Macroscopic Chirality Research Articles

Hollow Superhelices Based on Chiral Europium Coordination Polymers.

The construction of helical nanotubes based on chiral coordination polymers (CPs) is an intriguing but challenging task, which is important for the development of functional materials that combine macroscopic chirality with tube-related properties. Here, we selected a chiral europium phosphonate system, e. g., Eu(NO3)3/R-,S-pempH2, and carried out a systematic work. By controlling the hydrothermal reaction conditions such as the pH value of the reaction mixture, the molar ratio and concentration of the reactants, we obtained block-like crystals of R/S-1 b, rod-like crystals of R/S-3 r, hollow superhelices of R/S-2 hh, and solid superhelices of R/S-4 sh. In the latter two cases, the chirality has been successfully transferred and amplificated from the molecular level to the macroscopic level. Interestingly, compounds R/S-2 hh and R/S-4 sh have the same chemical composition of Eu(R/S-pempH)3⋅2H2O and show identical PXRD patterns, thus can be considered as the same material except for different morphologies. We further investigated their circularly polarized luminescence (CPL) properties and found that the hollow superhelix of R/S-2 hh had a larger dissymmetry factor than the solid superhelix of R/S-4 sh. This study not only provides the first example of hollow superhelices of chiral CPs, but also offers the possibility of modulating the chiroptical properties of CPs through morphological control.

Homochiral Covalent Organic Frameworks with Superhelical Nanostructures Enable Efficient Chirality-Induced Spin Selectivity.

Despite significant advancements in fabricating covalent organic frameworks (COFs) with diverse morphologies, creating COFs with superhelical nanostructures remains challenging. We report here the controlled synthesis of homochiral superhelical COF nanofibers by manipulating pendent alkyl chain lengths in organic linkers. This approach yields homochiral 3D COFs 13-OR with a 10-fold interpenetrated diamondoid structure (R=H, Me, Et, nPr, nBu) from enantiopure 1,1'-bi-2-naphthol (BINOL)-based tetraaldehydes and tetraamine. COF-13-OEt exhibits macroscopic chirality as right-handed and left-handed superhelical fibers, whereas others adopt spherical or non-helical morphologies. Time-tracking shows a self-assembly process from non-helical strands to single-stranded helical fibers and intertwined superhelices. Ethoxyl substituents, being of optimal size, balance solvophobic effects and intermolecular interactions, driving the formation of superhelical nanostructures, with handedness determined by BINOL chirality. The superhelical nature of these materials is evident in their chiral recognition and spin-filter properties, showing significantly improved enantiodiscrimination in carbohydrate binding (up to six times higher enantioselectivity) and a remarkable chiral-induced spin selectivity (CISS) effect with a 48-51 % spin polarization ratio, a feature absent in non-helical analogs.

Homochiral Covalent Organic Frameworks with Superhelical Nanostructures Enable Efficient Chirality‐Induced Spin Selectivity

AbstractDespite significant advancements in fabricating covalent organic frameworks (COFs) with diverse morphologies, creating COFs with superhelical nanostructures remains challenging. We report here the controlled synthesis of homochiral superhelical COF nanofibers by manipulating pendent alkyl chain lengths in organic linkers. This approach yields homochiral 3D COFs 13‐OR with a 10‐fold interpenetrated diamondoid structure (R=H, Me, Et, nPr, nBu) from enantiopure 1,1′‐bi‐2‐naphthol (BINOL)‐based tetraaldehydes and tetraamine. COF‐13‐OEt exhibits macroscopic chirality as right‐handed and left‐handed superhelical fibers, whereas others adopt spherical or non‐helical morphologies. Time‐tracking shows a self‐assembly process from non‐helical strands to single‐stranded helical fibers and intertwined superhelices. Ethoxyl substituents, being of optimal size, balance solvophobic effects and intermolecular interactions, driving the formation of superhelical nanostructures, with handedness determined by BINOL chirality. The superhelical nature of these materials is evident in their chiral recognition and spin‐filter properties, showing significantly improved enantiodiscrimination in carbohydrate binding (up to six times higher enantioselectivity) and a remarkable chiral‐induced spin selectivity (CISS) effect with a 48–51 % spin polarization ratio, a feature absent in non‐helical analogs.

Signatures of polarized chiral spin disproportionation in rare earth nickelates

In rare earth nickelates (RENiO3), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO3 thin films, we observe the chiral nature of the spin-disproportionated state, with spin spirals propagating along the crystallographic (101)ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO3 (101)ortho films and RENiO3 single crystals. Experimentally-constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments.

Lyotropic Chromonic Mesophases of Chiral Organopalladium(II) Complexes for Amplified Circularly Polarized Phosphorescence

AbstractHerein, it is reported that lyotropic liquid crystals that transfer carbon‐centered chirality to helical chirality and subsequently to macroscopic chirality in the mesophases. This process is accompanied by remarkable amplification of both emission quantum yield and dissymmetry factor of the circularly polarized luminescence (CPL). Cationic tridentate cyclometalated Pd(II) complexes, once functionalized with chiral hydrogen‐bonding motifs of amide, aggregated into head‐to‐tail dimers at low concentrations in acetonitrile and further self‐organized into chiral lyotropic chromonic mesophases upon concentrated to 50 wt.%. At 25 °C, the chiral chromonics display metal–metal‐to‐ligand charge‐transfer (MMLCT) phosphorescence at an emission maximum of 677 nm with quantum yields up to 38% and lifetimes up to 0.50 µs. Notably, the dissymmetry factors ranged from 0.10 to 0.76, varying with the sample thickness in the range of 200–15 µm. Comparison studies and theoretical calculations reveal that the hydrogen‐bonding amide group is pivotal for the formation of the staggered configuration in the helical superstructures. Additionally, the carbon‐centered chirality of the amide dictate the handedness of the helices and consequently influenced the properties of CPL.

Polymer-Enabled Assembly of Au Nanoclusters with Luminescence Enhancement and Macroscopic Chirality.

The construction of macroscopic chiral luminescent aggregates with well-defined structures not only contributes to the development of functional materials but also has significant implications for analyzing chiral transfer and amplification in biological systems and self-assembly systems. Meanwhile, achieving water-soluble chiral metal nanoclusters (NCs) with high photoluminescence (PL) intensity through a convenient method remains a challenge. Herein, we reported the enhanced luminescence of gold nanoclusters stabilized by D-/L-penicillamine (D-/L-AuNCs) induced by poly(allylamine hydrochloride) (PAH) through supramolecular self-assembly strategies. FT-IR spectra and zeta potential measurements revealed that supramolecular assembly was driven by the synergistic effect of hydrogen bonds and electrostatic interactions, which effectively limited the intramolecular vibration and rotation of the ligand and reduced nonradiative relaxation, thus improving the luminescence properties of nanoclusters. Interestingly, during the slow solvent evaporation process, chiral entanglement of assemblies was enhanced, forming macroscopic wheat-shaped superstructures. This study enriches the understanding of the self-assembly mechanism of nanoclusters and provides a pathway for constructing NC-based chiroptical materials.

Spatially Correlated Chirality in Chiral Two-Dimensional Perovskites Revealed by Second-Harmonic-Generation Circular Dichroism Microscopy.

Understanding the chiral mechanism of chiral hybrid perovskites is a prerequisite for developing relevant chiroptoelectronic applications. Although conventional circular dichroism (CD) spectroscopy can be used to characterize chirality in chiral perovskites, it has a low signal-to-noise ratio and can provide only information about macroscopic chirality. Herein, with the aim of revealing the microscopic chiral mechanism in chiral perovskites, we utilize a spacer cation alloying strategy to construct chiral two-dimensional perovskites. For the first time, we demonstrate second-harmonic-generation CD microarea imaging in chiral perovskite thin films to unveil their spatially correlated chirality. In combination with theoretical calculations, it is revealed that the spatially correlated chirality is caused by localized out-of-plane supramolecular orientations. This work will not only advance the understanding of the mechanism of chiroptical activity in chiral perovskites but also provide inspiration for the rational design and synthesis of perovskites for chirality-related nonlinear optoelectronic devices.

Asymmetric transformation of achiral gold nanoclusters with negative nonlinear dependence between chiroptical activity and enantiomeric excess

The investigation of chirality at the nanoscale is important to bridge the gap between molecular and macroscopic chirality. Atomically precise metal nanoclusters provide an ideal platform for this research, while their enantiopure preparation poses a challenge. Here, we describe an efficient approach to enantiopure metal nanoclusters via asymmetric transformation, that is, achiral Au23(SC6H11)16 nanoclusters are converted into chiral and enantiopure Au24(L)2(SC6H11)16 nanoclusters by a chiral inducer phosphoramidite (L). Two enantiomers of Au24(L)2(SC6H11)16 are obtained and the crystal structures reveal their hierarchical chirality, which originates from the two introduced chiral L molecules, the transformation-triggered asymmetric rearrangement of the staple motifs on the surface of the gold core, and the helical arrangement of nanocluster molecules. The construction of this type of enantiomerically pure nanoclusters is achieved based on the easy-to-synthesize and modular L. Lastly, the chirality-related chiroptical performance was investigated, revealing a negative nonlinear CD-ee dependence.

Arene-Perfluoroarene Force Driven Sublimation-Removable Chiral Coassemblies.

Multiple constituent coassembly is an emerging strategy to manipulate supramolecular chirality and chiroptical properties such as circularly polarized luminescence (CPL). However, the second or third constituent could not be removed from pristine self-assembly. Here we developed a constitute-removable chiral coassembly using sublimation that could realize coassembly with tunable supramolecular chirality, luminescence and CPL properties. Octafluoronapthalene (OFN) with small sublimation enthalpy formed coassemblies with perylene-conjugated peptoids via arene-perfluoroarene (AP) interaction that induced the emergence of macroscopic chirality and hypochromic 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.

Arene‐Perfluoroarene Force Driven Sublimation‐Removable Chiral Coassemblies

AbstractMultiple 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.

Soft nanostructures out of star-shaped triazines with flexible amide spacers: liquid crystals with a cubic to columnar transition with memory effect, gels and supramolecular chirality

This work reports the synthesis and characterization of a new family of star-shaped tricarboxamides with C3-symmetry that have flexible amide spacers linking a tris(triazolyl)triazine core with three trialkoxyphenyl groups. The presence of amide groups allows the formation of intermolecular hydrogen bonds that reinforce π-stacking and van der Waals interactions, promoting liquid crystalline behavior, and self-assembly in solvents leading to organogels. As determined by polarized optical microscopy, differential scanning calorimetry and X-ray diffraction on powder samples, all the three reported molecules present a hexagonal columnar (Colh) phase stable at room temperature. Interestingly, they show a transition to a cubic micellar mesophase (BCC) at high temperatures. A mechanism for this transition, which is consistent with the fragmentation of columns to form supramolecular spheres, was elucidated from X-ray studies on aligned samples. Moreover, on cooling from the BCC to the columnar phase a preferential orientation of columns occurs, according to which each cubic domain gives rise to four hexagonal domains. The ability of the synthesized structures to aggregate in solvent media was studied in a variety of organic solvents, and all of them were able to gel 1-octanol at low concentrations. X-ray studies of gels and xerogels were carried out and showed a molecular organization consistent with Colh order. FTIR studies were carried out to analyze the formation of hydrogen bonds and the influence of the length of the flexible spacer in the liquid crystalline state and in the organogels. Furthermore, the presence of a stereogenic center in the flexible amide spacer leads to macroscopic chirality in the liquid crystal state and the organogels in 1-octanol as demonstrated by circular dichroism spectroscopy.

PH and Salt-Assisted Macroscopic Chirality Inversion of Gadolinium Coordination Polymer.

The precise adjustment of handedness of helical architectures is important to regulate their functions. Macroscopic chirality inversion has been achieved in organic supramolecular systems by pH, metal ions, solvents, chiral and non-chiral additives, temperature, and light, but rarely in coordination polymers (CPs). In particular, salt-assisted macroscopic chirality inversion has not been reported. In this work, we carried out a systematic investigation on the role of pH and salt in regulating the morphology of CPs based on Gd(NO3)3 and R-(1-phenylethylamino)methylphosphonic acid (R-pempH2). Without extra NO3-, the chirality inversion from the left-handed superhelix R-M to the right-handed superhelix R-P can be achieved by pH modulation from 3.2 to 3.8. The addition of NaNO3 (2.0 eq) at pH 3.8 results in an inversion of chiral sense from R-P to R-M as a pure phase. To our knowledge, this is the first example of salt-assisted macroscopic helical inversion in artificial systems.

Probing the Origin of Chiral Charge Density Waves in the Two-Dimensional Limits.

Chirality generates spontaneous symmetry breaking and profoundly influences the topology, charge, and spin orders of materials. The chiral charge density wave (CDW) exhibits macroscopic chirality in the achiral crystal during the spontaneous electronic phase transitions. However, the mechanism of chiral CDW formation is shrouded in controversy. In this work, we report that two-dimensional H-phase TaS2 synthesized by molecular-beam epitaxy (MBE) shows a predominantly chiral CDW phase. Scanning tunneling microscopy (STM) imaging of the CDW reconstruction spots reveals a clockwise or anticlockwise intensity variation along the STM-imaged spots. First-principles calculations further show that the rotational symmetry of the momentum-dependent electron-phonon coupling is broken, giving rise to chirality. Our work provides new insights into the physical origin of the chiral charge-ordered states, shedding light on a general ordering rule in chiral CDWs.

Chiral Sum Frequency Generation Spectroscopy Detects Double-Helix DNA at Interfaces.

Many DNA-based technologies involve the immobilization of DNA and therefore require a fundamental understanding of the DNA structure-function relationship at interfaces. We present three immobilization methods compatible with chiral sum frequency generation (SFG) spectroscopy at interfaces. They are the "anchor" method for covalently attaching DNA on a glass surface, the "island" method for dropcasting DNA on solid substrates, and the "buoy" method using a hydrocarbon moiety for localizing DNA at the air-water interface. Although SFG was previously used to probe DNA, the chiral and achiral SFG responses of single-stranded and double-stranded DNA have not been compared systemically. Using the three immobilization methods, we obtain the achiral and chiral C-H stretching spectra. The results introduce four potential applications of chiral SFG. First, chiral SFG gives null response from single-stranded DNA but prominent signals from double-stranded DNA, providing a simple binary readout for label-free detection of DNA hybridization. Second, with heterodyne detection, chiral SFG gives an opposite-signed spectral response useful for distinguishing native (D-) right-handed double helix from non-native (L-) left-handed double helix. Third, chiral SFG captures the aromatic C-H stretching modes of nucleobases that emerge upon hybridization, revealing the power of chiral SFG to probe highly localized molecular structures within DNA. Finally, chiral SFG is sensitive to macroscopic chirality but not local chiral centers and thus can detect not only canonical antiparallel double helix but also other DNA secondary structures, such as a poly-adenine parallel double helix. Our work benchmarks the SFG responses of DNA immobilized by the three distinct methods, building a basis for new chiral SFG applications to solve fundamental and biotechnological problems.

Molecularly imprinted cholesteric materials for enhanced enantiomeric separation

A cholesteric network exhibiting two levels of chirality, i.e. a macroscopic chirality issued from cholesteric structure and a local chirality generated by the presence of chiral imprinted sites, was synthesized. The specific role of each level of chirality in enantio-recognition phenomena was investigated in gaz phase by comparing their sorption properties towards two enantiomers of a chiral amine. Both levels of chirality improves the separation, the chiral environment having a lower effect than the presence of chiral-specific molecular cavities.

Controllable Macroscopic Chirality of Coordination Polymers through pH and Anion-Mediated Weak Interactions.

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 , C6 H5 , 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.

Hierarchically Evolved Supramolecular Chirality Mediated by Arene-Perfluoroarene Interaction.

Rational utilization of diverse weak forces in directing multiple-constituent chiral coassemblies is of vital importance in fabricating functional chiroptical materials. In this work, arene-perfluoroarene (AP) and hydrogen bonds were orthogonally employed to afford synergistic binary and ternary coassemblies. On the supramolecular scale, amino acids were connected to achiral pyrene moieties, which packed into supramolecular tilt chirality individually. The modified aromatic amino acids coassembled with melamine and octafluoronaphthalene (OFN) through multiple hydrogen bond and AP interactions, respectively, to construct binary and ternary systems. The introduction of hydrogen bonds and AP interactions shall alter the nanostructures and luminescent properties. Emergence of macroscopic chirality at nanoscale was realized, accompanied by the inversion of circularly polarized luminescence. These interactions working in an orthogonal way regulated the supramolecular chirality, emission properties, nanostructure transformation, and chiroptical activities, which enriched the protocols in designing functional chiral composites.

Vortex-Induced Harmonic Light Scattering of Porphyrin J-Aggregates.

An understanding of macroscopic vortex-induced chirality can provide insights into the origin of the homochirality of life. While circular dichroism measurements in stirred solutions are useful for the analysis of chiral supramolecular structures induced by vortex motion, there are no reports on the application of other spectroscopic methods. To obtain a deeper understanding of macroscopic vortex-induced chirality, it is essential to develop novel in situ spectroscopic methods that provide information about changes in both the size and chirality in stirred solutions. Here, we report the first observation by harmonic light scattering of the mirror-symmetry-breaking process of porphyrin J-aggregates under the rotation of a magnetic stirrer. The chiral supramolecular structure observed during stirring is likely due to the formation of a chiral aggregate that consists of porphyrin J-aggregates. The dissociation of the structure proceeds in two steps (a fast step and a slow step), as indicated by the signal decay rate when stirring was stopped. This novel method is useful for analyzing the supramolecular structural changes of chiral aggregates induced by external stimuli.

Halogenation Regulates Supramolecular Chirality at Hierarchical Levels of Self-Assembled N-Terminal Aromatic Amino Acids.

Halogenation brings about dramatic variations to the performance of self-assembled organic species, such as luminescence and crystallinity, but it has seldom been utilized for chirality control. Here we show the halogenation effect of self-assembling organic building units on supramolecular chirality and chiroptical responses. N-terminal aromatic amino acids with different substituted halogen atoms at p-phenylalanine residues self-assembled into one-dimensional fibrous structures. Halogenation induced the emergence of macroscopic chirality regardless of halogen properties like electronegativity, generating exclusive homochiral helical structures. Solid-state X-ray structures and time-dependent density functional theory were utilized for calculated electronic circular dichroism spectra, which evidenced the diverse driving forces to enable chiral molecular arrangements, including H-bonds and halogen bonds. Red-shifted luminescence was observed in brominated building units, giving rise to active circularly polarized luminescence. This work elucidates the multiple roles of halogen in chiral self-assembly systems, which provides insight into the rational control over supramolecular chirality and their chiroptical applications.

Mirror-image antiparallel β-sheets organize water molecules into superstructures of opposite chirality

Biomolecular hydration is fundamental to biological functions. Using phase-resolved chiral sum-frequency generation spectroscopy (SFG), we probe molecular architectures and interactions of water molecules around a self-assembling antiparallel β-sheet protein. We find that the phase of the chiroptical response from the O-H stretching vibrational modes of water flips with the absolute chirality of the (l-) or (d-) antiparallel β-sheet. Therefore, we can conclude that the (d-) antiparallel β-sheet organizes water solvent into a chiral supermolecular structure with opposite handedness relative to that of the (l-) antiparallel β-sheet. We use molecular dynamics to characterize the chiral water superstructure at atomic resolution. The results show that the macroscopic chirality of antiparallel β-sheets breaks the symmetry of assemblies of surrounding water molecules. We also calculate the chiral SFG response of water surrounding (l-) and (d-) LK7β to confirm the presence of chiral water structures. Our results offer a different perspective as well as introduce experimental and computational methodologies for elucidating hydration of biomacromolecules. The findings imply potentially important but largely unexplored roles of water solvent in chiral selectivity of biomolecular interactions and the molecular origins of homochirality in the biological world.