemization reaction, substantial improvement in the yield can be obtained. We here demonstrate this approach using a metastable conglomerate salt of rac‐2‐phenylglycinamide with rac‐N‐acetyl tryptophan. [ABSTRACT FROM AUTHOR]

Enantiodivergent one‐pot synthesis of biaryls was developed using a catalytic amount of a single chiral source. A domino organocatalyst‐mediated enantioselective Michael reaction and aldol condensation provided centrally chiral dihydronaphthalenes with excellent enantioselectivity, from which an enantiodivergent chirality conversion from central‐to‐axial chirality was achieved. Both enantiomers of biaryls were obtained with excellent enantioselectivity. All transformations can be conducted in a single reaction vessel. A plausible reaction mechanism for the enantiodivergence is proposed. [ABSTRACT FROM AUTHOR]

This article discloses a study on a chiral bis‐phosphorylated‐helical ligand in the palladium‐catalyzed Tsuji‐Trost allylation. The use of 2,15‐bisphosphinite‐[6]‐helicenes revealed a remarkable ligand effect, in which the (R) and (S) isomeric products can be selectively formed as a direct function of the amount of ligand introduced. Investigation of the organometallic species involved through 31P NMR spectroscopic analysis of a model complex and X‐Ray diffraction analysis together with DFT calculations shed light on this phenomenon. [ABSTRACT FROM AUTHOR]

Tailoring of enzyme toward α‐tetralones, a class of bulky‐bulky ketones, is still a challenge. In this work, the mutants of carbonyl reductase BaSDR1 with improved catalytic performance toward α‐tetralone 1 a were obtained by adjusting the steric hindrance and hydrophobicity of the residues that affect the approach of α‐tetralone with the catalytic residues. The designed mutants also showed enhanced catalytic performance toward halogenated α‐tetralones 2 a–6 a. Remarkably, the activity of the mutant Q237V/I291F toward 7‐fluoro‐α‐tetralone 5 a was 16.3‐fold higher than the wildtype enzyme with improved stereoselectivity (98.8 % ee). More notably, the mutants Q139S and Q139S/V187S exhibited decreased or reversed stereoselectivity toward α‐tetralone 1 a, 5‐bromo‐α‐tetralone 2 a, 7‐fluoro‐α‐tetralone 5 a and 7‐chloro‐α‐tetralone 6 a, while the relatively high ee values were obtained in the presence of 6‐chloro‐α‐tetralone 3 a and 6‐bromo‐α‐tetralone 4 a as substrates. Further analysis showed the larger size of the substrates was beneficial for the substrates binding to the active cavity with a more specific binding mode, which endows the reaction with higher stereoselectivity. Moreover, the recombinant E. coli expressing the variant Q237V/I291F successfully catalyzed the reduction of a high concentration 7‐fluoro‐α‐tetralone 5 a. These results not only offered a potential tool for chiral α‐tetralols, but also provided guiding information for the enzyme engineering toward bulky‐bulky ketones. [ABSTRACT FROM AUTHOR]

The {Fe2Dy2} butterfly systems can show single molecule magnet (SMM) behaviour, the nature of which depends on details of the electronic structure, as previously demonstrated for the [Fe2Dy2(μ3‐OH)2(Me‐teaH)2(O2CPh)6] compound, where the [N,N‐bis‐(2‐hydroxyethyl)‐amino]‐2‐propanol (Me‐teaH3) ligand is usually used in its racemic form. Here, we describe the consequences for the SMM properties by using enantiopure versions of this ligand and present the first homochiral 3d/4 f SMM, which could only be obtained for the S enantiomer of the ligand for [Fe2Dy2(μ3‐OH)2(Me‐teaH)2(O2CPh)6] since the R enantiomer underwent significant racemisation. To investigate this further, we prepared the [Fe2Dy2(μ3‐OH)2(Me‐teaH)2(O2CPh)4(NO3)2] version, which could be obtained as the RS‐, R‐ and S‐compounds. Remarkably, the enantiopure versions show enhanced slow relaxation of magnetisation. The use of the enantiomerically pure ligand suppresses QTM, leading to the conclusion that use of enantiopure ligands is a "gamechanger" by breaking the cluster symmetry and altering the intimate details of the coordination cluster's molecular structure. [ABSTRACT FROM AUTHOR]

Chiral magnetic materials are proposed for applications in second‐order non‐linear optics, magneto‐chiral dichroism, among others. Recently, we have reported a set of tetra‐nuclear Fe(II) grid complex conformers with general formula C/S‐[Fe4L4]8+ (L: 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐dihydrobenzo[1,2‐d : 4,5‐d′]diimidazole). In the grid complexes, isomerism emerges from tautomerism and conformational isomerism of the ligand L, and the S‐type grid complex is chiral, which originates from different non‐centrosymmetric spatial organization of the trans type ligand around the Fe(II) center. However, the selective preparation of an enantiomerically pure grid complex in a controlled manner is difficult due to spontaneous self‐assembly. To achieve the pre‐synthesis programmable resolution of Fe(II) grid complexes, we designed and synthesized two novel intrinsically chiral ligands by appending chiral moieties to the parent ligand. The complexation of these chiral ligands with Fe(II) salt resulted in the formation of enantiomerically pure Fe(II) grid complexes, as unambiguously elucidated by CD and XRD studies. The enantiomeric complexes exhibited similar gradual and half‐complete thermal and photo‐induced SCO characteristics. The good agreement between the experimentally obtained and calculated CD spectra further supports the enantiomeric purity of the complexes and even the magnetic studies. The chiral resolution of Fe(II)‐ [2×2] grid complexes reported in this study, for the first time, might enable the fabrication of magneto‐chiral molecular devices. [ABSTRACT FROM AUTHOR]

Inspired by the synthetic and biological potential of organotellurium substances, a series of five‐ and six‐membered ring organotelluranes containing a Te−O bond were synthesized and characterized. Theoretical calculations elucidated the mechanism for the oxidation‐cyclization processes involved in the formation of the heterocycles, consistent with chlorine transfer to hydroxy telluride, followed by a cyclization step with simultaneous formation of the new Te−O bond and deprotonation of the OH group. Moreover, theoretical calculations also indicated anti‐diastereoisomers to be major products for two chirality center–containing compounds. Antileishmanial assays against Leishmania amazonensis promastigotes disclosed 1,2λ4‐oxatellurane LQ50 (IC50=4.1±1.0; SI=12), 1,2λ4‐oxatellurolane LQ04 (IC50=7.0±1.3; SI=7) and 1,2λ4‐benzoxatellurole LQ56 (IC50=5.7±0.3; SI=6) as more powerful and more selective compounds than the reference, being up to four times more active. A stability study supported by 125Te NMR analyses showed that these heterocycles do not suffer structural modifications in aqueous‐organic media or at temperatures up to 65 °C. [ABSTRACT FROM AUTHOR]

Recent investigations of supramolecular polymers based on chiral triphenylene‐2,6,10‐tricarboxamides (TTAs) showed how temperature‐induced changes in solvation can greatly influence the preferred helical conformation of the supramolecular polymers formed. Here, we combine chiral TTA with achiral copolymerization partners to further investigate temperature‐dependent solvation effects. Systematic variation of the system's composition shows clear impacts on the temperature window where the conformational change occurs. Further, simple chain length variations in the achiral comonomer greatly affect the ability to influence the conformational change in the copolymer, while the differences in the properties of the individual homopolymers are rather small. We herein highlight how subtle changes in the monomers can impact the observed copolymer properties drastically; an effect arising from the emerging complexity of multicomponent interactions in supramolecular copolymers with solvent‐solute interactions being more important than typically thought. [ABSTRACT FROM AUTHOR]

Carbon nanotubes (CNTs) are of interest in various industries owing to their high aspect ratio, electrical conductivity, and other properties. By maximizing the number of CNTs in their solvents or matrices, the electrical and mechanical performance in applications such as batteries, sensors, and transistors can be enhanced. However, the hydrophobicity of CNTs' surface induces aggregation that adversely impacts their performance. To overcome this obstacle, many researchers have been designing novel dispersants with performances exceeding that of existing commercial dispersants. This article reviews contemporary studies on CNT dispersants from 2015 to 2022, along with the comprehensive features of CNTs depending on their chirality, number of walls, synthesis methods, and functionalization. Studies of CNT dispersants are primarily organized according to whether aqueous or organic solvents are used. This review article provides a clear perspective of CNT dispersants development today and how to design new CNT dispersants depending on the solvents. A conclusion is given to identify major challenges to the implementation of CNT dispersion and an outlook on future avenues of research. [ABSTRACT FROM AUTHOR]

Controlling chromophore chirality in three‐dimensional space is crucial for understanding the structure–chiroptical relationship. Such control enables the prediction of ideal materials for use in chiral photonic applications. In this study, optically active multipyrene systems are synthesized on peptoids. Pyrene‐based chiral submonomers, (S)‐ and (R)‐1‐pyrenylethylamine (s1pye and r1pye), are successfully incorporated into peptoids as the respective (S)‐ and (R)‐N‐(1‐pyrenylethyl)glycine (Ns1pye and Nr1pye) units. NMR spectroscopy revealed length‐ and N‐acetylation‐dependent conformational homogeneity enhancement in solution, stabilizing cis‐amides in Ns1pye‐containing peptoids. The X‐ray crystal structure of Ns1pye tetramer displayed a polyproline type‐I (PPI)‐like helix. All of the pyrene‐related absorptions are circular dichroism (CD) active, and the CD signal related to the long‐axis‐polarized transition increased with helical stabilization. Intramolecular excimer generation yielded significant circularly polarized luminescence (CPL) in the excimer emission region. Early‐stage peptoids emitted left‐handed CPL, but upon acquiring a PPI‐like helix character, CPL handedness became inverted. The CPL dissymmetry factor (glum) was comparable or superior (10−2) to that of chiral organic dyes (10−5–10−2). This new class of helical pyrene‐containing peptoids provides a CPL‐active intramolecular excimer, modulating optical activity through peptoid secondary structure homogeneity. [ABSTRACT FROM AUTHOR]

A family of transition metal complexes of meso‐aryl‐2‐aza‐21‐carbaporphyrin (N‐confused porphyrin, NCP) derivatives acting as ortho‐metallating ligands for ruthenium(II), rhodium(III), and iridium(III) is synthesized and characterized by XRD, spectroscopic, and electrochemical methods. The chirality of these systems is shown by the separation of the enantiomers and analyzed by circular dichroism and DFT. A preliminary catalytic study indicates the activity of the iridium(III) ortho‐metallated complexes in the N‐heterocyclization of primary amines with diols. [ABSTRACT FROM AUTHOR]

Carbohydrates are the most abundant organic material on Earth and the structural "material of choice" in many living systems. Nevertheless, design and engineering of synthetic carbohydrate materials presently lag behind that for protein and nucleic acids. Bottom‐up engineering of carbohydrate materials demands an atomic‐level understanding of their molecular structures and interactions in condensed phases. Here, high‐resolution scanning tunneling microscopy (STM) is used to visualize at submolecular resolution the three‐dimensional structure of cellulose oligomers assembled on Au(1111) and the interactions that drive their assembly. The STM imaging, supported by ab initio calculations, reveals the orientation of all glycosidic bonds and pyranose rings in the oligomers, as well as details of intermolecular interactions between the oligomers. By comparing the assembly of D‐ and L‐oligomers, these interactions are shown to be enantioselective, capable of driving spontaneous enantioseparation of cellulose chains from its unnatural enantiomer and promoting the formation of engineered carbohydrate assemblies in the condensed phases. [ABSTRACT FROM AUTHOR]

Chiral magnetic oxide nanomaterials (CMONs), which combine the beneficial effects of chirality and magnetism in a single unit, have found applications in biomedical, optical, and electronic devices as well as in catalysis and sensing. This is largely due to the simultaneous presence of magnetic properties, catalytic activity, biocompatibility and optical activity, or magneto‐optical effects, which are circular polarization and magnetization dependent. This review summarizes the key findings derived from recent research works on the synthesis, properties, and applications of CMONs. The three main approaches in the synthesis and property tuning of CMONs, namely, post‐functionalization, in situ approach, and assembly with soft templates, are discussed. A summary and some future prospects of the CMONs with respect to their synthetic routes, chirality origin, and applications are also provided. [ABSTRACT FROM AUTHOR]

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well‐known dinaphtho[2,3‐b:2,3‐f]thieno[3,2‐b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field‐effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)‐DNTT and (S)‐DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices. [ABSTRACT FROM AUTHOR]

A series of chiral mechanochromic copper(I) cAAC (cAAC=cyclic (alkyl)(amino)carbene) complexes with a variety of amide ligands have been studied with regard to their photophysical and chiroptical properties to elucidate structure‐property relationships for the design of efficient triplet exciton emitters exhibiting circularly polarized luminescence. Depending on the environment, which determines the excited state energies, either thermally activated delayed fluorescence (TADF) from 1/3LLCT states or phosphorescence from 3LLCT/LC states occurs. However, neither chiral moieties at the carbene nor at the carbazolate ligands provide detectable luminescence dissymmetries glum. An exception is [Cu(phenoxazinyl)(cAAC)], showing orange to deep red TADF with λmax=601–715 nm in solution, powders and in PMMA. In this case, the amide ligand can undergo distortions in the excited state. This design motif leads to the first linear, non‐aggregated CPL‐active copper(I) complex with glum of −3.4 ⋅ 10−3 combined with a high radiative rate constant of 6.7 ⋅ 105 s−1. [ABSTRACT FROM AUTHOR]

Accurate identifying and in‐depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect‐activity relationships. Yet, atomically precise coinage‐metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed‐ligand strategy to synthesizing an intrinsically chiral and metal‐deficient copper hydride‐rich NC [Cu57H20(PET)36(TPP)4]+ (Cu57H20). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57H20 features a cube‐like Cu8 kernel embedded in a corner‐missing metal‐ligand shell of Cu49(PET)36(TPP)4. Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono‐lacunary polyoxometalates. Theoretical calculations demonstrate that the above‐mentioned point vacancy causes one surface hydride exposed as an interfacial capping μ3‐H−, which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well‐defined chiral metal‐deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have made great advance in direct X‐ray detection, however the presence of toxic lead and the requirement of high working voltages severely limit their applicability and operational stability. Thus, exploring "green" lead‐free hybrid perovskites capable of detecting X‐rays at zero bias is crucial but remains toughly challenging. Here, utilizing chiral R/S‐1‐phenylpropylamine (R/S‐PPA) cations, a pair of 0D chiral‐polar perovskites, (R/S‐PPA)2BiI5 (1R/1S) are constructed. Their intrinsic spontaneous electric polarization induces a large bulk photovoltage of 0.63 V, which acts as a driving force to separate and transport photogenerated carriers, thus endowing them with the capability of self‐driven detection. Consequently, self‐driven X‐ray detectors with a low detection limit of 270 nGy s−1 are successfully constructed based on high‐quality, inch‐sized single crystals of 1R. Notably, they show suppressed baseline drift under the self‐driven mode, exhibiting superior operational stability. This study realizes self‐driven X‐ray detection in a single‐phase lead‐free hybrid perovskite by exploiting the intrinsic bulk photovoltaic effect, which sheds light on future explorations of lead‐free hybrid perovskites toward "green" self‐driven radiation detectors with high performance. [ABSTRACT FROM AUTHOR]

The determination of molecular stereochemistry and absolute configuration is an important part of modern chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) spectroscopy is a widely used tool for chirality assignment, especially with porphyrin macrocycles employed as reporter chromophores. However, the mechanisms of induced ECD in porphyrin complexes are yet to be comprehensively rationalized. In this work, the ECD spectra of a sterically hindered hexa‐cationic porphyrin with two camphorsulfonic acids in dichloromethane and chloroform were experimentally measured and computationally analyzed. The influence of geometric factors such as the position of chiral guest molecules, distortion of the porphyrin macrocycle, and orientation of aromatic and non‐aromatic peripheral substituents on the ECD spectra was theoretically studied. Various potential pitfalls, such as a lack of significant conformations and accidental agreement of experimental and simulated spectra, are considered and discussed. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Aerobic oxidation has been catching more and more attention because of its atom economy and environmental friendliness. Oxidation of diols is a challenge due to various oxidative products. Thus, highly selective aerobic oxidation affording specific products is of current interest. In this work, a combination of Fe(NO3)3·9H2O/TEMPO/KCl catalysis has been identified as an efficient recipe for the aerobic oxidation of 1,4‐diols affording γ‐butyrolactones under mild conditions. The reaction exhibits decent chemo‐ and regioselectivity of symmetrical and unsymmetrical 1,4‐diols. The optically active γ‐lactones may also be prepared from optically active 1,4‐diols without erosion of the ee via this method. Furthermore, this approach was successfully applied to synthesize NBP, a commercial drug. [ABSTRACT FROM AUTHOR]

Silicon‐based compounds with stereochemical information and convertible functional units are valuable building blocks in synthetic chemistry. Si‐stereogenic aminochlorosilanes are built up by Si−N bond formation between an achiral dichlorosilane and a chiral enantiomerically pure primary amine. Both diastereomers could be isolated as stereochemically pure single‐crystals by fractional crystallization and were analyzed by X‐ray crystallography. Defined intermolecular interaction patterns were identified illustrating the role of N−H⋅⋅⋅π, C−H⋅⋅⋅π, and N−H⋅⋅⋅Cl contacts in the molecular crystalline packing arrangements. Stepwise functionalization of the silicon−chlorine and silicon−amine functions was carried out, demonstrating their potential for use as a chiral synthesis precursors. Via optically pure aminomethoxysilanes, enantiomerically enriched methoxysilanols, chloromethoxysilanes, and methoxysilanethiols were synthesized. The stereospecificity of the transformations was monitored. The (R)‐BINOL‐PSSLi method for determining the enantiomeric purity was found to be the tool of choice for acid‐sensitive silanols and silanethiols. [ABSTRACT FROM AUTHOR]

The reactive P−N bond in a racemic mixture of endo‐1‐phospha‐2‐azanorbornene (PAN) (RP/SP)‐endo‐1 is readily cleaved with enantiomerically pure lithium alkoxides followed by protonation to afford diastereomeric mixtures of P‐chiral 1‐alkoxy‐2,3‐dihydrophosphole derivatives. The isolation of these compounds is rather challenging due to the reversibility of the reaction (elimination of alcohols). However, methylation of the sulfonamide moiety of the intermediate lithium salts and sulfur protection of the phosphorus atom prevent the elimination reaction. The resulting air‐stable P‐chiral diastereomeric 1‐alkoxy‐2,3‐dihydrophosphole sulfide mixtures can be readily isolated and fully characterized. The diastereomers can be separated by crystallization. The 1‐alkoxy‐2,3‐dihydrophosphole sulfides are readily reduced with Raney nickel to afford phosphorus(III) P‐stereogenic 1‐alkoxy‐2,3‐dihydrophospholes with potential use in asymmetric homogeneous transition metal catalysis. [ABSTRACT FROM AUTHOR]

Chiral three‐dimensional hybrid organic–inorganic perovskites (3D HOIPs) would show unique chiroptoelectronic performance due to the combination of chirality and 3D structure. However, the synthesis of 3D chiral HOIPs remains a significant challenge. Herein, we constructed a pair of unprecedented 3D chiral halide perovskitoids (R/S‐BPEA)EA6Pb4Cl15 (1‐R/S) (R/S‐BPEA=(R/S)‐1‐4‐Bromophenylethylammonium, EA=ethylammonium), in which the large chiral cations can be contained in the big "hollow" inorganic frameworks induced by mixing cations. Notably, 3D 1‐R/S shows natural chiroptical activity, as evidenced by its significant mirror circular dichroism spectra and the ability to distinguish circularly polarized light. Moreover, based on the unique 3D structure, 1‐S presents sensitive X‐ray detection performance with a low detection limit of 398 nGyair s−1, which is 14 times lower than the regular medical diagnosis of 5.5 μGyair s−1. In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics. [ABSTRACT FROM AUTHOR]

The selective synthesis of nickel and copper complexes of 19‐benzoyl‐5,10,15‐triphenyl‐bilatrien‐1‐one (H2TPBT) is reported, a molecule which crystallizes as a molecular helix of one‐and‐a‐quarter which turns with a 5.7 Å radius and a 3.2 Å pitch, and all 26 participating atoms are sp2‐hybridized. UV/vis, ECD, ESR and cyclic voltammetry experiments reveal a strong interaction between metal and ligand and partial radical character when copper is coordinated instead of nickel. Strong ECD absorption in the 800 nm range is found which, using TD‐DFT calculations as well as literature spectra, is shown to be highly tunable both by metal coordination and variation of the aryl groups in the TPBT periphery. The radical character of the ligand in Cu(TPBT) enables rapid interconversion between (M)‐ and (P)‐enantiomers, possibly via intermittent breakage of a Cu−N bond. The 19‐benzoyl group kinetically stabilizes enantiopure (M/P)‐Ni(TPBT). The results are interpreted with regard to the application as circularly polarized light (CPL) detectors as well as to the chirality‐induced spin‐selectivity (CISS) effect which is currently lacking a concise theoretical model. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis of anthracene‐containing twisted cyclo[2]dipyrrin 1 by utilizing a non‐planar building block, 1,5‐dipyrrylanthracene (1,5‐DPA). The non‐planar nature of the macrocycle enhanced the solubility and helped in structural characterization. Macrocycle 1 adopts a twisted 'figure of eight' conformation stabilized by strong intramolecular H‐bonding interactions and exists as a pair of helical enantiomers, as revealed by X‐ray crystallographic analysis. More importantly, the sterically locked structure enabled facile optical resolution using chiral HPLC. The (P,P) and (M,M) enantiomers show moderate chiroptical properties, such as absorption dissymmetry factors |gabs| in the order of 10−3, and luminescence dissymmetry factors |glum| of 3.8×10−3 and 2.9×10−3 at 702 nm, respectively. [ABSTRACT FROM AUTHOR]

Racemic 3‐substituted oxindoles were successfully converted into enantiomerically pure or enriched material (up to 99 % ee) upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst (10 mol %). The photochemical deracemization process allows predictable editing of the stereogenic center at carbon atom C3. Light energy compensates for the associated loss of entropy and enables the decoupling of potentially reversible reactions, i.e. a hydrogen atom transfer to (photochemical) and from (thermal) the carbonyl group of the catalyst. The major enantiomer is continuously enriched in several catalytic cycles. The obtained oxindoles were shown to be valuable intermediates for further transformations, which proceeded with complete retention at the stereogenic center. [ABSTRACT FROM AUTHOR]

Dynamic covalent chemistry (DCC) has, in recent years, provided valuable tools to synthesize molecular architectures of increasing complexity. We have also taken advantage of imine DCC chemistry to prepare TPMA‐based supramolecular cages for molecular recognition applications. However, the versatility of this approach has as a major drawback the intrinsic hydrolytic lability of imines, which hampers some applications. We present herein a synthetic strategy that combines the advantages of a thermodynamic‐driven formation of a supramolecular structure using imine chemistry, together with the possibility to synthetize chiral hydrolytically stable structures through a [3,3]‐sigmatropic rearrangement. A preliminary mechanistic analysis of this one‐pot synthesis and the scope of the reaction are also discussed. [ABSTRACT FROM AUTHOR]

We report the concise synthesis and chir(optical) properties of an azaborathia[9]helicene consisting of two thienoazaborole motifs. The key intermediate, a highly congested teraryl with nearly parallel isoquinoline moieties, was generated as a mixture of atropisomers upon fusion of the central thiophene ring of the dithienothiophene moiety. These diastereomers were characterized by single crystal X‐ray analysis revealing intriguing interactions in the solid state. Subsequent insertion of boron into the aromatic scaffold via silicon‐boron exchange involving triisopropylsilyl groups fixed the helical geometry, thereby establishing a novel method for the preparation of azaboroles. The ligand exchange at boron in the final step afforded the blue emitter displaying a fluorescence quantum yield of 0.17 in CH2Cl2 and excellent configurational stability. Detailed structural and theoretical investigation of unusual atropisomers and the helicene provide insights into their isomerization processes. [ABSTRACT FROM AUTHOR]

In the last three decades, reacting sterically congested ortho‐substituted arenes to form atropochiral biaryls is an appealing venture and a challenging subject that has garnered significant attention. Therefore, there is interest in developing methods to prepare these compounds. In this study, an efficient approach to produce a new class 2,2' disubstituted biaryls bridgehead phosphine oxides with an unusual topology and exceptional conformational stability is presented. Our methodology demonstrates that depending on the substitution pattern on the aryl moieties, the methanophosphocine backbone could be rigid enough to observe a double atropochirality, resulting in an under covered class of molecules. Notably, our studies revealed that replacing only one hydrogen at the ortho position by a fluorine atom led to sufficiently restricted rotation at temperatures below 80 °C, extending "far away" the limits of atropostability. Finally, our investigations, which employed variable‐temperature NMR spectroscopy and DFT calculations, yielded unique insights into the isomerisation mechanism, indicating that the two biaryl motifs are fully independent in spite of their proximity. [ABSTRACT FROM AUTHOR]

Molecules stereogenic only at tetrahedral boron atoms show great promise for applications, for example as chiroptical materials, but are scarcely investigated due to their synthetic challenge. Hence, this study reports a two‐step synthesis of enantioenriched boron C,N‐chelates. First, the diastereoselective complexation of alkyl/aryl borinates with chiral aminoalcohols furnished boron stereogenic heterocycles in up to 86 % yield and d.r. >98 : 2. Treatment of these O,N‐complexes with chelate nucleophiles was surmised to transfer the stereoinformation via the ate‐complex into the C,N‐products. This chirality transfer succeeded by substitution of the O,N‐chelates with lithiated phenyl pyridine to give boron stereogenic C,N‐chelates in up to 84 % yield and e.r. up to 97 : 3. The chiral aminoalcohol ligands could be recovered after isolation of the C,N‐chelates. The chirality transfer tolerated alkyl, alkynyl and (hetero‐)aryl moieties at boron and could be further extended by post‐modification: transformations such as catalytic hydrogenations or sequential deprotonation/electrophilic trapping were feasible while maintaining the stereochemical integrity of the C,N‐chelates. Structural aspects of the boron chelates were studied by variable temperature NMR and X‐ray diffraction. [ABSTRACT FROM AUTHOR]

Chiral metamaterials comprise a promising platform for advanced optoelectronic and biomedical applications. However, conventional fabrication via lithography is limited by its complexity and high cost. Herein, the lithography‐free fabrication of terahertz chiral metamaterials and their enhancement for sensing the chirality of biocrystal enantiomers is presented. Chiral Au microstrip patterns (CHAMs) in a saw‐tooth shape are fabricated by combining two‐step buckling processes and glancing‐angle deposition. Non‐superimposable geometric chirality is achieved by controlling the tilt angle between the asymmetric and biaxial strain axes and the selective area deposition of the Au layers by using the shadow effect. The manufactured chiral metamaterials show mirror‐shaped terahertz circular dichroism (TCD) signals in the range of 0.2–2.5 THz. Coupling of the induced electric and magnetic dipoles to the chiral‐shaped Au surfaces results in effective optical chirality enhancement. Finite‐difference time‐domain computational simulations reveal the homogeneous distribution of optical chirality with an absolute maximum of 2.24 in the near field. Summing the TCD signals for enantiomeric cystine biocrystals onto the chiral metamaterials shows an ≈7‐fold amplification in magnitude. This enhancement can be attributed to the synergistic effects of superchiral field enhancement and the electromagnetic resonance between the CHAMs and biocrystals. [ABSTRACT FROM AUTHOR]

Herein, we describe Hiyama coupling via intramolecular substituent transfer from silicon on one blade of triptycenes to another to yield 1,8,13‐trisubstituted chiral triptycenes. This reaction is attributed to the proximity effect of substituents on triptycene, which plays an important role in not only the formation of the oxy‐palladacycle but also the activation of the silyl group to facilitate σ‐bond metathesis. After bromination and nucleophilic ring opening, the second intramolecular Hiyama coupling provided various 1,8,13‐trisubstituted chiral triptycenes. The optical resolution of 1,8,13‐triptycene afforded an optically active form for the first time. [ABSTRACT FROM AUTHOR]

Macrocyclization of the bendable 2,7‐dimethoxythianthrene with methylene linkages afforded a pair of homochiral macrocycles featuring a hex‐nut‐like geometry. Their structures were fully characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction analysis. Their stable planar chirality facilitates efficient resolution of the pair of enantiomers which could be readily derivatized. Installing phenylethynyl groups on their rims leads to luminescent tubular macrocycles exhibiting circularly polarized luminescence with a large dissymmetry value |glum| of 5×10−3. Supramolecular binding of electron‐deficient guests by the tube results in fluorescence quenching, which proved its potential for the future development of switchable chiroptical systems. [ABSTRACT FROM AUTHOR]

We have developed an efficient modular asymmetric synthesis of azahelicenes through an organocatalyzed asymmetric multicomponent reaction from readily available polycyclic aromatic amines, aldehydes, and (di)enamides, by employing a central‐to‐helical chirality conversion strategy. A series of aza[5]‐ and aza[4]helicenes bearing various substituents were readily afforded through this one‐pot sequential enantioselective Povarov reaction/oxidative aromatization process, with good yields and high enantioselectivities. The fruitful and diverse derivatizations of the chiral azahelicene products demonstrated the potential of this method, and a preliminary application of the azahelicene derivative as a chiral organocatalyst was showcased. The photophysical and chiroptical properties of these azahelicenes, particularly the acid/base‐triggered switching of these properties, were also well studied, which may find potential applications in the development of novel organic optoelectronic materials. [ABSTRACT FROM AUTHOR]

Fluorescent materials with large Stokes shifts have significant potential for use in optical applications. Typically, a synthetic design strategy is utilized for this purpose. In this study, we demonstrated a novel method by binding a chiral template to a nonchiral fluorescent agent without chemical modification. Specifically, α‐helical poly(L‐lysine) was employed as the chiral template, which interacted with a disulfonic fluorescent dye, such as NK2751. The dye caused excimer luminescence by inducing the formation of a chirally H‐aggregated dimer only when poly(L‐lysine) was in an α‐helical shape. The result was a Stokes shift of 230 nm. Similar effects were not observed when the chiral template was in a random coil condition and the Stokes shift was less than 40 nm. These findings imply that H‐aggregated dimerization, which often results in quenching, permits the electronic transitions necessary for fluorescence events by the formation of the chirally twisted state. In addition, we introduce for the first time the generation of circularly polarized luminescence using the chirality induction phenomena in a dye supported by poly(L‐lysine). [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]