Chirality Transfer Research Articles

Stereoselective Vinylogous Aza-Pummerer Reaction of β,β-Disubstituted Enesulfinamides.

Treatment of multisubstituted NH-enesulfinamides with tosyl isocyanate (TsNCO) at room temperature results in the formation of α-tosylcarbamoyloxy N-sulfenyl ketimines with high enantioselectivity. This process is believed to proceed via a vinylogous aza-Pummerer-type reaction pathway in which the sulfinyl oxygen atom in the enesulfinamides undergoes nucleophilic attack on tosyl isocyanate, triggering the subsequent transformations that enable the transfer of chirality from sulfur to carbon.

Photo-Controllable Förster Resonance Energy Transfer Based on Dynamic Chiral Self-Assembly of Sequence-Defined Amphiphilic Alternating Azopeptoids.

Endowing biomimetic sequence-controlled polymers with chiral functionality to construct stimuli-responsive chiral materials offers a promising approach for innovative chiroptical switch, but it remains challenging. Herein, it is reported that the self-assembly of sequence-defined chiral amphiphilic alternating azopeptoids to generate photo-responsive and ultrathin bilayer peptoidosomes with a vesicular thickness of ≈1.50nm and a diameter of around ≈290nm. The photoisomerization of azobenzene moiety facilitates a reversible structural transformation from isotropic peptoidosomes to anisotropic 1D helical nanoribbons (≈80nm width) under the alternating irradiation with UV and visible lights, consequently leading to the chirality expression and transfer from chiral asymmetric center to achiral azobenzene units. As a biomimetic model with deformation-induced energy transfer, a non-invasive azobenzene-based Förster resonance energy transfer system is unprecedentedly constructed via the introduction of a fluorescent donor of pyrene derivatives and sequentially photo-regulated the donor/acceptor ratio, displaying a reversible gradient fluorescent color variation from blue to yellow (a broad Stokes shift of ≈200nm) and a high-efficient energy transfer efficiency of 97.2%. The photo-controllable photoluminescence phenomenon endows these chiral aggregates with a proof-of-concept application on multi-colored information encryption. This work provides a prospective strategy to fabricate stimuli-responsive chiral biomimetic materials with a potential on the light-controllable switches.

CsPbBr3 Superstructures with Circularly Polarized Photoluminescence Obtained by the Self-Assembly and Annealing of Nanoclusters.

We report a two-step approach to fabricate CsPbBr3 superstructures with strongly circularly polarized photoluminescence by self-assembly of nanoclusters on a substrate, followed by their annealing. In the first step, the nanoclusters self-assemble upon solvent evaporation, a process that forms mesoscopic superstructures whose geometrical arrangement at the µm-scale confers them optical chirality. In the second step, mild annealing of such superstructures induces the coalescence of the nanoclusters, accompanied by a continuous red shift of the photoluminescence up to 530 nm, with preservation of the µm-scale wires bundles and the chiral properties of the sample (glum = 0.1). The successful chirality transfer from the initial nanoclusters assemblies to these final CsPbBr3 superstructures provides a convenient way to obtain circularly polarized emitters.

Structural relaxation chirality transfer enhanced circularly polarized luminescence in heteronuclear CeIII-MnII complexes.

Circularly polarized luminescence (CPL) materials have developed rapidly in recent years due to their wide application prospects in fields like 3D displays and anti-counterfeiting. Utilizing energy transfer processes to transfer chirality has been proven as an efficient way to obtain CPL materials. However, the physics behind energy-transfer induced CPL is still not clear. Herein, in a well-designed heteronuclear CeIII-MnII complex system [(Ce((R/S)-L)Br(μ-Br))2]MnBr4 [(R/S)-L = (2R,3R)- or (2S,3S)-2,3-dimethyl-1,4,7,10,13,16-hexaoxacyclooctadecane] with intra energy transfer from CeIII to MnII, the luminescence dissymmetry factor of MnII obtained by excitation of CeIII is around 10 times higher than that obtained by direct excitation of MnII, while the CeIII center itself shows an almost negligible CPL. To address this unusual phenomenon, we proposed a new mechanism named structural relaxation chirality transfer (SRCT) where structural relaxation of the excited chiral donor amplified chirality transfer to the acceptor by intramolecular interactions. As an assistant proof, a mixture of CeIII-ZnII and LaIII-MnII complexes with inter energy transfer showed no CPL amplification. These results will inspire more breakthroughs in the physics nature and development of energy-transfer induced CPL.

Engineering Perfluoroarenes for Enhanced Molecular Barrier Effect and Chirality Transfer in Solutions

Engineering Perfluoroarenes for Enhanced Molecular Barrier Effect and Chirality Transfer in Solutions

Hierarchical amplification of chirality in anion-coordinated tetrahedral cages

Upon the self-assembly and subsequent host-guest chemistry, a hierarchical chiral system at the supramolecular level was established, featuring controllable chiral transfer and amplification.

Peptide-induced chirality transfer and circularly polarized luminescence in achiral BODIPY emitters via halogen bonding.

This study explores peptide-mediated chiral induction and circularly polarized luminescence (CPL) in achiral BODIPY dyes, leading to a high glum value of up to -1.2 × 10-2 through orthogonal halogen bonding and hydrogen bonding. It unravels the impact of these combined directional interactions on the formation of heterostructures and their thermal stability.

Dynamic supramolecular snub cubes.

Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids1 and ferritin2 offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C-H hydrogen bonds3. The enantiomerically pure snub cubes, which have external diameters of 5.1 nm, contain 2,712 atoms and chiral cavities with volumes of 6,215 Å3. The stereospecific assembly of left- and right-handed snub cubes was achieved by means of a hierarchical chirality transfer protocol4, which was streamlined by diastereoselective crystallization. In addition to their reversible photochromic behaviour, the snub cubes exhibit photocontrollable elasticity and hardness in their crystalline states. The snub cubes can accommodate numerous small guest molecules simultaneously and encapsulate two different guest molecules separately inside the uniquely distinct compartments in their frameworks. This research expands the scope of artificial supramolecular assemblies to imitate the chiral superstructures, dynamic features and binding properties of spherical biomacromolecules and also establishes a protocol for construction of crystalline materials with photocontrollable mechanical properties.

Generating Strong Circularly Polarized Luminescence from Self-assembled Films of Chiral Selenium Nanoparticles and Upconversion Nanoparticles.

Circularly polarized luminescence (CPL) has garnered significant research attention. Achieving a high luminescence dissymmetry factor (glum) is a key challenge in this field. Herein, we reported, for the first time, the fabrication of a chiral assembled film consisting of chiral D-/L-Selenium nanoparticles (D-/L-Se NPs) and DSPE-PEG-NH2 modified upconversion nanoparticles (DPNUCNPs) with remarkable CPL properties that were generated by the interfacial self-assembly technique. The chiral Se/DPNUCNPs films, consisting of three layers (3L) of D-/L-Se films and 3L DPNUCNPs films, exhibited the highest circular dichroism (CD) response and the strongest CPL signals. Under laser excitation at 980 nm, the 3L D-/L-Se/3L DPNUCNPs assembled films displayed symmetric CPL signals between 400 and 600 nm, with a maximum |glum| value of 0.68. The interaction between DPNUCNPs and Se NPs involves energy transfer and chirality transfer, along with the formation of spin-polarized excitons, thereby resulting in CPL activity. Furthermore, the chiral Se/DPNUCNPs films were patterned for anti-counterfeit and encryption applications. Our study provides a novel guide for fabricating chiral nanomaterials with strong CPL response.

Generating Strong Circularly Polarized Luminescence from Self‐assembled Films of Chiral Selenium Nanoparticles and Upconversion Nanoparticles

Circularly polarized luminescence (CPL) has garnered significant research attention. Achieving a high luminescence dissymmetry factor (glum) is a key challenge in this field. Herein, we reported, for the first time, the fabrication of a chiral assembled film consisting of chiral D‐/L‐Selenium nanoparticles (D‐/L‐Se NPs) and DSPE‐PEG‐NH2 modified upconversion nanoparticles (DPNUCNPs) with remarkable CPL properties that were generated by the interfacial self‐assembly technique. The chiral Se/DPNUCNPs films, consisting of three layers (3L) of D‐/L‐Se films and 3L DPNUCNPs films, exhibited the highest circular dichroism (CD) response and the strongest CPL signals. Under laser excitation at 980 nm, the 3L D‐/L‐Se/3L DPNUCNPs assembled films displayed symmetric CPL signals between 400 and 600 nm, with a maximum |glum| value of 0.68. The interaction between DPNUCNPs and Se NPs involves energy transfer and chirality transfer, along with the formation of spin‐polarized excitons, thereby resulting in CPL activity. Furthermore, the chiral Se/DPNUCNPs films were patterned for anti‐counterfeit and encryption applications. Our study provides a novel guide for fabricating chiral nanomaterials with strong CPL response.

Studies on the Stereoselective Synthesis of Sacubitril via a Chiral Amine Transfer Approach.

We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto™. Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)-pyroglutamic acid as a key building block and Cu(I)-mediated Csp2-Csp3 cross-coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents-based stereoselective synthesis. This involved the E-selective construction of γ-ylidene-butenolide from readily available biphenyl bromide and 4-pentynoic acid, the conversion of this butenolide to its ene-lactam using chiral amine, and substrate-controlled diastereoselective reduction of ene-lactam using Et3SiH or Pd/C, H2 (overall chiral amine transfer) as key transformations. Antipodal lactam intermediates were synthesized using corresponding chiral amines, and the stereochemical outcomes during the ene-lactam reduction with Et3SiH were rationalized by DFT studies.

Dynamic Covalent Bonds‐Mediated Color‐Switchable Circularly Polarized Luminescence in Helical Assemblies of Achiral Liquid Crystal Block Copolymer Films

Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three‐dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non‐contact modulation of CPL remain challenging. In this work, color‐switchable homochiral CPL films with high luminescence asymmetry factor (glum~0.11) were constructed based on the co‐assembly of a liquid crystal block copolymer (poly (ethylene oxide)‐b‐poly (methyl methacrylate) bearing cyanostilbene group) with axial chiral dinaphthalene diamine derivatives (R/S‐DINBPA). Mechanistic investigation revealed that the efficient stacking of R/S‐DINBPA with cyanostilbene groups and the liquid crystal field provide the driving force for chiral transfer and amplification. The dynamic covalent bonds of the cyanostilbene groups endow the film with chiral fixation ability and enable precise modulation of CPL luminescence bands under UV light irradiation, making it suitable for chiral patterned anti‐counterfeit encryption. This facile strategy provides a general platform for designing intelligent chiroptical materials.

Dynamic Covalent Bonds-Mediated Color-Switchable Circularly Polarized Luminescence in Helical Assemblies of Achiral Liquid Crystal Block Copolymer Films.

Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three-dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non-contact modulation of CPL remain challenging. In this work, color-switchable homochiral CPL films with high luminescence asymmetry factor (glum~0.11) were constructed based on the co-assembly of a liquid crystal block copolymer (poly (ethylene oxide)-b-poly (methyl methacrylate) bearing cyanostilbene group) with axial chiral dinaphthalene diamine derivatives (R/S-DINBPA). Mechanistic investigation revealed that the efficient stacking of R/S-DINBPA with cyanostilbene groups and the liquid crystal field provide the driving force for chiral transfer and amplification. The dynamic covalent bonds of the cyanostilbene groups endow the film with chiral fixation ability and enable precise modulation of CPL luminescence bands under UV light irradiation, making it suitable for chiral patterned anti-counterfeit encryption. This facile strategy provides a general platform for designing intelligent chiroptical materials.

Seeding Control in Chirality Triggering of Red-Emitting Organic Charge-Transfer Cocrystal Helixes from Achiral Molecules.

Supramolecular chirality has gained immense attention for great potential, in which the rational engineering strategy facilitates unique helical stacking/assembly, high chiroptical behavior, and prime biomedical activity. In this study, we reported a novel chiral organic donor-acceptor cocrystal based on asymmetrical components of benzo(b)naphtho(1,2-d)thiophene (BNT) and 9-oxo-9H-indeno(1,2-b)pyrazine-2,3-dicarbonitrile (DCAF) that exhibited red emission using a simple solution approach. During the self-assembly, a kinetically controlled growth of polar solvent or substrate induction led to the chiral packing and helical morphology twisted by the cooperation of electrostatic potential energy and chirality. Intriguingly, a "seeding-control" mechanism was newly developed for the production of c-BNT-DCAF helical crystals with a defined uniform chiral form, which enables chirality transfer and amplification from the microscopic to macroscopic level via supramolecular stacking. By introducing chiral additives or even a small break at the edge, the first nucleus acted as a chiral seeding to guide the donor/acceptor molecule alignment into the same handedness. A remarkably high dissymmetry factor (glum) value of 0.1 was demonstrated on the chiral manipulated ribbons, which is the highest among the reported charge-transfer complexes. This work offers us more paths for the design of chiral supramolecular systems for vital applications in organic optoelectronics, micro/nanomechanics, and biomimetics.

Sensitive Detection of Hg2+ and l-Cysteine through Optical Asymmetry-Tuned Fluorescence Switch Off-On Behavior in N-Doped Chiral Carbon Dot.

Blue-emissive nitrogen-doped chiral carbon dots (d-NCD230 and l-NCD230) exhibiting antipodal chiroptical activity, synthesized from the thermal pyrolysis of citric acid and d/l-aspartic acid in 1:2 molar ratios, have been explored as chirality-based fluorescent turn-off/on probes for the detection of Hg2+ and l-cysteine (l-Cys). Circular dichroism (CD) spectroscopy revealed that the chiroptical activity originates from a synergy among intrinsic chirality, chiral precursors on the NCD surface, and hybridization of lower energy levels within the embedded chiral chromophore. Quantitative analysis of optical asymmetry using the Kuhn asymmetry factor (g) at the CD signal of 312 nm showed a higher value for d-NCD230 (1.03 × 10-4) compared to l-NCD230 (1.13 × 10-5). Moreover, we have demonstrated chirality transfer and chiral inversion phenomena in d/l-NCDs by preparing carbon dots with different precursor ratios at different temperatures and probing them through CD spectroscopy. The NCDs exhibited selective fluorescence quenching in the presence of Hg2+, demonstrating linearity in the Stern-Volmer plot. Limits of detection (LODs) for Hg2+ were calculated to be 129 and 192 nM for d-NCD230 and l-NCD230, respectively, in the 0-150 μM concentration range. The quenching mechanism involves nonradiative electron transfer due to Hg2+ binding to oxygen-rich functional groups on the d/l-NCD230 surface. The slight variation in LOD values between d-NCD230 and l-NCD230 indicates the negligible effect of the chirality on Hg2+ sensing. Notably, the fluorescence intensity of d/l-NCD230 could be restored upon adding l-cysteine, with d-NCD230 showing a more pronounced enhancement than l-NCD230. This differential response is attributed to a preferential stereoselective interaction arising from the homochirality of d-NCD230/Hg2+ and l-cysteine. These findings demonstrate the potential of chiral nitrogen-doped carbon dots as sensitive and selective probes for Hg2+ and l-cysteine, with implications for environmental monitoring and biological sensing applications.

Dispersion Forces-Driven Hierarchical Assembly of Protein-Like Lanthanide Octamers and Emergent CPL.

Hierarchical self-assembly driven by non-covalent interactions is a prevalent strategy employed by nature to construct sophisticated biomacromolecules, such as proteins. However, the construction of protein-like superstructures that rely on weaker dispersion forces-driven hierarchical assembly remains largely unexplored. Here, we report the first example of dispersion forces driving the high-order assembly of the lanthanide trinuclear circular helicate [HNEt₃]₃[Eu₃(LL)₆] (ΔΔΔ-1) into a protein-like lanthanide octamer ((ΔΔΔ-1)₈-2). Within the octamer, the forty-eight (48) menthol groups on the ligands and eighty-four (84) 1,4-dioxane solvent molecules contribute to enhanced dispersion forces through conformational adaptation and size-matching effects. These enhanced dispersion forces not only drive the formation of the hierarchical superstructure but also result in a four-level chirality transfer from the menthol to the octamer. Benefiting from the homochirality of Eu3+, the octamer is endowed the strong circularly polarized emission (|glum|=0.34, Φoverall=41 %). This understanding of how dispersion forces drive hierarchical self-assembly provides a foundation for the directed fabrication of more fascinating superstructures.

Enantiospecific Synthesis of Planar Chiral Rhodium and Iridium Cyclopentadienyl Complexes: Enabling Streamlined and Computer-Guided Access to Highly Selective Catalysts for Asymmetric C-H Functionalizations.

Chiral cyclopentadienyl (CpX) metal complexes are frequently used in asymmetric catalysis by virtue of their high reactivity and selectivity. Planar-chiral-only rhodium and iridium cyclopentadienyl complexes are particularly promising due to unrestricted chemical space for CpX ligand design while retaining structural simplicity. However, they are currently still niche because of a lack of efficient synthetic strategies that avoid lengthy chiral auxiliary routes or chiral preparatory HPLC resolution of the complexes. To streamline access to such planar-chiral-only CpX-metal complexes, we designed a straightforward, highly enantiospecific, point-to-planar chirality transfer complexation via facially selective concerted-metalation-deprotonation between metal-carboxylate precursor [M(olefin)2OAc]2 and a chiral cyclopentadiene. This entirely avoids the typical stereoablative complexation of an achiral cyclopentadienyl anion that detrimentally yields a racemate. Exploiting the described enantiospecific complexation protocol and a simple divergent synthetic route to suitable chiral cyclopentadienes, we generated a structurally diverse library of new planar chiral Cp-Rh(I), Cp-Ir(I), Cp-Rh(III), and Cp-Ir(III) complexes. Moreover, the enantiospecific complexation step can be concatenated with a preceding Au-catalyzed cyclization in an efficient one-pot process that likely involves an elaborate point-to-axial-to-point-to-planar chirality transfer. Guided by computational selectivity predictions, the structure of a CpX-Rh complex in our library was tuned to optimize reactivity and selectivity in the asymmetric C-H functionalization of a benzamide with various challenging alkenes. With an optimized CpX-Rh complex in hand, we showcased its excellent catalytic performance and high selectivity for refractory alkene substrates that reacted in poor selectivity with previous CpX-Rh catalysts.

Strong Magneto‐chiroptical Effects through Introducing Chiral Transition‐metal Complex Cations to Lead Halide

The interplay between chirality with magnetism can break both the space and time inversion symmetry and have wide applications in information storage, photodetectors, multiferroics and spintronics. Herein, we report the chiral transition‐metal complex cation‐based lead halide, R‐CDPB and S‐CDPB. In contrast with the traditional chiral metal halides with organic cations, a novel strategy for chirality transfer from the transition‐metal complex cation to the lead halide framework is developed. The chiral complex cations directly participate the band structure and introduce the d‐d transitions and tunable magneto‐chiroptical effects in both the ultraviolet and full visible range into R‐CDPB and S‐CDPB. Most importantly, the coupling between magnetic moment of the complex cation and chiroptical properties is confirmed by the magneto‐chiral dichroism. For the band‐edge transition, the unprecedented modulation of +514% for S‐CDPB and ‐474% for R‐CDPB was achieved at ‐1.3 Tesla. Our findings demonstrate a novel strategy to combine chirality with magnetic moment, and provide a versatile material platform towards magneto‐chiroptical and chiro‐spintronic applications.

Strong Magneto-Chiroptical Effects through Introducing Chiral Transition-Metal Complex Cations to Lead Halide.

The interplay between chirality with magnetism can break both the space and time inversion symmetry and have wide applications in information storage, photodetectors, multiferroics and spintronics. Herein, we report the chiral transition-metal complex cation-based lead halide, R-CDPB and S-CDPB. In contrast with the traditional chiral metal halides with organic cations, a novel strategy for chirality transfer from the transition-metal complex cation to the lead halide framework is developed. The chiral complex cations directly participate the band structure and introduce the d-d transitions and tunable magneto-chiroptical effects in both the ultraviolet and full visible range into R-CDPB and S-CDPB. Most importantly, the coupling between magnetic moment of the complex cation and chiroptical properties is confirmed by the magneto-chiral dichroism. For the band-edge transition, the unprecedented modulation of +514 % for S-CDPB and -474 % for R-CDPB was achieved at -1.3 Tesla. Our findings demonstrate a novel strategy to combine chirality with magnetic moment, and provide a versatile material platform towards magneto-chiroptical and chiro-spintronic applications.

Mechanically Twisting-Induced Top-Down Chirality Transfer for Tunable Full-Color Circularly Polarized Luminescent Fibers.

Circularly polarized luminescence (CPL) materials with rich optical information are highly attractive for optical display, information storage, and encryption. Although previous investigations have shown that external force fields can induce CPL activity in nonchiral systems, the unique role of macroscopic external forces in inducing CPL has not been demonstrated at the level of molecule or molecular aggregate. Here, a canonical example of CPL generation by mechanical twisting in an achiral system consisting of a polymer matrix with embedded fluorescent molecules is presented. By carefully adjusting the twisting parameters in time and space, in conjunction with circular dichroism (CD), CPL, and 2D wide-angle X-ray scattering (2D WAXS) studies, a twisting-induced top-down chiral transfer mechanism derived from the molecular-level asymmetric rearrangement of fluorescent units is elucidated within polymers under external torsional forces. This top-down chiral transfer provides a simple, scalable, and versatile mechanical twisting strategy for the fabrication of CPL materials, allowing for fabricating full-color and handedness-tunable CPL fibers, where the macroscopic twist direction determines the CPL handedness. Moreover, the weavability of CPL fibers greatly extend their applications in anti-counterfeit encryption, as demonstrated by using embroidery techniques to design multilevel encryption patterns.