Search

We investigate a ring polymer under the influence of chiral active Brownian forces in two dimensions using coarse-grained computer simulations. We observe a non-monotonic behavior of the radius of gyration of an active Brownian ring as a function of active force. However, the shrinkage of the ring in the intermediate strength of active forces becomes more pronounced in the presence of chiral active forces, and the shrinkage is monotonic at a given activity level as a function of the angular frequency controlling the direction of the active force. The distribution of radius of gyration, inter-monomer distance, and radial distribution suggest that the monomers come close to each other, eventually leading to the shrinkage of the ring. Moreover, the bond-correlation suggests that the chirality introduces a local folding of the monomers. Furthermore, using the diameter correlation function, we show that the ring performs tank-treading motion with a frequency following power-law relation with active force with exponent 3/2. The mean squared displacement of the monomers further assists the tank-treading dynamics by exhibiting oscillatory behavior. [ABSTRACT FROM AUTHOR]

Motivated by experimental reports on chirality induced spin selectivity, we investigate a minimal model that allows us to calculate the charge and spin conductances through helical molecules analytically. The spin–orbit interaction is assumed to be non-vanishing on the molecule and negligible in the reservoirs (leads). The band structure of the molecule features four helical modes with spin-momentum locking that are analogous of edge-currents in the quantum spin Hall effect. While charge is conserved and therefore the charge current is independent of where it is measured—reservoirs or molecule—our detailed calculations reveal that the spin currents in the left and right leads are equal in magnitudes but with opposite signs (in linear response). We predict that transport currents flowing through helical molecules are accompanied by a spin accumulation in the contact region with the same magnetization direction for source and drain. Furthermore, we predict that the spin-conductance can be extracted directly from measuring the (quasi-static) spin accumulation—rather than the spin current itself, which is very challenging to obtain experimentally. [ABSTRACT FROM AUTHOR]

The side chain dynamics of poly(quinoxaline-2,3-diyl)s (PQXs) are expected to influence their conformation. To investigate these dynamics experimentally, quasielastic neutron scattering (QENS) was performed for PQXs in deuterated tetrahydrofuran (THF-d8) and deuterated 1,1,2-trichloroethane/THF (1,1,2-TCE-d3/THF-d8), in which they formed right-handed and left-handed helical structures, respectively. The mean-square displacement of the PQX side chains in 1,1,2-TCE-d3/THF-d8 was lower than that in THF-d8. Furthermore, QENS complementary studies and molecular dynamics simulations unraveled a coupling between the main-chain and side chain dynamics of PQXs, suggesting the possibility of controlling the main-chain helical chirality through the dynamics of chiral side chains. These insights present a novel strategy for the design of synthetic helical macromolecules with precise chirality control. [ABSTRACT FROM AUTHOR]

We investigate the quantum interference of the electron–hole conversions from the two interfaces in a Weyl semimetal (WSM)-based hybrid structure, in which a superconducting WSM is sandwiched in between two normal ones. The quantum interference is characterized by the chirality-anomaly-manipulation (CAM). It is found that only low energy is in favor for s -wave BCS pairing states. The Andreev reflection (AR) chirality blockade can be tuned by the stagger angle α for the relative orientation of paired Weyl points, accompanied by an AR bipolar chirality diode. Thus, a strong CAM is indicated for the electron–hole conversion. However, the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) pairing states have no energy preference, with the weak and strong CAMs being near and far away from the zero energy, respectively. More interestingly, a perfect AR with the normal reflection suppressed thoroughly can be obtained at any α as a result of the FFLO paring with the same chirality. In addition, the conductance or noise power, which incorporates the contributions of the two paired Weyl nodes, not only, in turn, embodies the respective features of their contributions but also can be experimentally measured to discern between the BCS and FFLO paring states. [ABSTRACT FROM AUTHOR]

Chirality ubiquitously appears in nature; however, its quantification remains obscure owing to the lack of microscopic description at the quantum-mechanical level. We propose a way of evaluating chirality in terms of the electric toroidal monopole, a practical entity of time-reversal even pseudoscalar (parity-odd) objects reflecting relevant electronic wave functions. For this purpose, we analyze a twisted methane molecule at the quantum-mechanical level, showing that the electric toroidal monopoles become a quantitative indicator for chirality. In the twisted methane, we clarify that the handedness of chirality corresponds to the sign of the expectation value of the electric toroidal monopole and that the most important ingredient is the modulation of the spin-dependent imaginary hopping between the hydrogen atoms, while the relativistic spin–orbit coupling within the carbon atom is irrelevant for chirality. [ABSTRACT FROM AUTHOR]

Molecular chirality has traditionally been viewed as a binary property where a molecule is classified as either chiral or achiral, yet in recent decades, mathematical methods for quantifying chirality have been explored. Here, we use toy molecular systems to systematically compare the performance of two state-of-the-art chirality measures: (1) the Continuous Chirality Measure (CCM) and (2) the Chirality Characteristic (χ). We find that both methods exhibit qualitatively similar behavior when applied to simple molecular systems such as a four-site molecule or the polymer double-helix, but we show that the CCM may be more suitable for evaluating the chirality of arbitrary molecules or abstract structures such as normal vibrational modes. We discuss a range of considerations for applying these methods to molecular systems in general, and we provide links to user-friendly codes for both methods. We aim for this paper to serve as a concise resource for scientists attempting to familiarize themselves with these chirality measures or attempting to implement chirality measures in their own work. [ABSTRACT FROM AUTHOR]

Chiral molecules can exhibit strong spin–orbit coupling, which can result in a large spin polarization. This is due to the fact that the energy levels of the electrons in a chiral molecule are strongly influenced by the chiral structure of the molecule, which can result in the separation of the energy levels for electrons with different spin orientations. We report a controlled spin-selective transmission of electrons through 20 base-paired poly-cytosine molecules functionalized with MoS2 flakes on ITO glass via the quantum mechanical tunneling effect. A reversion in spin polarization was observed after the silver ions interact with poly-cytosine due to the strong coordination of Ag(I) with cytosine–cytosine (C–C) mismatches, indicating the formation of duplex structural motifs, as confirmed by the circular dichroism spectroscopy at room temperature. Manipulating the spin of an electron through such a small molecule merely controlled by special cations could pave the way for major advances in spin-independent charge transport, advanced bioanalytical system design, and related applications. [ABSTRACT FROM AUTHOR]

Chiral molecules can exhibit strong spin–orbit coupling, which can result in a large spin polarization. This is due to the fact that the energy levels of the electrons in a chiral molecule are strongly influenced by the chiral structure of the molecule, which can result in the separation of the energy levels for electrons with different spin orientations. We report a controlled spin-selective transmission of electrons through 20 base-paired poly-cytosine molecules functionalized with MoS2 flakes on ITO glass via the quantum mechanical tunneling effect. A reversion in spin polarization was observed after the silver ions interact with poly-cytosine due to the strong coordination of Ag(I) with cytosine–cytosine (C–C) mismatches, indicating the formation of duplex structural motifs, as confirmed by the circular dichroism spectroscopy at room temperature. Manipulating the spin of an electron through such a small molecule merely controlled by special cations could pave the way for major advances in spin-independent charge transport, advanced bioanalytical system design, and related applications. [ABSTRACT FROM AUTHOR]

Molecular chirality is represented as broken mirror symmetry in the structural orientation of constituent atoms and plays a pivotal role at every scale of nature. Since the discovery of the chiroptic property of chiral molecules, the characterization of molecular chirality is important in the fields of biology, physics, and chemistry. Over the centuries, the field of optical chiral sensing was based on chiral light–matter interactions between chiral molecules and polarized light. Starting from simple optics-based sensing, the utilization of plasmonic materials that could control local chiral light–matter interactions by squeezing light into molecules successfully facilitated chiral sensing into noninvasive, ultrasensitive, and accurate detection. In this Review, the importance of plasmonic materials and their engineering in chiral sensing are discussed based on the principle of chiral light–matter interactions and the theory of optical chirality and chiral perturbation; thus, this Review can serve as a milestone for the proper design and utilization of plasmonic nanostructures for improved chiral sensing. [ABSTRACT FROM AUTHOR]

Chiral hybrid lead halide perovskites show interesting chiral optoelectronic properties. The extent of chirality is often estimated by their circular dichroism (CD) response. Here, we show that the CD data depend strongly on film morphology. Four of the six chiral hybrid lead halide films prepared, 2D (R- and S-MBA)2PbI4 and 1D (R- and S-MBA)PbI3 (MBA: methylbenzylammonium), form homogenous non-textured films and show an isotropic CD signal. In contrast, the other two samples, 1D (R- and S-MBA)PbBr3, form textured films, showing uncorrelated CD signals from different parts of the film. Therefore, the role of film morphology needs to be verified before designing and comparing the chiroptic and chiral optoelectronic properties of hybrid perovskites. [ABSTRACT FROM AUTHOR]

In connection to the chiral-induced spin selectivity effect, we theoretically analyze the electronic and spin states of edges of a finite p-orbital helical atomic chain with the intra-atomic spin–orbit interaction. This model can host the spin-filtering state in which two up-spins propagate in one direction and two down-spins propagate in the opposite direction without breaking the time-reversal symmetry (TRS). The enhancement of charge modulations concentrated at the edges due to the evanescent states is induced, although the spin density is absent because of the TRS. A Zeeman field at an edge of the atomic chain, which breaks the TRS, yields a finite spin polarization, whose direction depends on the chirality of the molecule. The chirality change induces a reasonable amount of the energy difference, which may provide an insight into the enantioselective adsorption of chiral molecules on the ferromagnetic surface. [ABSTRACT FROM AUTHOR]

Motivated by the booming development of spintronics based on chiral helical microstructures, we employed the standard nonequilibrium Green's function theory to study nonreciprocity and chirality of the heat generation and spin filtering in ferromagnetic helical chains. Our results demonstrate that magnetization, spin–orbit interaction, and nonstep electrostatic potential distribution by bias jointly determine nonreciprocity of the heat generation, and only spin–orbit interaction determines nonreciprocity of the spin-polarized current. Chirality of the heat generation and spin-polarized current is determined by both magnetization and spin–orbit interaction, and some quantitative relationships related to chirality were discovered. However, a transverse field can break these relations and suppress heat generation significantly and modulate nonreciprocity and chirality of the spin-polarized current effectively. By further simulating the critical electrostatic potential distribution, we found with the transverse field applied, compared to the case with zero temperature, that the finite temperature less than one characteristic phonon energy can suppress nonreciprocity of the heat generation while enhancing that of the spin filtering. In terms of chirality, compared to the left-handed helical structure, the right-handed one is more advantageous for designing spin filtering diodes. [ABSTRACT FROM AUTHOR]

The ability to accurately monitor chiral biological molecules is of great significance for their potential applications in disease diagnosis and virus detection. As the existing chiral detection technologies are mainly relying on an optical method by using left/right circularly polarized light, the universality is low and the operation is complicated. Moreover, large quantity of chiral molecules is required, causing low detection efficiency. Here, a self-assembled monolayer of polypeptides has been fabricated to realize trace detection of chirality based on spin selectivity of photon–electron interaction. We have utilized Kerr technique to detect the rotation angle by the molecular monolayer, which indicates the chirality of polypeptides. The chiral structure of a biological molecule could result in spin-selectivity of electrons and thus influence the interaction between electron spin and light polarization. A Kerr rotation angle of ∼3° has been obviously observed, equivalent to the magneto-optic Kerr effect without magnetic material or magnetic field. Furthermore, we have provided a novel solution to achieve chirality discrimination and amplification simultaneously through an optical fiber. The proposed design is applicable for chiral detection via increasing their differential output signal, which clearly demonstrates a useful strategy toward chirality characterization of biological molecules. [ABSTRACT FROM AUTHOR]

By now, it is well known that chiral molecules can affect the spin of electrons passing through. In addition, the magnetization of, e.g., nanomagnets covered by chiral molecules can be affected by the presence of molecules. We are studying the mechanisms that explain various observations involving combinations of magnets and chiral molecules. We find that there exists a molecule induced contribution to the magnetic anisotropy of the magnets. Out of equilibrium, when electrons are actually being transported through a nano-magnet covered with chiral molecules, a molecule induced torque acting on the magnetization is emerging. It is of the spin-transfer-torque kind, already discussed in other parts of spintronics. This current induced torque can help explain the observed breaking of the Onsager reciprocity principle in experiments involving magnets and chiral molecules. [ABSTRACT FROM AUTHOR]

Chiral materials exhibit many interesting physical properties including circular dichroism, circularly polarized photoluminescence, and spin selectivity. Since its discovery, chirality-induced spin selectivity (CISS) has been demonstrated in many chiral material systems, which indicates promising applications in spintronic devices. Thus, searching for compounds that possess both sizable chirality and excellent spin transport properties is in order. Hybrid organic–inorganic perovskites have attracted intensive research interest due to their long carrier lifetime, high carrier mobility, chemically tunable electronic properties, and long spin lifetime, which make this emerging class of semiconductors promising candidate for spintronics. Moreover, hybrid perovskites integrate inorganic octahedral framework and organic ligands, which may introduce chirality into the materials, especially in quasi-two-dimensional structures. Recently, CISS has been observed in 2D chiral hybrid perovskites, showing the spin filtering effect. Studies of CISS in chiral hybrid perovskites not only help deepen our understanding of CISS mechanism but also shed new light on designing novel spintronic devices. In this review, we summarize the state-of-the-art studies of CISS effect in 2D chiral hybrid organic–inorganic perovskites system. We also discuss the remaining challenges and research opportunities of employing CISS in next-generation spintronic devices. [ABSTRACT FROM AUTHOR]

Chiral macrocyclic arenes possess confined three-dimensional asymmetric cavities, electron-rich structures, chiral luminescence properties and excellent enantioselective recognition properties and have become a frontier and hotspot of macrocyclic chemistry and supramolecular chemistry. In recent years, there has been growing interest in the development of novel chiral macrocyclic arenes, which have found applications in various research areas. In this review, the construction, properties and functional applications of novel chiral macrocyclic arenes in enantioselective recognition, chiral sorting and construction of chiral luminescent materials according to their chiral types, including central, axial, planar, and inherent chiralities, are summarized. It is expected that this review will be helpful for research on supramolecular chemistry and for promoting the development of synthetic chemistry, materials chemistry and biochemistry. [ABSTRACT FROM AUTHOR]

Several BINOL‐derived C2‐symmetric aldehydes were synthesized to investigate chiral self‐sorting phenomena during macrocycle formation in the presence of aliphatic and aromatic bisamines. While self‐sorting was unsuccessful with aliphatic amines, aromatic amine dictated complete homochiral self‐sorting, confirmed by 1H NMR analysis and molecular modelling. Additionally, the impact of macrocyclization on the chiroptical properties of these macrocycles was examined. The Cotton effects band red‐shifted for aromatic amines owing to extended conjugation. Notably, a substantial increase in specific rotation was observed upon macrocycle formation. [ABSTRACT FROM AUTHOR]

A family of chiral perylene diimides (PDIs) was newly developed as excellent circularly polarized luminescence (CPL) materials. They are asymmetrically derivatized with a double‐alkyl‐chained L‐ or D‐glutamate unit and a linear or branched alkyl chain. When water is added to the tetrahydrofuran (THF) solution of glutamate‐PDI‐linear‐alkyl chain compounds, kinetically formed H‐aggregates are formed in globular nanoparticles (NPs). These NPs undergo spontaneous transformation into thermodynamically stable nanotubes via helical nanostructures, which showed structured broad spectra originating from the strong coupling of delocalized Frenkel excitations (FE) and charge transfer excitations (CTE). Significant enhancement of circular dichroism (CD), fluorescence quantum yield, and circularly polarized luminescence (CPL) with luminescence dissymmetry factor (glum) are observed during the transformation of NPs to the FE/CTE‐coupled helical and tubular structures. This transformation process is significantly accelerated by applying physical stimuli, i.e. ultrasonication or adding helical aggregates as seed crystals, a feature unique to living supramolecular polymerization. Meanwhile, the branched chain‐containing PDIs only form H‐aggregates and did not show FE/CTE hybrid exciton states with living supramolecular polymerization properties. This study unveils that suitably designed chiral PDI derivatives show FE/CTE coupling accompanied by high fluorescence quantum yields, enhanced chiroptical properties, and supramolecular living polymerization characteristics. [ABSTRACT FROM AUTHOR]

"Inadequate understanding of chirality has potentially disastrous consequences. "Genius on the left, madman on the right" is not an exaggerated verse in the field of chiral research, but a realistic warning..." [ABSTRACT FROM AUTHOR]

The atomic precision of metal nanoclusters and variability of surface ligands pave the way for their rational design and functionalization, whereas the property strengthening in multiple ways has been long challenging. Herein, improved amphiphilicity, chirality, thermostability, and strong CPL (circularly polarized luminescence) properties have been accomplished by facile ligand exchange of [Au23(CHT)16]− with HCapt (HCHT and HCapt denote cyclohexanethiol and captopril). In addition, the obtained chiral [Au23(SR)16]− (short for [Au23(CHT)16‐x(Capt)x]−) clusters show specific binding affinity to remote‐diamines (such as arginine and single/double strand DNA), originating from the hydrogen bonding and Van der Waals interaction among the surface Capt ligands and the di‐amine groups. [ABSTRACT FROM AUTHOR]

[2.2]Paracyclophanes ([2.2]PCs) with substituents at specific positions possesses planar chirality and stands as a promising building unit for the development of chiroptical materials associated with polarized light. However, one of the easily accessible starting materials, bromo‐substituted [2.2]PC, shows low reactivity, and effective methods for π‐extension of planar chiral [2.2]PC are limited. Herein, an effective π‐extension method has established for chiral [2.2]PC with four substitutions from 4,7,12,15‐tetrabromo[2.2]PC. This has led to tetrakis(trimethylsilylphenyl)‐[2.2]PC that serves as a versatile building resource for radial‐type chiral π‐conjugated compounds with a [2.2]PC core. In this study, synthesizing compounds are further succeeded with the introduction of carbazole (Cbz4‐[2.2]PC and tBuCbz4‐[2.2]PC) and investigated their chiroptical properties and chiral induction ability in achiral π‐conjugated polymers. A thin film of [Poly[9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)]] (F8BT) with 3wt% Cbz4‐[2.2]PC prepared by spin‐coating exhibits circularly polarized luminescence (CPL) properties with a high dissymmetry factor (|glum| = 0.01), which is much higher than that of Cbz4‐[2.2]PC in CH2Cl2 solution. By contrast, the doped film of F8BT with 3wt% tBuCbz4‐[2.2]PC exhibited only weak CPL properties. In addition, these chiral compounds show facile redox properties owing to the presence of carbazole units. Furthermore, Cbz4‐[2.2]PC undergoes electropolymerization to produce an insoluble thin film on the electrode. [ABSTRACT FROM AUTHOR]

Herein, an efficient homogenization procedure is extended based on a Haydock representation of the microscopic wave operator for the calculation of the retarded macroscopic dielectric response of a binary periodic composite to the case of an arbitrary number of components of arbitrary composition. As a test, this numerical procedure is applied to the calculation of the optical properties of a Bouligand structure, made up of a large number of anisotropic layers stacked on top of each other and progressively rotated. This system constitutes a photonic crystal with circularly polarized electromagnetic normal modes, naturally occurring in the cuticle of several arthropods. It presents a gap for one helicity, which corresponds to the observation of circularly polarized strong metallic like reflections. This numerical procedure is validated through its good agreement with the results of alternative formulations, including an analytical solution for this simple chiral system. [ABSTRACT FROM AUTHOR]

Organic circularly polarized luminescence (CPL) plays crucial roles in chemistry and biology for the potential in chiral recognition, asymmetric catalysis, 3D displays, and biological probes. The long‐lived luminescence, large Stokes shift, and unique chiroptical properties make organic circularly polarized room‐temperature phosphorescence (CPP) a new research hotspot in recent years. Nevertheless, achieving high‐performance organic CPP is still challenging due to the sensitivity and complexity of integrating triplet excitons and polarization within organic materials. This review summarizes the latest advances in organic CPP, ranging from design strategies and photophysical properties to underlying luminescence mechanisms and potential applications. Specifically, the design strategies for generating CPP are systemically categorized and discussed according to the interactions between chiral units and chromophores. The applications of organic CPP in organic light‐emitting diodes, sensing, chiral recognition, afterglow displays, and information encryption are also illustrated. In addition, we present the current challenges and perspectives on developing organic CPP. We expect this review to provide some instructive design principles to fabricate high‐performance organic CPP materials, offering an in‐depth understanding of the luminescence mechanism and paving the way toward diverse practical applications. [ABSTRACT FROM AUTHOR]

Chirality at the metal center is a well‐established concept, exemplified by numerous four‐ and six‐coordinated complexes. Here, a pioneering example of linear chirality‐at‐metal is described: [Ag(NHC)2]+ (NHC=N‐heterocyclic carbene). In solution, stabilizing π‐π interactions preserve the chiral information of the solid state. Consequently, a novel class of atropisomers is identified, whose stereogenicity arises from hindered rotation around a C−Ag−C axis, instead of a typical C−C bond. [ABSTRACT FROM AUTHOR]

We introduce (co)homology theory for multiple group racks and construct cocycle invariants of compact oriented surfaces in the 3-sphere using their 2-cocycles, where a multiple group rack is a rack consisting of a disjoint union of groups. We provide a method to find new rack cocycles and multiple group rack cocycles from existing rack cocycles and quandle cocycles. Evaluating cocycle invariants, we determine several symmetry types, caused by chirality and invertibility, of compact oriented surfaces in the 3-sphere. [ABSTRACT FROM AUTHOR]

The chiral ligand (R)-sirtinol and its ferric derivative, compound (I), have been used in a wide range of chemical and biological studies which should be sensitive to their chirality inasmuch as enantioselectivity is of primordial importance in such processes. It is, therefore, imperative that the chiral nature of the iron-containing molecule should be recognized; and, if the metal is chiral, the expectation is that its function(s) may be stereospecific. Surprisingly enough, until now little or nothing has been elucidated concerning its stereochemical character, probably because the chiral nature of a seven-fold coordinated environment is often overlooked and not commonly encountered in 3d compounds. Below, we address these issues because (I) crystallizes with Z′ = 2.0; thus, the chiral nature of its two diastereoisomers must be clearly understood in order to properly interpret the results of future chemical and biochemical investigations. We found that there is a novel form of crystallization in (I) characterized by: (1) there are two distinct diastereoisomeric species in the asymmetric unit differing in the magnitude and/or sign of relevant torsional angles; (2) the sirtinol ligand itself bears an (R) carbon in both, as expected from Z′ = 2.0. Thus, if the chirality of the ligand carbon is momentarily ignored, the crystals are simple examples of a kryptoracemate. If not, we have discovered a new crystalline form for which we propose a suitable nomenclature as this is now needed. In analogy to the classical example of “racemic mimics” recognized a long time ago, we name it kryptoracemic mimic. In essence, there are two different conditions to consider: the kryptoracemic character of the iron (in this case), and the pure enantiomeric character of the sirtinol ligand, and they must be properly described in the name of such species. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The first catalytic asymmetric total synthesis of (+)‐propolisbenzofuran B, enabled by a highly enantioselective rhodium‐catalyzed hydrogenation of a tetrasubstituted olefin, was described. Other noteworthy aspects include the construction of the central hydrodibenzo[b,d]furan core through a sequence of Zn(II)‐mediated regioselective benzofuran formation and Dieckmann condensation, as well as C‐H oxidations, involving a visible light‐induced Fe(III)‐catalyzed benzylic C(sp3)‐H oxidation. Additionally, the absolute configuration was confirmed by X‐ray analysis of a carbonate intermediate. [ABSTRACT FROM AUTHOR]

In a previous paper the authors with M. Conder proved that the alternating group A n and the symmetric group S n are pseudo-Hurwitz for any n > 23 , as well as are A 18 , A 19 , A 21 , A 22 and A 23 , and also S 10 , S 17 , S 19 , S 20 , S 21 and S 22. In this paper, we provide geometric tools for constructing all pseudo-Hurwitz groups up to a "small" degree. This construction, applied up to degree 23, shows that there are no other degrees for which A n and S n are pseudo-Hurwitz. In the second part of this paper we show that there are both reflexible and chiral pseudo-Hurwitz maps with automorphism group A n and S n , for every n ⩾ 36. [ABSTRACT FROM AUTHOR]

Towards complex coupled molecular motions, the remote handedness inversion of a helicene moiety was achieved by a rotary molecular motor. The use of a specifically engineered dynamic helicene stator in a novel overcrowded‐alkene second‐generation molecular motor based on a fluorinated dibenzofluorene fragment allows for an unprecedented control over helicity inversion. This is achieved by the mechanical coupling of the rotation of the rotor to the helicene inversion of the stator half via a remote chirality transmission process. Thus, the unidirectional rotary motion generated upon irradiation is used to invert the dynamic stereochemistry of a helicene, leading to a 6‐step cycle with eight intermediates. In this cycle, both alternation between P and M configurations of the helicene stator and dynamic thermal interconversion (paddling motion) can be achieved. In‐depth computational and spectroscopic studies were performed to support the associated mechanism. The control over coupled motion and dynamic helicity offers prospects for the development of complex responsive systems. [ABSTRACT FROM AUTHOR]

Two new structural motifs within the class of heteroleptic PdnAnBn assemblies, namely syn‐cis‐Pd3A3B3 bowls and bowl‐ (syn) or saddle‐ (anti) shaped cis‐Pd4A4B4 rings are introduced. All of the ten examples share a common longer fluorenone‐based bis‐monodentate ligand, equipped with meta‐pyridine donor groups. The ring size (3‐ vs. 4‐membered) and conformational preference (bowl vs. saddle) are controlled by the choice of the shorter ligand. These carry para‐pyridine donors, different aromatic backbones (benzene, thiophene or selenophene) and either no or small or bulky endohedral substituents, serving to control the nuclearity of the heteroleptic rings through different effects (ligand angle, charge distribution or backbone bulk). Moreover, the luminescence of the fluorenone ligand is conserved in the formed architectures. Emission intensity as well as host–guest properties vary depending on the inward‐pointing functions. All Pd3A3B3 assemblies are shown to bind chiral guest BINOL bis‐sulfonate which imparts its chirality to the entire host–guest complex. This results in a guest‐induced circular dichroism (CD) and circularly polarized luminescence (CPL) with dissymmetry factor glum up to 10−3. [ABSTRACT FROM AUTHOR]

Most synthetic self-assemblies grow indefinitely into size-unlimited structures, whereas some biological self-assemblies autonomously regulate their size and shape. One mechanism of such self-regulation arises from the chirality of building blocks, inducing their mutual twisting that is incompatible with their long-range ordered packing and thus halts the assembly's growth at a certain stage. This self-regulation occurs robustly in thermodynamic equilibrium rather than kinetic trapping, and therefore is attractive yet elusive. Until now, studies of self-regulating assemblies have focused on non-responsive systems, whose equilibrium point and corresponding size and shape are hardly changeable. Here, we demonstrate a stimuli-responsive, self-regulating assembly. This assembly consists of chiral and magnetically orientable nanorods, where the effective chirality can be changed by balancing chirality-induced twisting and magnet-induced flattening between nanorods. Consequently, the strength of self-regulation in the assembly is modulable by magnetic field intensity, allowing robust, tunable, and reversible control of its size and shape. Our strategy would provide more biomimetic materials with precision and responsiveness. The self-regulation of self-assembled systems is well understood for non-responsive systems, but responsive systems are less studied. Here, the authors report the development of a stimuli-responsive, self-regulating assembly of chiral and magnetically responsive nanorods, with control over the chirality of the system. [ABSTRACT FROM AUTHOR]

Chirality — a characteristic handedness that distinguishes 'left' from 'right'—is a fundamental property of quantum particles under broken symmetry intimately connected to their spins. Chiral fermions have been identified in Weyl semimetals through their unique electrodynamics arising from 'axial' charge imbalance between pairs of chiral Weyl nodes—the topologically protected 'relativistic' crossings of electronic bands. Chiral magnetotransport phenomena critically depend on the details of electronic band structure. However, the putative emergence of chiral electronic channels through shape altering of Weyl nodes is yet to be revealed. Here, we detect chirality-endowed linear conduction channels promoted by a tilt of Weyl bands in inversion-symmetric Weyl ferromagnet MnSb2Te4. The tuning of Weyl nodes is controlled with ionic hydrogen, which heals the system's (Mn-Te) bond disorder and lowers the internode scattering. The reshaped Weyl states feature a doubled Curie temperature ≳50 K and a strong angular transport chirality synchronous with a rare field-antisymmetric longitudinal resistance—a low-field tunable 'chiral switch' that is rooted in the interplay of Berry curvature, chiral anomaly and a hydrogen-mediated form of Weyl nodes. The possibility of tuning the shape of the Weyl nodes in topological magnets could open an avenue towards engineering their electrical behaviour. Here, the authors report the tuning of Weyl nodes and associated magnetotransport in MnSb2Te4 by diffusion-controlled ionic hydrogen insertion. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The first catalytic asymmetric total synthesis of (+)‐propolisbenzofuran B, enabled by a highly enantioselective rhodium‐catalyzed hydrogenation of a tetrasubstituted olefin, was described. Other noteworthy aspects include the construction of the central hydrodibenzo[b,d]furan core through a sequence of Zn(II)‐mediated regioselective benzofuran formation and Dieckmann condensation, as well as C‐H oxidations, involving a visible light‐induced Fe(III)‐catalyzed benzylic C(sp3)‐H oxidation. Additionally, the absolute configuration was confirmed by X‐ray analysis of a carbonate intermediate. [ABSTRACT FROM AUTHOR]

Controlling and channeling light emissions from unpolarized quantum dots into specific directions with chiral polarization remains a key challenge in modern photonics. Stacked metasurface designs offer a potential compact solution for chirality and directionality engineering. However, experimental observations of directional chiral radiation from resonant metasurfaces with quantum emitters remain obscure. In this paper, we present experimental observations of unidirectional chiral emission from a twisted bi-layer metasurface via multi-dimensional control, including twist angle, interlayer distance, and lateral displacement between the top and bottom layers, as enabled by doublet alignment lithography (DAL). First, maintaining alignment, the metasurface demonstrates a resonant intrinsic optical chirality with near-unity circular dichroism of 0.94 and reflectance difference of 74%, where a high circular dichroism greater than 0.9 persists across a wide range of angles from −11 to 11 degrees. Second, engineered lateral displacement induces a unidirectional chiral resonance, resulting in unidirectional chiral emission from the quantum dots deposited onto the metasurface. Our bi-layer metasurfaces offer a universal compact platform for efficient radiation manipulation over a wide angular range, promising potential applications in miniaturized lasers, grating couplers, and chiral nanoantennas. Simultaneous control of the direction and polarization of quantum emission using photonic nanostructures is a long-standing challenge in photonics. Here, the authors experimentally demonstrate unidirectional chiral emission from a twisted bilayer metasurface with multi-dimensional control. [ABSTRACT FROM AUTHOR]

A series of unprecedented supramolecular complexes of covalently modified Anderson‐type polyoxometalates (POMs) and α‐cyclodextrins (α‐CDs) have been obtained and characterized in solid state by single‐crystal X‐ray diffraction, and in aqueous solution using various techniques including 1H DOSY NMR, 2D NOESY 1H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time‐of‐flight mass spectroscopy (ESI‐TOF‐MS). It has been demonstrated that the supramolecular assembly process could be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α‐CD complexes featuring organic‐inorganic pseudo‐rotaxane structures, which are in good contrast to those of POM/γ‐CD complexes of poly‐rotaxane structures. Moreover, it is delighted to find that these pseudo‐rotaxanes of POM/α‐CD complexes exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/CD assemblies. [ABSTRACT FROM AUTHOR]

This essay presents the viewpoint of the author on the topic of chirality and optical activity in nanostructures. It particularly focuses on the interaction of chiral molecules with plasmonic and excitonic nanocrystals and on induction of circular dichroism in such achiral nanocrystals. It discusses recent developments in the shape symmetry breaking of achiral metal nanostructures using photochemical processes induced by asymmetric localized plasmonic hot spots excited through circularly polarized light illumination. Finally, it addresses symmetry breaking in intrinsically chiral inorganic nanocrystals using chiral ligands during their formation, leading to 100 % enantiomeric excess in the nanocrystals of TbPO4⋅H2O. These nanocrystals exhibit an interesting nucleation mechanism, which leads to very high chiral amplification (secondary nucleation). [ABSTRACT FROM AUTHOR]

Dynamic molecules with tunable chemical and physical properties in response to external stimuli hold great potential for applications in various fields such as information storage, smart molecular machines, and biomimetics. Among them, supramolecular springs and spin‐crossover (SCO) complexes can both undergo visible macroscopic changes under heat or light stimulation. In this study, we synthesized a unique trinuclear Fe(II)‐SCO complex, [(R−L)FeII{Au(CN)2}2] (R 1), using a chiral chelating ligand decorated with rotatable benzyl rings. The [FeAu2] trinuclear molecules form a 21‐helical supramolecular chain via elastic Au ⋯ ${\cdots }$ Au contacts. Interestingly, the synergy between the multiple dynamic factors (SCO event, rotation of the rings, and flexibility in Au ⋯ ${\cdots }$ Au distance) endows the complex with multiple switchings in both magnetism and structure, as well as the most intriguing characteristic of giant and anisotropic “breathing” feature in thermal expansion within two distinct temperature regimes. Specifically, complex R 1 undergoes two hysteretic magnetic transitions: a non‐spin transition between 360 and 380 K and an unsymmetric SCO transition in the region of 160–280 K, associated with a symmetry‐breaking event between the non‐polar and polar space groups (P212121↔P21). Both transitions are triggered/accompanied by the rotation (inward vs. outward) of the benzyl rings. Correspondingly, reversible spring‐like motions of the helical chains with the helical pitches varying from 11.345140 K to 12.509280 K then back to 11.630380 K Å are observed in the two distinct temperature regimes. This work demonstrates a significant success in incorporating both SCO and spring‐like motion in one system, paving the way for designing multifunctional dynamic materials for future devices. [ABSTRACT FROM AUTHOR]

Chirality is a fundamental property of nature, and recognizing chirality is crucial for human life. In this paper, a theoretical study on highly sensitive determination of the Pasteur parameter in chiral measurement is presented using long‐range surface plasmon polariton (LRSPP) resonance. The method is based on a thorough analysis of electromagnetic wave propagating in multilayer planar waveguide structures containing a chiral medium. Both the handedness and magnitude can be determined simultaneously, either by measuring the relative direction and separation of the spectral shift of the reflected right‐ and left‐handed circularly polarized components under the condition of an excited “bright” LRSPP mode, or by detecting the relative direction and amount of intensity split in the region of a “dark” LRSPP mode. The method offers improved measurement of the Pasteur parameter of 10−3 level for the “bright” mode and allows for an ultrasensitive measurement of 10−5 level for the “dark” mode. It is also immune to spectrum fluctuations or drifts caused by variations in the host refractive index or absorption loss. It is hoped that this work will inspire further optical techniques for high‐sensitivity chiral sensing and detection. [ABSTRACT FROM AUTHOR]

It remains challenging to elucidate the fundamental mechanisms behind the dynamic chirality inversion of supramolecular assemblies with pathway complexity. Herein, metal coordination driven assembly systems based on pyridyl-conjugated cholesterol (PVPCC) and metal ions (Ag+ or Al3+) are established to demonstrate pathway-directed, recyclable chirality inversion and assembly polymorphism. In the Ag(I)/PVPCC system, a competitive pathway leads Ag-Complex to form either kinetically controlled supramolecular polymer (Ag-SP I) or thermodynamically favored Ag-SP II, accompanied by reversible chiroptical inversion. Conversely, the Al(III)/PVPCC system displays a solvent-assisted consecutive pathway: the Al-Complex initially forms ethanol-containing Al-SP II, and subsequently converts into ethanol-free Al-SP I with opposite chiroptical performance upon thermal treatment. Moreover, stable chirality inversion in the solid state enables potential dynamic circularly polarized luminescence encryption when Ag(I)/PVPCC is co-assembled with thioflavin T. These findings provide the guidance for the dynamic modulation of chirality functionality in supramolecular materials for applications in information processing, data encryption, and chiral spintronics. Elucidation of the fundamental mechanisms behind the dynamic chirality inversion of supramolecular assemblies with pathway complexity is challenging. Here, the authors report metal coordination driven assembly systems based on pyridyl-conjugated cholesterol and show that metal ions facilitate pathway-directed, recyclable chirality inversion and assembly polymorphism. [ABSTRACT FROM AUTHOR]

Chiral polycyclic aromatic hydrocarbons with monkey saddle topology are a fascinating class of negatively curved compounds. To make the monkey‐saddles valuable building blocks for chirality‐assisted synthesis (CAS) approaches, the inversion barriers between the two possible enantiomers need to be high enough to prevent interconversion under CAS conditions. By molecular editing, aza monkey saddles were converted to the corresponding chromene monkey saddles that are configurationally stable even at temperatures of 220 °C over a period of 47 days. Their structures were studied by single X‐ray diffraction and enantiomers were separated to study the chiroptical properties. Furthermore, mechanistic assumptions of the formation of the chromene monkey saddles by DFT calculations are discussed. [ABSTRACT FROM AUTHOR]

Chiral helicenes are widely used in fields related to organic materials and molecular machines relevant molecules, as well as serving as privileged frameworks for chiral ligands and catalysts. Therefore, the research into asymmetric routes for the synthesis of chiral helical compounds has garnered significant interest in recent years. In this regard, chirality conversion/transfer from chiral precursors has emerged as a powerful strategy for the construction of chiral helicenes, allowing the synthesis of various types of chiral helical compounds. This strategy has become and will remain a prominent research topic in the field of asymmetric synthesis. In this review article, described between 2012 and 2024, the approaches for the synthesis of chiral helicenes by chirality conversion or transfer from centrally chiral precursors are summarized. [ABSTRACT FROM AUTHOR]

The realization of persistent luminescence and in particular circularly polarized luminescence (CPL) of organic radicals remains a challenge due to their sensitivity to oxygen at ambient conditions and elusive excited state chirality control. Here, it is reported that UV‐irradiation on a supramolecular gel from a chiral triarylamine derivative, TPA‐Ala, led to the formation of luminescent radicals with bright CPL. TPA‐Ala can form an organogel in chloroform with blue emission and supramolecular chirality as demonstrated by both CD and CPL signals. Upon UV 365 nm irradiation, an emission color change from blue to cyan is observed due to the formation of photo‐induced radicals. Interestingly, it is found that the supramolecular gel radicals showed stable luminescence with a lifetime ≈ 10 days in dark environments and inverted CPL, which represents a scarce example with persistent CPL from doublet‐state due to oxygen isolation ability of the gel network. Furthermore, doping a guest dye, Rhodamine B (RhB), into the supramolecular gel (RhB/TPA‐Ala = 30% in molar ratio) successfully obtained a transient white‐light CPL through the superposition of photo‐induced radical and guest dye emissions. This work provides a useful methodology for the fabrication of radical‐based CPL materials via a supramolecular assembly approach. [ABSTRACT FROM AUTHOR]