Achiral Units Research Articles

Optically active persistent luminescence in supramolecular nanoassemblies constructed from entirely achiral building blocks

Optically active persistent luminescent materials have attracted significant attention due to their distinctive luminescent characteristics and ability to exhibit rich circular polarization information. Despite extensive efforts to develop circularly polarized persistent luminescence (CPPL) materials using chiral molecules or polymers, fabricating CPPL materials from achiral units remains a big challenge. In this work, we introduce an efficient co-assembly strategy to create CPPL materials using entirely achiral organic molecules. The optical activities of co-assembled complexes are attributed to structural chirality, which arises from chiral nanohelices formed during symmetry breaking in the self-assembly process of C3-symmetric molecules. Achiral molecules with long-lasting phosphorescence can adhere to these chiral nanostructures via hydrogen bonding, and during the drying phase, form nanocrystals that align along helical fibers, resulting in circularly polarized, long-lasting phosphorescence. Enhanced CPPL efficiency, ranging from blue to yellow with a dissymmetry factor over 1.2 × 10−2 and lifetime of up to 0.6 s at room temperature, is achieved through hydrogen bonding driven co-assembly. Additionally, the CPPL spectra of these co-assemblies are captured using a homemade time-resolved circularly polarized long afterglow detection platform. This study not only presents a new approach for the high-efficiency design of CPPL materials from achiral building blocks but also significantly broadens the research possibilities in real-time CPPL analysis, offering a horizon in the exploration of CPPL materials.

Coupled Ferroelectricity and Optical Activity in Optically Active Ferroelectrics.

Ferroelectricity was initially discovered in 1921 in Rochelle salt (potassium sodium tartrate tetrahydrate), a chiral compound containing a chiral unit. However, the inherent relationship between coupled ferroelectricity and optical activity in chiral ferroelectrics derived from achiral units, as well as in polar ferroelectrics, remains insufficiently explored. In this regard, we propose a fresh concept of optically active ferroelectrics, specifically those crystallizing in seven optically active point groups (1, 2, 4, 3, 6, m, mm2). Subsequently, we elucidate the mechanism of coupled ferroelectricity and optical activity, emphasizing the cooperative interplay of chirality and polarity flipping under the influence of an electric field. Finally, we expound on the applications of this principle for the in situ generation of chiral enantiomers and polar isomers, thereby providing valuable insights into the chiral/polar research community and advancing our comprehension of ferroelectricity.

Quartz‐Like Structure, Optical Activity, and High Stability in the First Chiral Cation‐Coordinated Perovskite Semiconductor

AbstractPoor stability is a significant challenge to organic–inorganic hybrid perovskites for practical optoelectronic applications, which results from their inherent ionic nature and soft structures. The coordination bonding strategy is supposed to be a valid approach by enhancing the interaction between the cations and inorganic frameworks. Herein, the first pair of cation‐coordinated perovskites with high stability, achieved through coordination bonds between the cations and [PbXn] anions instead of the weak hydrogen bonds and van der Waals force presented in conventional ionic perovskites, is reported. In L/R‐(4HOPD)PbBr3 (4HOPD = 4‐hydroxypiperidine cation) (L/R=Left/Right–handed), one of the six halogen atoms is replaced by an oxygen atom from the cation. The PbO bond contributes to the high stability under a double 85 test. L/R‐(4HOPD)PbBr3 crystallizes in the tetragonal system, belonging to one of 11 enantiomorphic space group types, P41212 and P43212. Similar to quartz, the chirality originates from the helical assembly of achiral units. The chirality‐induced optical rotatory power is 16.84° mm−1 at 404 nm. Moreover, the uniaxial negative birefringent property with a comparable Δn value makes it a good alternative to quartz. The remarkable stability of this new perovskite presents significant potential for further investigation into stable perovskites and their applications in optical rotation and polarizing optics.

Chiral Lattice Resonances in 2.5-Dimensional Periodic Arrays with Achiral Unit Cells.

Lattice resonances are collective electromagnetic modes supported by periodic arrays of metallic nanostructures. These excitations arise from the coherent multiple scattering between the elements of the array and, thanks to their collective origin, produce very strong and spectrally narrow optical responses. In recent years, there has been significant effort dedicated to characterizing the lattice resonances supported by arrays built from complex unit cells containing multiple nanostructures. Simultaneously, periodic arrays with chiral unit cells, made of either an individual nanostructure with a chiral morphology or a group of nanostructures placed in a chiral arrangement, have been shown to exhibit lattice resonances with different responses to right- and left-handed circularly polarized light. Motivated by this, here, we investigate the lattice resonances supported by square bipartite arrays in which the relative positions of the nanostructures can vary in all three spatial dimensions, effectively functioning as 2.5-dimensional arrays. We find that these systems can support lattice resonances with almost perfect chiral responses and very large quality factors, despite the achirality of the unit cell. Furthermore, we show that the chiral response of the lattice resonances originates from the constructive and destructive interference between the electric and magnetic dipoles induced in the two nanostructures of the unit cell. Our results serve to establish a theoretical framework to describe the optical response of 2.5-dimensional arrays and provide an approach to obtain chiral lattice resonances in periodic arrays with achiral unit cells.

Defect-Free Synthesis of a Fully π-Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders.

Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically-active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with the degree of polymerization of more than 15 showed a strong circular dichroism with the dissymmetry factor of up to 1.7 × 10-2 and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well supported by molecular dynamics simulation.

Defect‐Free Synthesis of a Fully π‐Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders**

AbstractFully π‐conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect‐free synthesis and resolution of a fully π‐conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid‐promoted alkyne benzannulations of a rationally designed, random‐coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix‐inversion barrier, the isolated excess one‐handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10−2 and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well‐supported by molecular dynamics simulation.

Tuning of the Supramolecular Helicity of Peptide-Based Gel Nanofibers.

Helical supramolecular architectures play important structural and functional roles in biological systems. The helicity of synthetic molecules can be tuned mainly by the chiral manipulation of the system. However, tuning of helicity by the achiral unit of the molecules is less studied. In this work, the helicity of naphthalimide-capped peptide-based gel nanofibers is tuned by the alteration of methylene units present in the achiral amino acid. The inversion of supramolecular helicity has been extensively studied by CD spectroscopy and morphological analysis. The density functional theory (DFT) study indicates that methylene spacers influence the orientation of π-π stacking interactions of naphthalimide units in the self-assembled structure that regulates the helicity. This work illustrates a new approach to tuning the supramolecular chirality of self-assembled biomaterials.

Homologous and Heterologous Chiral Supramolecular Polymerization from Exclusively Achiral Building Blocks

AbstractAmong the enticing issues of chiral origins are: how chirality is born from the initial achiral units and the mechanisms for the transfer of chiral information. In this work, by combining a physical vortex and chiral seeds, a general process is revealed to generate chiral supramolecular polymers from achiral C3‐symmetric molecules. The symmetry‐broken assemblies from the achiral molecules could work as chiral seeds to initiate the polymerization of either homologous or heterologous achiral monomers. Concomitantly, the fragmentation of the polymer caused by the vortex during the nucleation‐elongation stages is shown to enlarge the domains of the chiral nuclei and then guide the polymer to grow into the predominant helicity with a high reactivity ratio. Moreover, the chiral structural information can be stored in different forms of assemblies. These new polymerization modes will provide guidance for the preparation of chiral materials.

Homologous and Heterologous Chiral Supramolecular Polymerization from Exclusively Achiral Building Blocks.

Among the enticing issues of chiral origins are: how chirality is born from the initial achiral units and the mechanisms for the transfer of chiral information. In this work, by combining a physical vortex and chiral seeds, a general process is revealed to generate chiral supramolecular polymers from achiral C3 -symmetric molecules. The symmetry-broken assemblies from the achiral molecules could work as chiral seeds to initiate the polymerization of either homologous or heterologous achiral monomers. Concomitantly, the fragmentation of the polymer caused by the vortex during the nucleation-elongation stages is shown to enlarge the domains of the chiral nuclei and then guide the polymer to grow into the predominant helicity with a high reactivity ratio. Moreover, the chiral structural information can be stored in different forms of assemblies. These new polymerization modes will provide guidance for the preparation of chiral materials.

White‐Light Emission and Circularly Polarized Luminescence from a Chiral Copper(I) Coordination Polymer through Symmetry‐Breaking Crystallization

AbstractAchieving white‐light emission, especially white circularly polarized luminescence (CPL) from a single‐phase material is challenging. Herein, a pair of chiral CuI coordination polymers (1‐M and 1‐P) have been prepared by the asymmetrical assembly of achiral ligands and Cu2I2 clusters. The compounds display dual emission bands and can be used as single‐phase white‐light phosphors, achieving a “warm”‐white‐light‐emitting diode with an ultra‐high color rendering index (CRI) of 93.4 and an appropriate correlated color temperature (CCT) of 3632 K. Meanwhile, corresponding CPL signals with maximum dissymmetry factor |glum|=8×10−3 have been observed. Hence, intrinsic white‐light emission and CPL have been realized simultaneously in coordination polymers for the first time. This work gains insight into the nature of chiral assembly from achiral units and offers a prospect for the development of single‐phase white‐CPL materials.

White-Light Emission and Circularly Polarized Luminescence from a Chiral Copper(I) Coordination Polymer through Symmetry-Breaking Crystallization.

Achieving white-light emission, especially white circularly polarized luminescence (CPL) from a single-phase material is challenging. Herein, a pair of chiral CuI coordination polymers (1-M and 1-P) have been prepared by the asymmetrical assembly of achiral ligands and Cu2 I2 clusters. The compounds display dual emission bands and can be used as single-phase white-light phosphors, achieving a "warm"-white-light-emitting diode with an ultra-high color rendering index (CRI) of 93.4 and an appropriate correlated color temperature (CCT) of 3632 K. Meanwhile, corresponding CPL signals with maximum dissymmetry factor |glum |=8×10-3 have been observed. Hence, intrinsic white-light emission and CPL have been realized simultaneously in coordination polymers for the first time. This work gains insight into the nature of chiral assembly from achiral units and offers a prospect for the development of single-phase white-CPL materials.

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Engineering Strongly Chiral Plasmonic Lattices with Achiral Unit Cells for Sensing and Photodetection

AbstractAlthough the concept of chirality has its origin in chemistry, the field of photonics is actively exploring and utilizing it. A new family of 2D chiral lattices constructed from fully achiral unit cells is introduced here. This type of chiral structure differs fundamentally from previously reported arrays made of chiral unit cells. In this system, circular dichroism (CD) appears due to the electromagnetic interaction between unit cells and the formation of lattice plasmons (LP). Importantly, the CD is strongly enhanced for anisotropic rectangular lattices, whereas the chiral signal in square lattices is found to be relatively weak. The results cover two configurations. The first has an index‐matched environment, and the second includes an asymmetric arrangement of refractive indices. The index‐matched model is preferable and supports ultrasharp LP resonances. Overall, excellent control of the spectral position and broadening of the CD peaks is also demonstrated by tuning the geometry and matrix refractive indices. These results can be useful for engineering polarization filters and chiral biosensors.

Luminescent Chiral Exciplexes with Sky-Blue and Green Circularly Polarized-Thermally Activated Delayed Fluorescence.

Luminescent exciplexes based on a chiral electron donor and achiral acceptors are reported as a new approach to design circularly polarized (CP) and thermally activated delayed fluorescence (TADF) emitters. This strategy results in rather high CP luminescence (CPL) values with glum up to 7×10-3 , one order of magnitude higher in comparison to the CPL signal recorded for the chiral donor alone (glum ∼7×10-4 ). This increase occurs concomitantly with a CPL sign inversion, as a result of the strong charge-transfer emission character, as experimentally and theoretically rationalized by using a covalent chiral donor-acceptor model. Interestingly, blue, green-yellow and red chiral luminescent exciplexes can be obtained by modifying with the electron accepting character of the achiral unit while keeping the same chiral donor unit. These results bring new (inter)molecular guidelines to obtain simply and efficiently multi-color CP-TADF emitters.

Unexpected Role of Achiral Glycine in Determining the Suprastructural Handedness of Peptide Nanofibrils.

Helical supramolecular architectures play important structural and functional roles in biological systems. Although their occurrence is widely perceived to correlate to fundamental chiral units including l-amino acids and d-sugars, the detailed relationship between molecular and supramolecular handedness is still unclear. At the same time, although achiral units are practically always in close proximity to chiral ones by covalent linkage along a polymeric chain, their effect on supramolecular handedness has received relatively less attention. Here, we designed a set of short amphiphilic peptides, in which an achiral glycine residue was incorporated at the interface between the hydrophobic and hydrophilic segments. We observed that glycine incorporation caused dramatic variations in suprastructural handedness in self-assembled peptide nanofibrils, and the effect of the hydrophilic charged residue at the C-terminus on supramolecular handedness was demolished, leading to chiral truncation. Furthermore, molecular dynamics simulations and quantum chemistry calculations revealed that the unanticipated role of the glycine residue in regulating supramolecular handedness originated from its effect on the conformational preference of single β-strands. Importantly, reduced density gradient analyses on single β-strands indicated that, due to the lack of a side chain in glycine, intricate noncovalent interactions were produced among the neighboring amino acid side chains of the incorporated glycine and its local backbone, resulting in diverse β-strand conformations.

Chirality-selective transparency induced by lattice resonance in bilayer metasurfaces

Chiral optical responses of bilayer metasurfaces made of twisted metallic nanorods are investigated in detail with focus on the collective effect due to lattice resonance (LR). Using an analytical approach based on the coupled dipole method (supported by full wave simulation), we find optical chirality is dramatically increased by the coupling between localized surface plasmon resonances and LR. The collective effect results in significant chiral signal even for metasurfaces made of achiral unit cells. The interlayer coupling generally destroys the Wood’s anomaly and the associated transparency. While making use of Pancharatnam–Berry (PB) phase and propagation phase, one can modulate the optical activity effectively and achieve chirality-selective transparency induced by LR in a designed structure with a g-factor of absorption as high as 1.99 (close to the upper limit of 2). Our studies not only reveal a new mechanism of modulating chiral optical response by combination effects from PB phase, propagation phase, and LR, but also give a quantitative relationship between the geometry configuration and chiral optical properties, thus providing helpful guidance for device design.

Optically Active Polymers with Cationic Units Connected through Neutral Spacers: Helical Conformation and Chirality Transfer to External Molecules

Cationic chiral polymers consisting of a chiral “Arg monomeric unit” consisting of two l-arginine moieties joined together through an oxyhexane-1,6-diyloxy spacer unit and achiral “Sp monomeric unit” based on the spermine moiety where the two units are connected through a 1,4-dioxobutane-1,4-diyl spacer unit (“C2 monomeric unit”) were prepared in the cationic form as a salt of p-toluenesulfonic acid. Polymer conformation could not be directly deduced from circular dichroism (CD) spectra based on the amide group bands (200–240 nm), which are generally used to quantify α-helical, β-sheet, and random coil residues because of spectral overlapping with the p-toluenesulfonate bands. On the other hand, a helical conformation was proposed on the basis of the relation between CD intensity and Arg monomeric unit ratio of polymers, while the proposed conformation may not be highly ordered but rather fragmented and partial. The helix-forming propensity of a polymer consisting of a higher Arg monomeric unit ratio was supported by MD simulations in water and in vacuum. The copolymer consisting of 100% Arg monomeric units [poly(Arg100-C2)], the one consisting of 42% Arg monomeric units and 58% Sp monomeric units [poly(Arg50-C2–Sp50-C2)], and the one consisting of 20% Arg monomeric units and 80% Sp monomeric units [poly(Arg25-C2–Sp75-C2)] exhibited chirality transfer to methyl orange (MO), where transfer was most efficient with poly(Arg50-C2–Sp50-C2). Chirality transfer efficiency also remarkably varied depending on the standing time of polymer solution in H2O before it is mixed with MO, the time after mixing, and the concentration of the polymer. Theoretical calculations of absorbance and CD spectra of polymer–MO complexes suggested that the induced CD spectra mostly having bisignet spectral patterns are not based on exciton coupling between two MO molecules bound to the polymer chain but are composed of independent excitation bands. The design of chiral macromolecules introduced in this work based on a chain composed of charged chiral and achiral units separated by neutral achiral linker (spacer) units has not been studied from a view of chiral polymeric materials. Such a design of polymer chain may be applicable to a wider variety of chemical structures and will largely widen the scope of optically active polymers with helical conformation.

Plasmonic chirality of one-dimensional arrays of twisted nanorod dimers: the cooperation of local structure and collective effect.

We study the chiral optical properties of one-dimensional arrays of plasmonic twisted nanorod dimers. By using finite-difference time-domain (FDTD) simulation and analytical approach based on the coupled dipole model, we have revealed unusual chiral optical responses due to the cooperation of local structure and collective effect. It is found that one-dimensional arrays of achiral unit may show chiral optical responses. Moreover, besides the classical bisignate lineshape of circular dichroism (CD) induced by localized surface plasmon resonance, a new CD peak/dip appears, originating from Wood anomaly. Near the Wood anomaly frequency, the optimal twist angle to achieve the highest CD has been shifted compared with that of single twisted nanorod dimer. The universal geometric configurations of the strongest chiral optical responses have been found.

Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal-Organic Assemblies.

Herein we elucidate the interplay of chiral, chelate, solvent, and hydrogen-bonding information in the self-assembly of a series of new three-dimensional metal-organic architectures. Enantiopure ligands, each containing H-bond donors and acceptors, form different structures, depending on the ratio in which they are combined: enantiopure components form M4L4 assemblies, whereas racemic mixtures form M3L3 stacks. Chiral amplification within M3L3 enantiomers was observed when a 2:1 ratio of R and S subcomponent enantiomers was employed. Simply switching the solvent (from MeCN to MeOH) or chelating unit (from bidentate to tridentate) increased the diversity of structures that can be generated from these building blocks, leading to the selective formation of novel M2L2 and M3L2 assemblies. The addition of achiral ligand building blocks resulted in the formation of further structures: When an achiral subcomponent was combined with its R and S chiral congeners, a three-layer heteroleptic architecture was generated, with the achiral unit sitting at the top of the stack. When combined with the S enantiomer only, however, the achiral unit assembled in the center of the structure, thus demonstrating the selective placement of achiral units within chiral systems. Further sorting experiments revealed that combining R and S stereocenters within a single ligand led to diastereoselective product generation. These results show how geometric complementarity between different ligands impacts upon the degree of hydrogen-bonding within the assembly, stabilizing specific low-symmetry architectures from among many possible structural outcomes.

Formation of co-racemic uranyl chromate constructed from chiral layers of different topology

Four new inorganic uranyl chromates were obtained by evaporation and hydrothermal methods: [(CH3)2NH2]2[(UO2)2(CrO4)3(H2O)](H2O) (1), K(Rb0.6K0.4)[(UO2)2(CrO4)3(H2O)](H2O)3 (2) [(CH3)3CNH3]2[(UO2)2(CrO4)3H2O] (3), [(CH3)2NH2]4[(UO2)2(CrO4)3H2O]2(H2O) (4). Their structures are based on two-dimensional chiral or achiral units with the composition [(UO2)2(CrO4)3(H2O)]2− and two types of topologies (A or/and B). The structural architecture of (4) is unique amongst all known uranyl-based structures, and unusual among hybrid organic/inorganic structures in general as it contains layers of identical composition, but of different topology. The unique structural configurations and non-centrosymmetry in (1) and (4) is governed by selective formation of hydrogen bonding rather than by the formation of hydrophobic and hydrophilic zones in the organic interlayer. It is shown that chiral architectures in uranyl systems may form from achiral building units as observed in (3) and (4). This is somewhat analogous to certain organic compounds, where achiral molecules are also able to form chiral layers. Within the concept of such an interpretation the structure of (3) can then be described as a racemate consisting of two A and A′ chiral layers. In a similar approach the structure of (4) can be interpreted as being formed by four chiral layers. Layer pairs AA′ and BB′ can then be considered as racemic pairs and the whole structure is a co-racemate built by a combination of two racemates. Two-stage formation can be suggested for (4).