Chiral supramolecular high-order structure based on co-assembly of star-shaped block copolymer and chiral additive and manufacturing method thereof

Abstract

The present application relates to a chiral supramolecular high-order structure based on co-assembly of a star-shaped block copolymer and a chiral additive and post-treatment, and a manufacturing method thereof. A chiral supramolecular high-order structure according to embodiments of the present application is formed through co-assembly of an achiral star-shaped block copolymer and a chiral additive, wherein the achiral star-shaped block copolymer is capable of multiple hydrogen bonds with the chiral additive, and can provide a unimolecular micelle environment linked by covalent bonds. Therefore, the chiral supramolecular high-order structure of the present application has a remarkably high yield rate compared to a chiral molecular structure comprising a conventional linear block copolymer, has a distinct helical direction of the supramolecular structure transferred from the molecular chirality, and has an asymmetric factor level of 0.038, so that strong supramolecular chirality occurs in a wide wavelength range of ultraviolet to visible light.

Description

Chiral supramolecular higher-order structures based on co-assembly of star-shaped block copolymers and chiral additives and methods for preparing the same

[0001] The present invention relates to a chiral supramolecular higher-order structure and a method for preparing the same based on co-assembly and post-processing of a star-shaped block copolymer and a chiral additive.

[0002] The field of chiral materials has grown significantly, inspired by the abundance of chiral structures found in nature. Among these, chiral supramolecular assemblies have attracted considerable attention due to their complexity and diversity in structural and chiroptical behavior. These assemblies derive their supramolecular chirality from the asymmetric arrangement of constituent molecules via non-covalent bonds, which serve as bridges for the hierarchical transfer of chirality. Supramolecular chirality can arise from the self-assembly of chiral molecules, the co-assembly of chiral and achiral molecules, or the self-assembly of achiral molecules under chiral environmental influences or conditions. Careful control of several parameters allows for manipulation of the generation of supramolecular chirality. The kinetics and thermodynamics of chiral supramolecular assemblies can be controlled by carefully designing the molecular structures of the building blocks, or by controlling dynamic non-covalent interactions, solvent effects, stoichiometry, temperature, and time. This has led to the creation of various chiral supramolecular structures, such as helical nanotubes, helical microtoroids, and spiral tubes. Interestingly, chiral supramolecular assembly can also be induced in systems composed solely of achiral molecules. This can be achieved by applying external stimuli such as asymmetric mechanical forces, circularly polarized light irradiation, or magnetic forces. This extensive exploration of chiral supramolecular assembly offers exciting prospects for the development of advanced materials and functional systems with interesting properties and applications in various research fields.

[0003] Circularly polarized luminescence (CPL) active materials have attracted increasing attention in materials science and chirality-related applications due to their significant potential in circularly polarized organic light-emitting diodes (OLEDs), information encryption, circularly polarized photodetectors, and spintronic devices. Recently, several strategies have been devised to construct CPL active materials, including chemical coupling of chiral molecules with luminescent chromophores, introduction of circularly polarized liquid crystal filters, and circularly polarized fluorescence energy transfer from chiral fluorescent polymers to achiral fluorescent chromophores. In particular, chiral configuration of achiral fluorescent dye molecules via chiral supramolecular assembly has been extensively studied. In this approach, chiral information is transferred to achiral dye molecules participating in co-assembly via noncovalent interactions. This approach offers advantages such as low manufacturing cost, high stability, and excellent processability. Furthermore, it can generate full-color CPL emission, which is essential for display technology, and improves luminescence efficiency by preventing fluorescence quenching due to aggregation. Despite these advances, the luminescence dissymmetry factor (g) of the manufactured CPL active materials lum ) value is usually 10 -3 10 in -2 However, these materials fall short of expectations and do not meet practical application requirements. Therefore, a robust and versatile approach is urgently needed to construct robust CPL materials with stable handedness, high luminescence quantum yield (QY), and significantly high asymmetry factors.

[0004] Star-shaped polymers represent a relatively simple yet intriguing 3D deviation from linear polymers, with linear arms extending from a central branching core via covalent bonds. Compared to linear block copolymers (BCPs), unimolecular star-shaped BCPs exhibit enhanced stability and resilience to external stimuli such as pH, heat, solvent, or salt concentration. To date, exploration of chiral supramolecular assemblies has been limited to chiral star-shaped polymers with low grafting densities (i.e., three-armed polymers).

[0005] To date, research on chiral supramolecular assembly has primarily focused on achiral linear BCPs complexed with chiral additives. However, this approach, which relies on linear BCPs, has revealed several limitations. Specifically, these include low production yields of helical structures and the weak generation of supramolecular chirality in the ultraviolet region. These results are primarily due to the dynamic and unpredictable assembly process of linear BCPs, which are sensitive to environmental changes.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] (Patent Document 1) Republic of Korea Patent Publication No. 10-2022-0007002

[0009] (Patent Document 2) Republic of Korea Patent Publication No. 10-2023-0064850

[0010] (Patent Document 3) Republic of Korea Patent Publication No. 10-2022-0072504

[0011] (Patent Document 4) Republic of Korea Patent Publication No. 10-2517428

[0012] [Non-patent literature]

[0013] (Non-patent Document 1) DA Siriwardane, O. Kulikov, JF Reuther, BM Novak, "Rigid, Helical Arm Stars through Living Nickel Polymerization of Carbodiimides", Macromolecules 2017, 50, 832.

[0014] The present invention provides a chiral supramolecular higher-order structure and a method for preparing the same based on co-assembly and post-processing of a star-shaped block copolymer and a chiral additive.

[0015] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0016] The first aspect of the present invention provides a chiral supramolecular higher-order structure, comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral additive, wherein the polyacrylic acid and the chiral additive non-covalently interact, and the handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive.

[0017] The second aspect of the present invention provides a circularly polarized light-emitting structure comprising a chiral supramolecular higher-order structure according to the first aspect; and an achiral fluorescent substance, wherein the circularly polarized light-emitting direction of the circularly polarized light-emitting structure is determined according to the handedness of the chiral supramolecular higher-order structure.

[0018] The third aspect of the present invention provides a method for producing a chiral supramolecular higher-order structure, comprising: preparing a mixed solution comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a chiral additive, and a solvent; stirring the mixed solution; and applying and thermally annealing the stirred mixed solution, wherein the polyacrylic acid and the chiral additive interact non-covalently, and the handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive.

[0019] The chiral supramolecular higher-order structures according to the embodiments of the present disclosure are formed through co-assembly of an achiral star-shaped block copolymer and a chiral additive, wherein the achiral star-shaped block copolymer is capable of multiple hydrogen bonds with the chiral additive and can provide a unimolecular micelle environment linked by covalent bonds. Therefore, the chiral supramolecular higher-order structures of the present disclosure have a significantly higher yield than chiral molecular structures including conventional linear block copolymers, have a distinct helical direction of the supramolecular structures transferred from molecular chirality, and have the characteristics of strong supramolecular chirality occurring in a wide wavelength range from ultraviolet to visible light with an asymmetry factor of 0.038.

[0020] The method for manufacturing a chiral supramolecular higher-order structure according to the embodiments of the present invention has the characteristic of establishing a hierarchical supramolecular chiral structure evolution mechanism by controlling the thermodynamics and kinetics of co-assembly to form a chiral supramolecular higher-order structure by controlling the thermal annealing time.

[0021] A circularly polarized light-emitting structure formed by integrating an achiral fluorescent agent into a chiral supramolecular higher-order structure according to the embodiments of the present invention has a light-emitting asymmetry factor of up to 0.11 and exhibits improved light-emitting efficiency.

[0022] FIG. 1 is a schematic diagram of a step-by-step process for preparing a CPL-active hybrid film through co-assembly of achiral star-shaped PAA-b-PS, R / S-MA, and achiral fluorescent dye molecules in one embodiment of the present invention.

[0023] FIGS. 2A to 2C are atomic force microscope (AFM) height images comparing a pure star-shaped PAA-b-PS film (a) and a star-shaped PAA-b-PS film incorporating R-MA (b) and S-MA (c) molecules in one embodiment of the present invention.

[0024] FIGS. 3A to 3C illustrate the distribution of hydrodynamic radii observed in pure star-shaped PAA-b-PS (a), star-shaped PAA-b-PS including R-MA (b), and star-shaped PAA-b-PS including S-MA (c) in one embodiment of the present invention.

[0025] FIG. 4 shows FTIR spectra of MA molecules including star-shaped PAA-b-PS (a), MA (b), and star-shaped PAA-b-PS (c) in one embodiment of the present invention.

[0026] FIG. 5 shows, in one embodiment of the present invention, the formation of hydrogen bonds between PAA and S-MA and the hydrogen bond energy calculated using density functional theory (DFT).

[0027] Figures 6a and 6b show SEM images of chiral supramolecular fiber-like structures formed through co-assembly of R-MA (a) and S-MA (b) and achiral star-shaped PAA-b-PS in one embodiment of the present invention.

[0028] Figures 7a and 7b show SEM images with progressively increased magnification of a right-handed fiber-like structure (a) formed by co-assembly of achiral star-shaped PAA-b-PS and R-MA and a left-handed fiber-like structure (b) formed by co-assembly of achiral star-shaped PAA-b-PS and S-MA in one embodiment of the present invention.

[0029] FIG. 8 is an AFM image with progressively increased magnification of right-handed fiber-like structures formed by co-assembly of achiral star-shaped PAA-b-PS and R-MA in one embodiment of the present invention, showing nanoscale belt-like structures composed of densely packed dot-like aggregates.

[0030] Figures 9a and 9b show the CD and corresponding absorption spectra of chiral supramolecular fiber-like structures formed by co-assembly of R / S-MA (a) and (b) achiral star-shaped PAA-b-PS and R / S-MA in deionized water in one embodiment of the present invention.

[0031] FIG. 10 shows a spectrum of g-factor values ​​for a chiral supramolecular structure formed through co-assembly of achiral star-shaped PAA-b-PS and R / S-MA having a molar ratio of AA repeating units to MA of 1:2 in one embodiment of the present invention.

[0032] FIGS. 11a to 11f show, in one embodiment of the present invention, a DMT modulus image of a chiral supramolecular fiber-like structure formed through co-assembly of achiral star-shaped PAA-b-PS and R-MA (a) and S-MA (b), a DMT modulus image of a pure star-shaped PAA-b-PS film (c), a force-distance curve of a chiral supramolecular fiber-like structure formed through co-assembly of achiral star-shaped PAA-b-PS and R-MA (d) and S-MA (e), and a force-distance curve of a pure star-shaped PAA-b-PS film (f).

[0033] FIG. 12 shows a 60°C annealing time-dependent CD spectrum of a complex comprising star-shaped PAA-b-PS and S-MA in one embodiment of the present invention.

[0034] FIGS. 13a to 13c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60°C for 1 hour in one embodiment of the present invention.

[0035] FIGS. 14a to 14c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60°C for 2 hours in one embodiment of the present invention.

[0036] FIGS. 15 a to 15 c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60° C. for 3 hours in one embodiment of the present invention.

[0037] Figures 16a to 16c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60°C for 4 hours in one embodiment of the present invention.

[0038] Figures 17a to 17c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60°C for 8 hours in one embodiment of the present invention.

[0039] Figures 18a to 18c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60°C for 12 hours in one embodiment of the present invention.

[0040] FIGS. 19 a to 19 c show a low-resolution SEM (LR-SEM) image (a), a high-resolution SEM (HR-SEM) image (b), and an AFM image (c) of a composite film comprising star-shaped PAA-b-PS and S-MA after thermal annealing at 60° C. for 24 hours in one embodiment of the present invention.

[0041] Figure 20 illustrates a plausible mechanism for forming hierarchical chiral supramolecular structures through co-assembly by continuous thermal annealing and gradual solvent evaporation in one embodiment of the present invention.

[0042] Figures 21a to 21f are SEM images and g-factor spectra (a and d) of chiral supramolecular structures formed through co-assembly of star-shaped PAA homopolymer and R-MA in one embodiment of the present invention; star-shaped PAA-b-PS (M n, PAA = 100 kg·mol -1 , M n, PS = 250 kg·mol -1 ) and R-MA; SEM images and g-factor spectra (b and e) of chiral supramolecular structures formed via co-assembly; and star-shaped PAA-b-PS (M n, PAA = 100 kg·mol-1 , M n, PS = 320 kg·mol -1 ) and R-MA co-assembly, SEM images and g-factor spectra (c and f) are shown.

[0043] Figure 22 is, in one embodiment of the present invention, a star-shaped PAA-b-PS(M n, PAA = 100 kg·mol -1 , M n, PS = 190 kg·mol -1 ) and chiral supramolecular structures formed through co-assembly of R-MA (concentration 1 mg ml -1 , 2.5 mg·ml -1 , and 5 mg·ml -1 ) shows the g-factor spectrum.

[0044] Figures 23 a to c are, in one embodiment of the present invention, star-shaped PAA-b-PS (M n, PAA = 100 kg·mol -1 , M n, PS = 190 kg·mol -1 ) and chiral supramolecular structures formed through co-assembly of R-MA (concentration 1 mg ml -1 (a), 2.5 mg·ml -1 (b), and 5 mg·ml -1 (c)) shows the SEM image.

[0045] Figures 24a to 24c show FTIR spectra of PAA-b-PS / MA, achiral dye molecules, and PAA-b-PS / MA including achiral dye molecules in one embodiment of the present invention, in which PCA (a), OG (b), and RhB (c) are used as dye molecules, respectively.

[0046] Figures 25a to 25c show CD and corresponding absorption spectra of a chiral supramolecular hybrid film incorporating PCA (a), OG (b), and RhB (c) molecules in one embodiment of the present invention.

[0047] Figures 26a to 26c show the g-factor spectra of chiral supramolecular hybrid films incorporating PCA (a), OG (b), and RhB (c) molecules in one embodiment of the present invention.

[0048] Figures 27a to 27f show the CPL spectra and luminescence asymmetry factor (g) of a chiral supramolecular hybrid film integrated with PCA molecules excited at 350 nm (a,d), OG molecules excited at 488 nm (b,e), and RhB molecules excited at 350 nm in one embodiment of the present invention. lum ) spectrum (the inset image is a photograph of the CPL-active hybrid film under 365 nm light irradiation).

[0049] FIGS. 28 a and b show SEM images of a CPL-active supramolecular hybrid film comprising PAA-b-PS / R-MA and PCA molecules (a) and PAA-b-PS / S-MA and PCA molecules (b) in one embodiment of the present invention.

[0050] FIGS. 29 a and b show SEM images of a CPL-active supramolecular hybrid film comprising PAA-b-PS / R-MA and OG molecules (a) and PAA-b-PS / S-MA and OG molecules (b) in one embodiment of the present invention.

[0051] FIGS. 30 a and b show SEM images of a CPL-active supramolecular hybrid film comprising PAA-b-PS / R-MA and RhB molecules (a) and PAA-b-PS / S-MA and RhB molecules (b) in one embodiment of the present invention.

[0052] Figures 31 a and b show the CPL spectrum and luminescence asymmetry factor (g) of a chiral supramolecular hybrid film incorporating CsPbBr3 nanocrystals in one embodiment of the present invention. lum ) is a spectrum representation.

[0053] Hereinafter, with reference to the attached drawings, implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be implemented in various different forms and is not limited to the implementation examples and embodiments described herein. In addition, in the drawings, parts irrelevant to the description have been omitted to clearly explain the present invention, and similar parts have been designated with similar drawing reference numerals throughout the specification.

[0054] Throughout this specification, when a part is said to be "connected" to another part, this includes not only cases where it is "directly connected" but also cases where it is "electrically connected" with another element in between.

[0055] Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0056] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0057] The terms "about," "substantially," and the like used in this specification are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which exact or absolute values ​​are mentioned to aid understanding of the present application.

[0058] The terms “step of” or “step of” as used throughout this specification do not mean “step for”.

[0059] Throughout this specification, the term "combination(s) thereof" included in the expressions in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the expressions in the Makushi format, and means including one or more selected from the group consisting of said components.

[0060] Throughout this specification, references to “A and / or B” mean “A or B, or A and B.”

[0061] As used throughout this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms and all possible isomers thereof. For example, the alkyl or alkyl group may be a methyl group (Me), an ethyl group (Et), an n-propyl group ( n Pr), iso-profiler ( i Pr), n-butyl group ( n Bu), iso-butyl group( i Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group (sec-Bu, sec Bu), n-pentyl group ( n Pe), iso-pentyl group ( iso Pe), sec-pentyl group ( sec Pe), tert-pentyl group ( t Pe), neo-pentyl group ( neo Pe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethylpentyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, but may not be limited thereto.

[0062] Below, the implementation examples of the present invention are described in detail, but the present invention may not be limited thereto.

[0063] The first aspect of the present invention provides a chiral supramolecular higher-order structure, comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral additive, wherein the polyacrylic acid and the chiral additive non-covalently interact, and the handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive.

[0064] In one embodiment of the present invention, the core block polymer, polyacrylic acid, and the chiral additive may non-covalently interact through hydrogen bonding.

[0065] In one embodiment of the present invention, the core block polymer and the chiral additive may interact non-covalently, so that the chirality of the chiral additive is transferred to the core block polymer.

[0066] In one embodiment of the present invention, the preferred handedness of the chiral supramolecular higher-order structure may be determined depending on the chirality of the chiral additive. For example, when the chiral additive is mandelic acid (MA), the chiral supramolecular higher-order structure loaded with S-MA may produce a left-handed fiber-like structure, and the chiral supramolecular higher-order structure loaded with R-MA may produce a right-handed fiber-like structure.

[0067] In one embodiment of the present invention, the shell block polymer may be a hydrophobic polymer.

[0068] In one embodiment of the present invention, the hydrophobic polymer may include one or more selected from polystyrene, polyethylene, polypropylene, polybutadiene, polyaniline, polythiophene, poly(phenylene vinylene), and derivatives thereof, but may not be limited thereto.

[0069] In one embodiment of the present invention, the polythiophene may be a polyalkylthiophene including, but not limited to, poly(3-ethylthiophene), poly(3-butylthiophene), poly(3-pentylthiophene), or poly(3-hexylthiophene).

[0070] In one embodiment of the present invention, the chiral additive may include a chiral carbon having molecular chirality; and a carboxylic acid group and / or a hydroxyl group as a functional group capable of multiple hydrogen bonds with the acrylic acid (AA) repeating unit of the polyacrylic acid.

[0071] In one embodiment of the present invention, the chiral additive may include one or more selected from mandelic acid, tartaric acid, aspartic acid, tyrosine, ibuprofen, and hydroxymandelic acid, but may not be limited thereto.

[0072] In one embodiment of the present invention, the achiral star-shaped block copolymer may have a star-shaped structure including a plurality of arms extending from the core block polymer. The achiral star-shaped block copolymer may have a star-shaped structure including 21 arms extending from the core block polymer.

[0073] In one embodiment of the present invention, the achiral star-shaped block copolymer may include a plurality of arms extending from the core block polymer, and the shell block polymer may be formed by bonding to each of the plurality of arms.

[0074] In one embodiment of the present invention, the achiral star-shaped block copolymer may be an amphiphilic polymer comprising a hydrophilic core block polymer and a hydrophobic shell block polymer. In one embodiment of the present invention, the core block polymer is a hydrophilic polymer and the shell block polymer is a hydrophobic polymer, and when forming a chiral supramolecular higher-order structure through co-assembly, phase separation may occur due to chemical incompatibility between the core block polymer and the shell block polymer.

[0075] In one embodiment of the present invention, the achiral star-shaped block copolymer can form multiple hydrogen bonds with a chiral additive and provide a unimolecular micelle environment connected by covalent bonds. Therefore, the chiral supramolecular higher-order structure of the present invention has a significantly higher yield compared to a chiral molecular structure including a conventional linear block copolymer, has a distinct helical direction of the supramolecular structure transferred from molecular chirality, and has an asymmetry factor of approximately 0.038, so that strong supramolecular chirality occurs over a wide wavelength range from ultraviolet to visible light.

[0076] In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, but may not be limited thereto. In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, about 1:1 to about 1:3, or about 1:1 to about 1:2, but may not be limited thereto.

[0077] In one embodiment of the present invention, the chiral supramolecular higher-order structure may form a belt-shaped structure.

[0078] In one embodiment of the present invention, the chiral supramolecular higher-order structure may form a helical fiber-shaped structure.

[0079] In one embodiment of the present invention, the chiral supramolecular higher-order structure may be formed through a series of co-assembly processes of an achiral star block copolymer and a chiral additive, including the chirality of the chiral additive being transferred to the core block polymer to form a chiral star block copolymer, the chiral star block copolymer agglomerating to form aggregates, the aggregates packing to form a belt-shaped structure, and the belt-shaped structure packing to form a helical fiber-shaped structure.

[0080] In one embodiment of the present invention, the belt-shaped structure may have a nano-size ranging from about 50 nm to about 500 nm. In one embodiment of the present invention, the fiber-shaped structure may have a micro-size ranging from about 1 μm to about 100 μm.

[0081] In one embodiment of the present invention, the dissymmetry factor (g-factor) value of the chiral supramolecular higher-order structure may be about 0.03 or more, or about 0.03 to about 0.038. In one embodiment of the present invention, the dissymmetry factor value of the chiral supramolecular higher-order structure may be greater than the dissymmetry factor value observed in a chiral supramolecular structure formed through co-assembly of an achiral linear block copolymer and a chiral additive; and in the self-assembly of a chiral block copolymer.

[0082] In one embodiment of the present invention, the chiral supramolecular higher-order structure may be formed into the helical fiber-shaped structure, so that when a thin film is formed, the mechanical properties of elastic modulus or hardness (H) may be improved.

[0083] In one embodiment of the present invention, the elastic modulus value of the chiral supramolecular higher-order structure may be about 0.1 GPa or more, or about 0.1 GPa to about 0.106 GPa.

[0084] The second aspect of the present invention provides a circularly polarized light-emitting structure comprising a chiral supramolecular higher-order structure according to the first aspect; and an achiral fluorescent substance, wherein the circularly polarized light-emitting direction of the circularly polarized light-emitting structure is determined according to the handedness of the chiral supramolecular higher-order structure.

[0085] Detailed explanations of parts that overlap with the first aspect of the present application have been omitted, but the contents described in the first aspect of the present application may be equally applied even if the explanation is omitted in the second aspect of the present application.

[0086] In one embodiment of the present invention, the achiral fluorescent substance comprises a dye compound comprising at least one selected from 1-pyrenecarboxylic acid, Oregon Green 488, rhodamine, anthracene-9-carboxylic acid, terephthalic acid, naphthalene dicarboxylic acid, coumarin-6-carboxylic acid, 7-hydroxy-4-methylcoumarin-3-carboxylic acid, and naphthalene-1,8-dicarboxylic acid; a semiconductor compound comprising at least one selected from CdS, CdSe, and PbS; a perovskite nanocrystal compound comprising at least one selected from CsPbX3 (cesium lead halide) and MAPbX3 (methylammonium lead halide); Or it may be an upconversion nanoparticle comprising at least one selected from NaYF4:Yb, Er (ytterbium (Yb) and erbium (Er) doped sodium yttrium fluoride (NaYF4)) and NaYF4:Yb, Tm (Yb and thulium (Tm) doped NaYF4).

[0087] In one embodiment of the present invention, the CsPbX3 is, as a non-limiting example, CsPbF 3- , CsPbCl3, CsPbBr3, CsPbI3, CsPbBr2I ,Or it can be CsPbBrI2. In one embodiment of the present invention, the MAPbX3 is, as a non-limiting example, MAPbF 3- , MAPbCl3, MAPbBr3, MAPbI3, MAPbBr2I , Or it could be MAPbBrI2.

[0088] In one embodiment of the present invention, the dye compound may include a carboxylic acid group as a functional group. In one embodiment of the present invention, the dye compound may hydrogen bond with the acrylic acid repeating unit of the chiral supramolecular higher-order structure and the chiral additive by including a carboxylic acid group as a functional group.

[0089] In one embodiment of the present invention, the semiconductor compound, the perovskite nanocrystal compound, and the upconversion nanoparticles may be grown and included within the core block polymer, polyacrylic acid.

[0090] In one embodiment of the present invention, the luminescence asymmetry factor value of the circular polarization light-emitting structure may be about 0.03 or more, or about 0.03 to about 0.11.

[0091] In one embodiment of the present invention, the circularly polarized light-emitting structure may have a higher luminescence quantum yield (QY) than a film including a pure achiral phosphor.

[0092] The third aspect of the present invention provides a method for producing a chiral supramolecular higher-order structure, comprising: preparing a mixed solution comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a chiral additive, and a solvent; stirring the mixed solution; and applying and thermally annealing the stirred mixed solution, wherein the polyacrylic acid and the chiral additive interact non-covalently, and the handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive.

[0093] Detailed descriptions of overlapping parts with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect of the present application.

[0094] In one embodiment of the present invention, by stirring the mixed solution, a non-covalent interaction (hydrogen bond) is formed between the acrylic acid repeating unit of the polyacrylic acid and the chiral additive, so that a complex (chiral star block copolymer) including the achiral star block copolymer and the chiral additive can be formed.

[0095] In one embodiment of the present invention, the stirring may be performed for about 1 day or more, about 2 days or more, or about 1 day to about 10 days, but may not be limited thereto.

[0096] In one embodiment of the present invention, the solvent may include at least one selected from dimethylformamide, toluene, tetrahydrofuran, ethyl acetate, 1,4-dioxane, dimethyl sulfoxide, acetonitrile, acetone, ethanol, and methanol, but may not be limited thereto. In one embodiment of the present invention, the solvent may have excellent solubility for both the achiral star block copolymer and the chiral additive, thereby helping to form non-covalent interactions (hydrogen bonds) between the acrylic acid repeating units of the polyacrylic acid and the chiral additive.

[0097] In one embodiment of the present invention, during the thermal annealing process, the chiral additive that does not form a hydrogen bond with the acrylic acid repeating unit may be thermally decomposed. Therefore, in order to enable efficient chirality transfer by forming hydrogen bonds (non-covalent interactions) with all the acrylic acid repeating units, the mixed solution may contain an excess of the chiral additive relative to the number of the acrylic acid repeating units.

[0098] In one embodiment of the present invention, the molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the chiral additive may be about 1:1 to about 1:3, but may not be limited thereto. In one embodiment of the present invention, the molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the chiral additive may be about 1:1 to about 1:3, about 1:1 to about 1:2.5, about 1:1 to about 1:2, about 1:1.5 to about 1:3, about 1:1.5 to about 1:2.5, or about 1:1.5 to about 1:2, but may not be limited thereto.

[0099] In one embodiment of the present invention, co-assembly of the achiral star-shaped block copolymer and the chiral additive may be performed through the thermal annealing, thereby forming the chiral supramolecular higher-order structure.

[0100] In one embodiment of the present invention, the formation mechanism of the chiral supramolecular higher-order structure over time of the thermal annealing is described in more detail:

[0101] 1) In the above mixed solution, a complex (chiral star block copolymer) including the achiral star block copolymer and the chiral additive is formed as a primary structure. 2) In the initial stage of the thermal annealing, as the solvent evaporates, the concentration of the complex gradually increases, and the complexes aggregate with each other to form irregular dot-shaped aggregates having a diameter in the nanometer range. 3) As the thermal annealing progresses, the dot-shaped aggregates form a belt-shaped structure through an elongated packing. 4) As the thermal annealing continues, the belt-shaped structure helically packs to form a fiber-shaped structure having a specific handedness.

[0102] In one embodiment of the present invention, the thermal annealing may be performed at a temperature range of about 50°C to about 70°C, but may not be limited thereto. In one embodiment of the present invention, the thermal annealing may be performed at a temperature range of about 50°C to about 70°C, about 50°C to about 65°C, about 55°C to about 70°C, or about 55°C to about 65°C, but may not be limited thereto.

[0103] In one embodiment of the present invention, the thermal annealing may be performed for about 1 hour to about 48 hours, but may not be limited thereto.

[0104] In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, but may not be limited thereto. In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, about 1:1 to about 1:3, or about 1:1 to about 1:2, but may not be limited thereto.

[0105] In one embodiment of the present invention, the achiral star-shaped block copolymer may be an amphiphilic polymer comprising a hydrophilic core block polymer and a hydrophobic shell block polymer. In one embodiment of the present invention, the core block polymer is a hydrophilic polymer and the shell block polymer is a hydrophobic polymer, and when forming a chiral supramolecular higher-order structure through co-assembly, phase separation may occur due to chemical incompatibility between the core block polymer and the shell block polymer.

[0106] In one embodiment of the present invention, when the volume ratio of the core block polymer and the shell block polymer is less than about 1:1, sufficient phase separation between the core block polymer and the shell block polymer may not occur, so that an irregular chiral supramolecular higher-order structure with a low asymmetry factor may be formed, and when the volume ratio of the core block polymer and the shell block polymer is more than about 1:4, a problem may occur in which a chiral supramolecular higher-order structure is formed that is not thermodynamically stable even after thermal annealing for an appropriate period of time and is dynamically trapped.

[0107] In one embodiment of the present invention, the concentration of the mixed solution is 1 mg·mL -1 Exceeding or exceeding about 10 mg mL -1It may be, but may not be limited thereto. In one embodiment of the present invention, the concentration of the mixed solution is 1 mg·mL. -1 Exceeding or exceeding about 10 mg mL -1 , 1 mg·mL -1 Exceeding or exceeding about 7 mg mL -1 , 1 mg·mL -1 Exceeding or exceeding about 5 mg mL -1 , 1 mg·mL -1 Excess to about 3 mg mL -1 , about 2 mg·mL -1 About 10 mg·mL -1 , about 2 mg·mL -1 About 7 mg·mL -1 , about 2 mg·mL -1 About 5 mg·mL -1 , or about 2 mg·mL -1 About 3 mg·mL -1 It may be, but may not be limited thereto. In one embodiment of the present invention, the concentration of the mixed solution is 1 mg·ml -1 In the case below, the chiral supramolecular higher-order structure does not exhibit a distinct handedness, so the chirality is weak, and the concentration of the mixed solution is about 10 mg ml -1 If it is excessive, problems may arise that hinder the evolution of chiral supramolecular higher-order structures.

[0108] In one embodiment of the present invention, the method for producing the chiral supramolecular higher-order structure may further include adding an achiral fluorescent agent to the stirred mixed solution and stirring the same before performing the thermal annealing.

[0109] In one embodiment of the present invention, the achiral fluorescent substance comprises a dye compound comprising at least one selected from 1-pyrenecarboxylic acid, Oregon Green 488, rhodamine, anthracene-9-carboxylic acid, terephthalic acid, naphthalene dicarboxylic acid, coumarin-6-carboxylic acid, 7-hydroxy-4-methylcoumarin-3-carboxylic acid, and naphthalene-1,8-dicarboxylic acid; a semiconductor compound comprising at least one selected from CdS, CdSe, and PbS; a perovskite nanocrystal compound comprising at least one selected from CsPbX3 (cesium lead halide) and MAPbX3 (methylammonium lead halide); Or it may be an upconversion nanoparticle comprising at least one selected from NaYF4:Yb, Er (ytterbium (Yb) and erbium (Er) doped sodium yttrium fluoride (NaYF4)) and NaYF4:Yb, Tm (Yb and thulium (Tm) doped NaYF4).

[0110] In one embodiment of the present invention, the CsPbX3 is, as a non-limiting example, CsPbF 3- , CsPbCl3, CsPbBr3, CsPbI3, CsPbBr2I , Or it can be CsPbBrI2. In one embodiment of the present invention, the MAPbX3 is, as a non-limiting example, MAPbF3, MAPbCl3, MAPbBr3, MAPbI3, MAPbBr2I , Or it could be MAPbBrI2.

[0111] In one embodiment of the present invention, the dye compound may include a carboxylic acid group as a functional group. In one embodiment of the present invention, the dye compound may hydrogen bond with the acrylic acid repeating unit of the chiral supramolecular higher-order structure and the chiral additive by including a carboxylic acid group as a functional group.

[0112] In one embodiment of the present invention, the semiconductor compound, the perovskite nanocrystal compound, and the upconversion nanoparticles may be grown and included within the core block polymer, polyacrylic acid.

[0113] In one embodiment of the present invention, when the achiral fluorescent substance is the dye compound, the molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the dye compound may be about 1:0.05 to about 0.3, about 1:0.05 to about 0.25, about 1:0.1 to about 0.3, or about 1:0.1 to about 0.25, but may not be limited thereto.

[0114] In one embodiment of the present invention, adding an achiral fluorescent substance to the stirred mixed solution and stirring may be performed for about 1 day or more, about 2 days or more, or about 1 day to about 10 days, but may not be limited thereto.

[0115] Hereinafter, the present invention will be described in more detail using examples. However, the following examples are provided only to help understand the present invention, and the contents of the present invention are not limited to the following examples.

[0116] [Example]

[0117] 1. Experimental method

[0118] 1-1. Materials

[0119] Toluene (99.5%), dichloromethane (DCM) (>99.5%), α-bromoisobutyryl bromide (BiBB) (98%), anisole (99%), 2-butanone (methyl ethyl ketone) (99.0%), anhydrous dimethylformamide (anhydrous DMF) (>99.8%), anhydrous 1-methyl-2-pyrrolidinone (anhydrous NMP) (99.5%), N,N,N',N',N''-pentamethyldiethylene triamine; PMDETA) (99%), trifluoroacetic acid (TFA) (99.9%), diethyl ether (anhydrous, 99.0%), ethanol (anhydrous, 99.5%), calcium hydride (CaH2) (for synthesis), sodium bicarbonate (NaHCO3) (99.7%), aluminum oxide powder (activated, neutral, ~325 mesh), tetrahydrofuran (THF) (99.0%), acetone (99.5%), magnesium sulfate (MgSO4) (anhydrous, 99.5%), benzyl alcohol (BA) (anhydrous, 99.8%), diphenyl ether (DPE) (99%), deuterated Deuterated chloroform (CDCl3) (99.96%), acetic acid (99.7%), and rhodamine B (RhB) (≥95%) were purchased from Sigma-Aldrich and used without further purification.D-(-)-mandelic acid (R-MA) (>99.0%) and L-(+)-mandelic acid (S-MA) (>99.0%) were purchased from Tokyo Chemical Industry. 2',7'-Difluorofluorescein (Oregon Green™ 488, OG) was supplied by Thermo Fisher Scientific and used without further purification. β-cyclodextrin (β-CD) (>97.0%, Sigma-Aldrich) was dried under vacuum at 60°C for 48 h, azeotropically distilled from toluene at 120°C for 2 h, and then esterified. Copper (I) bromide (CuBr) (98%, Sigma-Aldrich) was stirred in acetic acid for 2 h, filtered, washed with ethanol and diethyl ether, and finally dried under vacuum overnight at room temperature. Styrene (St) (99.9%, Sigma-Aldrich) and tert-butyl acrylate (tBA) (98%, Sigma-Aldrich) were distilled under reduced pressure with CaH2 before use. 1-Pyrenecarboxylic acid (PCA (>97.0%) purchased from TCI was purified by crystallization using ethanol as a solvent.

[0120] 1-2. Synthesis of star-shaped PAA-b-PS

[0121] 1) Synthesis of brominated β-CD initiator (Br-β-CD)

[0122] First, β-CD (2.5 mmol) was dissolved in anhydrous NMP (40 mL) and the solution was cooled to 0°C using an ice bath. BiBB (105 mmol) was then slowly added to the solution while stirring vigorously for 1 h. After complete addition of BiBB, the mixture was stirred at 0°C for an additional 1 h. The mixture was then slowly warmed to room temperature and stirred for an additional 24 h. The resulting crude solution was dispersed in DCM and then washed repeatedly with saturated aqueous NaHCO3 solution and deionized water. The final product was obtained by evaporating the DCM using a rotary evaporator, and then drying the residue in a vacuum oven at room temperature overnight.

[0123] 2) Synthesis of star-shaped poly(tert-butyl acrylate) (poly(tert-butyl acrylate; PtBA)

[0124] In the first step, Br-β-CD (macro-initiator), CuBr (catalyst), PMDETA (ligand), tBA (monomer), and MEK (solvent) were combined in an ampoule. The molar ratios of the reaction components Br-β-CD, CuBr, PMDETA, MEK, and tBA were maintained at 1:1:2:2000:1000. After that, the mixture was purged with N2 for 1 h to remove oxygen. The ampoule was then sealed and immersed in an oil bath preheated to 60°C. After polymerization for a certain period of time, to stop the polymerization, the ampoule was removed from the oil bath, quickly cooled in an ice bath, and then exposed to air. The resulting crude solution was diluted with acetone and passed through a neutral alumina column to remove the catalyst. After that, it was precipitated in a water / methanol mixture (v:v=1:1). After filtration, the final product was dried in a vacuum oven at room temperature.

[0125] 3) Synthesis of star-shaped poly(tert-butyl acrylate)-block-polystyrene (PtBA-b-PS)

[0126] The prepared star-shaped PtBA polymer, CuBr, PMDETA, styrene, and anisole were placed in an ampoule and purged with nitrogen gas for 1 hour to remove oxygen. The molar ratios of bromine, CuBr, PMDETA, anisole, and St in the star-shaped PtBA as reaction components were set to 1:1:2:2000:1000. The ampoule was then sealed and immersed in an oil bath set at 90°C. After a certain time of polymerization, the ampoule was removed from the oil bath, cooled in an ice bath, and then exposed to the atmosphere to stop the polymerization. The resulting crude solution was diluted with THF, passed through a neutral alumina column to extract the catalyst, and then precipitated in a water / methanol mixture (v:v=1:1). After filtration, the final product was dried in a vacuum oven at room temperature.

[0127] 4) Synthesis of star-shaped poly(acrylic acid)-block-polystyrene (PAA-b-PS)

[0128] The PtBA-b-PS star-shaped block copolymer was dissolved in anhydrous DCM. Hydrolysis was then initiated by slowly adding TFA with vigorous stirring at room temperature. After 24 h, the DCM was removed using a rotary evaporator. The product, PAA-b-PS, was then purified through a dissolution-precipitation process using DMF and methanol. Finally, the product was dried in a vacuum oven at room temperature.

[0129] 1-3. Fabrication of chiral fiber-shaped supramolecular structures

[0130] Chiral fiber-like supramolecular structures were obtained through co-assembly of star-shaped BCP and R / S-MA. First, star-shaped PAA-b-PS (2.5 mg) and R / S-MA were dissolved in 1 mL of DMF and stirred at room temperature for at least 2 days to ensure sufficient hydrogen bonding interactions between the AA repeating units and R / S-MA. The molar ratio of AA repeating units to MA was maintained at 1:2. The mixed solution was purified by passing it through a 200 nm PTFE filter and then evenly applied (drop casting) onto a substrate such as silica, glass, or quartz. The film was then annealed at 60°C for 24 h, during which time the solvent slowly evaporated and the fiber-like structures gradually formed.

[0131] 1-4. Fabrication of CPL-Activated Hybrid Film

[0132] Star-shaped PAA-b-PS (2.5 mg) and R / S-MA were mixed in 1 mL of DMF. The mixture was then stirred at room temperature for at least 48 h, maintaining the molar ratio of AA repeating units to MA at 1:2. Subsequently, achiral fluorescent dye molecules were dissolved in a small amount of DMF (<100 μL) and added to the mixed solution of PAA-b-PS and R / S-MA. The molar ratios of 1-Pyrenecarboxylic acid (PCA) (blue dye), Oregon Green™ 488 (OG) (green dye), and rhodamine B (RhB) (red dye) to AA repeating units were maintained at 1:0.25, 1:0.1, and 1:0.1, respectively. Afterwards, the mixture was stirred in a dark room at 5 to 10°C for 24 hours to prevent decomposition by light and heat. The solution was then filtered through a 200 nm PTFE syringe filter and uniformly applied to a substrate (e.g., silica, glass, or quartz). The resulting film was annealed at 60°C overnight to allow the solvent to slowly evaporate and form a chiral supramolecular structure.

[0133] 2. Results

[0134] 2-1. A versatile strategy for constructing CPL-active hybrid films using star-shaped BCP-based chiral supramolecular templates.

[0135] Figure 1 illustrates a detailed step-by-step process for fabricating CPL-activated hybrid films. This process utilizes a chiral supramolecular co-assembly technique mediated by non-covalent interactions. The first step in this procedure involves introducing the chiral additive, R / S-MA, into a star-shaped PAA-b-PS solution in DMF. This results in the formation of swollen chiral star-shaped BCPs. The interaction between the PAA block and MA is induced by hydrogen bonding, which facilitates efficient chirality transfer from MA to the polymer chain. The resulting mixed solution is then uniformly coated onto a substrate. This is followed by thermal annealing, which promotes higher-order helical phase transitions within the chiral supramolecular co-assembly. Given an appropriate annealing time, chiral supramolecular structures with preferred handedness are formed, where the preferred handedness is determined by the chirality of R / S-MA. In the next step of this process, various achiral fluorescent dye molecules with multiple hydrogen bonding sites are added, and the same procedure is repeated to utilize noncovalent interactions and chiral co-assembly via thermal annealing. Interestingly, chiral supramolecular structures incorporating achiral dye molecules are obtained. These structures emit characteristic CPL emission whose orientation is determined by the handedness of the supramolecular structure, indicating that the dye molecules are successfully arranged in a chiral manner. The overall process highlights an interesting and versatile approach for incorporating chiral and achiral components to induce CPL emission.

[0136] 2-2. Incorporation of chiral additives into star-shaped BCPs

[0137] Hereinafter, a step-by-step process for synthesizing a star-shaped amphiphilic unimolecular poly(acrylic acid)-block-polystyrene (PAA-b-PS) is described in detail. First, the 21 hydroxyl terminal groups of β-CD were converted to bromine groups through esterification, forming a 21-Br-β-CD macroinitiator. Proton nuclear magnetic resonance (PNMR) 1 H-NMR) was used to confirm that the 21 hydroxyl groups of β-CD were esterified. The conversion efficiency was calculated to be 98% considering the ratio of the integrated area of ​​the residual protons of β-CD to the integrated area of ​​the methyl protons. Utilizing the 21-Br-β-CD macroinitiator, a series of atom transfer radical polymerization (ATRP) reactions were performed with tBA and St monomers, resulting in the formation of well-defined diblock copolymers with a narrow molecular weight distribution, poly(tert-butyl acrylate)-block-polystyrene (PtBA-b-PS). Finally, the hydrophobic PtBA block inside was converted to a hydrophilic PAA block by extensive hydrolysis of the tert-butyl group of PtBA. Through this conversion, amphiphilic star-shaped PAA-b-PS diblock copolymers were generated. To ensure successful hydrolysis, further confirmation was performed by Fourier transform infrared spectrum (FTIR) measurement. After hydrolysis, 2500 cm -1 3600 cm inland -1The broad absorbance across the range confirmed the formation of carboxylic acid groups. In addition, the carbonyl stretching peak was observed at 1727 cm of PtBA-b-PS. -1 1700 cm of PAA-b-PS -1 This finding provides further evidence of the successful hydrolysis process and conversion of PtBA blocks into PAA blocks.

[0138] Enantiopure MA star-shaped PAA-b-PS (M n, PAA = 100 kg·mol -1 , M n, PS = 190 kg·mol -1) was achieved through noncovalent interactions between multiple functional groups. To facilitate complexation between the two components, PAA-b-PS and R / S-MA were mixed in DMF, which serves as a good solvent for both the polymer block and R / S-MA. The molar ratio of AA repeating units to R / S-MA was set to 1:2. The resulting mixture was then analyzed for size and morphology using atomic force microscopy (AFM) in comparison with pure star-shaped PAA-b-PS (Figures 2a to 2c). Spherical unimolecular micelles were clearly observed regardless of whether PAA-b-PS and R / S-MA were complexed. However, it is noteworthy that the average diameter of the star-shaped micelles increased from 30.5 nm to 37 nm after binding enantiopure MA. This size expansion was further confirmed by dynamic light scattering (DLS) measurements, which showed an increase in the hydrodynamic diameter from 19.7 nm to 26.9 nm for R-MA and 27.3 nm for S-MA (Figs. 3a–c). Since each technique captures different states of the structure, it should be noted that the folded and stretched states of the samples used in AFM and DLS measurements may result in different sizes.

[0139] The noncovalent interactions between the star-shaped PAA-b-PS and enantiopurine MA were investigated using FTIR and density functional theory (DFT) calculations. In the FTIR spectra (Fig. 4), the stretching vibration bands of the carbonyl groups in both the PAA block and MA of the star-shaped BCP were shifted to 1700 cm -1 and 1709 cm -1 was observed. In particular, the bands were observed at 1640 cm when complexed. -1 1740 cm in height -1It is split into several bands within a wide range, indicating the presence of more complex interactions. Also, at 3438 cm -1 3423 cm from -1 An interesting shift in the methylenic OH stretching mode of MA was observed upon complexation. This shift may be due to the formation of hydrogen bonding interactions between the MA and the PAA blocks of the star-shaped BCP. Additional insights gained from computational studies using DFT showed that a single MA molecule can favorably form two intermolecular hydrogen bonds, represented by [OH…O] linkages, with the AA repeating unit (Figure 5). This interaction exhibited a negative hydrogen bond energy, indicating that the formation of this bond is energetically favorable. This result provides strong evidence for the presence of strong hydrogen bonding interactions between the MA and PAA blocks. The importance of these non-covalent interactions is underscored by the fact that they act as a major driving force for the transfer of chirality from chiral additives to the originally achiral star-shaped BCP. The DFT findings showing strong hydrogen bonding support this mechanism and provide a plausible explanation for the efficient transfer of chirality from MA to the PAA chains.

[0140] 2-3. Formation of chiral supramolecular structures through co-assembly

[0141] Chiral supramolecular structures with specific handedness were successfully synthesized through a co-assembly process by coating a DMF solution containing PAA-b-PS and enantio-pure MA, followed by thermal annealing at 60°C. As the annealing time increased, the chirality was easily transferred from the chiral additive to the hierarchical co-assembly, forming macroscopic helical fiber-like structures. Scanning electron microscopy (SEM) images (Fig. 6a and b) clearly show the handedness of the resulting fiber-like structures, which is determined by the molecular chirality of the chiral additive MA. Specifically, the star-shaped BCP films loaded with R-MA produced right-handed fiber-like structures, whereas the star-shaped BCP films loaded with S-MA produced left-handed fiber-like structures. The structures exhibited an average width of 3.5 μm. Importantly, these chiral structures contrast with the self-assembled structures observed in pure star-shaped BCP films exposed to the same thermal annealing conditions. In the absence of chiral additives, SEM and AFM images revealed a mixed morphology consisting of lamellae and spheres. Closer observation using high-magnification SEM (Figures 7a and b) revealed that the micro-sized fiber-like structures were composed of nano-sized belt-like structures. Further analysis using atomic force microscopy (AFM) revealed that the nano-sized belt-like structures were composed of densely packed dot-like structures (Figure 8).

[0142] Surprisingly, the chiral supramolecular fibrous structures exhibited strong supramolecular chirality, which was significantly different from the molecular chirality of R / S-MA. The CD spectrum of pure R / S-MA dissolved in deionized water exhibited a strong peak corresponding to the n-π* transition of the carboxylic acid group (Figure 9a), indicating molecular-level chiral optical (chiroptical) activity attributed to the chiral center of MA. However, after hybridization of R / S-MA with achiral star-shaped BCPs and subsequent thermal annealing-induced co-assembly, a new broad mirror-image CD band appeared in the wavelength range from 200 nm to 500 nm (Figure 9b). This CD response can be attributed to the supramolecular chirality of the resulting chiral supramolecular fibrous structures, which is induced through chirality transfer from the chiral additive to the star-shaped BCPs. The magnitude of supramolecular chirality was quantitatively assessed using the dissymmetry factor (g-factor), reaching a maximum value of 0.038 (Figure 10). This value surpasses that observed in chiral supramolecular structures constructed through co-assembly of achiral linear BCPs and chiral additives, and in self-assembly of chiral BCPs.

[0143] An interesting observation is that MA molecules, when dissolved in DMF without complexing with the star-shaped BCP, underwent thermal decomposition during thermal annealing under the same conditions. This decomposition phenomenon was indicated by the disappearance of the CD reaction and can be attributed to the formation of a melt phase at high temperatures. This result supports the low supramolecular chirality observed with a g-factor of 0.003 at a molar ratio of AA repeat units to MA of 1:1. In this particular system, the amount of MA was not sufficient to generate significant supramolecular chirality, as some of the MA molecules that did not form hydrogen bonds with AA underwent thermal decomposition. Therefore, an excess of MA relative to the number of AA repeat units is required to ensure that all AA units form hydrogen bonds with MA molecules to enable efficient chirality transfer.

[0144] The influence of helical packing driven by co-assembly on the mechanical properties of coated polymer films was investigated using AFM nanoindentation. This well-established technique quantitatively determines the elastic properties of materials at the nanoscale using the Derjaguin-Muller-Toporov (DMT) model. The DMT modulus images of chiral supramolecular fiber-like structures show a distribution of DMT moduli aligned in a specific direction, corresponding to the handedness of the fiber-like structures, as shown in Figures 11a and b. In contrast, the DMT modulus images of pure star-shaped BCP films exhibited a random DMT modulus distribution without any discernible direction (Figure 11c). To estimate the elastic modulus values, the post-contact deformation behavior, obtained from force-distance curves (Figures 11d to f), was analyzed. The reduced elastic modulus (E r) was calculated using the following equation (1), where S represents the contact stiffness measured as the slope of the tangent line to the unloading curve at maximum load, and A is the projected contact area (P) evaluated at maximum load. max ) is represented. The sample elastic modulus (E) is expressed as E in the following equation (2). r is related to, where, υ s and υ i are the Poisson's ratios of the sample and the indenter, respectively, and E s and E i are the elastic moduli of the sample and the indenter, respectively.

[0145] [Formula 1]

[0146]

[0147] [Formula 2]

[0148]

[0149] Importantly, the elastic modulus of the chiral supramolecular fiber-like structure showed a significant increase of 0.106 GPa compared to the expected value of 0.082 GPa for the pure star-shaped BCP film. In addition, the hardness (H), which can be calculated using the following equation (3), was 8.4 × 10 that of the pure BCP film. -3 N·m -2 1.5×10 chiral supramolecular fiber-like structures in -2 N·m -2 , which was significantly increased. These results strongly indicate that the tight helical packing induced by co-assembly with chiral additives contributes to the improvement of mechanical properties.

[0150] [Formula 3]

[0151]

[0152] 2-4. Study on the hierarchical chirality transfer mechanism into supramolecular structures

[0153] To gain insight into the formation of chiral supramolecular structures during the co-assembly process under prolonged thermal annealing, time-dependent monitoring of the CD response was performed (Figure 12). For the complex comprising star-shaped PAA-b-PS and S-MA, a unique bisignate exciton-type cotton effect centered at 250 nm was observed after thermal annealing at 60°C for 1 h. This CD behavior indicates that active chromophore-chromophore interactions occur as the components approach each other, facilitated by the gradual evaporation of solvent molecules during thermal annealing. As the annealing time increased to 4 h, the bisignate cotton effect weakened, and two CD peaks with opposite signs merged to produce a single CD peak with a positive sign. Upon further annealing for 24 h, the CD band broadened and intensified across a broad wavelength range, indicating the full emergence of supramolecular chirality. This finding highlights the need for extended thermal annealing times up to 24 h to induce optimized supramolecular chirality in co-assembled structures.

[0154] Furthermore, we investigated the time-dependent morphological transformation of chiral supramolecular fiber-like structures during thermal annealing. To investigate the chiral hierarchical supramolecular co-assembly mechanism, SEM and AFM techniques were utilized, and images were collected at various annealing times. First, after thermal annealing at 60°C for 1 h, the concentration of the complex consisting of star-shaped PAA-b-PS and S-MA increased due to gradual solvent evaporation. This resulted in the adhesion of swollen spherical micelles to each other, reducing the interfacial energy and forming irregular, dot-like aggregates (Figures 13a to 13c). These small aggregates were evenly distributed on the substrate. Interestingly, when the annealing time was extended to 2 h, larger spherical aggregates containing numerous dot-like small aggregates with diameters in the hundreds of nanometers were observed (Figures 14a to 14c). The presence of dark edge regions in these large spherical aggregates can be attributed to height differences caused primarily by accelerated solvent evaporation from the top layer. As the annealing time continued for up to 3 hours (Figures 15a to c), the large spherical aggregates underwent shrinkage and decreased in size as the solvent evaporated. Finally, after 4 hours of annealing, the large spherical aggregates completely disappeared (Figures 16a to c). This observation suggests that the large spherical aggregates are nonequilibrium metastable structures that are temporarily formed during the annealing process, driven by dynamics.

[0155] After 4 h of annealing, directional co-assembly began to occur. When the annealing time was extended to up to 8 h (Figures 17a to c), elongated belt-like structures formed by densely packed, point-like small aggregates with a width of approximately 300 nm. These belt-like structures exhibited a preferred structural growth direction as they aggregated with each other. This observation suggests that structural evolution toward a thermodynamically stable structure begins after at least 8 h of annealing. When the annealing time was further extended to 12 h (Figures 18a to c), the belt-like structures underwent further shrinkage, further reducing their width. This shrinkage may be due to the continuous evaporation of solvent molecules from both the point-like aggregates and the belt-like structures as the annealing process progressed for longer periods of time. Furthermore, the belt-like structures became entangled with each other, forming a dense structure that served as a nucleation site for the growth of the fiber-like structures. Finally, after 24 h of annealing, the belt-like structures exhibited a tight packing with a specific handedness, forming chiral fiber-like structures (Fig. 19a to c). These structures were completely shrunk as the solvent molecules completely evaporated during the long-term thermal annealing.

[0156] Based on the overall results above, we propose a possible hierarchical supramolecular co-assembly mechanism (Figure 20). Initially, chiral star-shaped BCPs are formed as primary structures through hybridization with MA, where the molecular chirality of MA is transferred to the conformational chirality of the PAA chains via hydrogen bonding. In the early stages of thermal annealing, as solvent molecules begin to evaporate from the coating solution, the primary structures approach each other, forming small, irregular aggregates on the surface. The presence of DMF, which has a high boiling point (153°C), plays a crucial role in the co-assembly process. This facilitates high polymer mobility over the extended thermal annealing process, allowing the helical polymer chains to efficiently evolve into thermodynamically stable structures with specific handedness during the slow solvent evaporation process. As DMF slowly evaporates, a concentration gradient is induced in the composite film. Therefore, the irregular dot-shaped aggregates in the upper layer first undergo an elongated packing, forming a belt-like structure as a secondary structure on the composite film. The belt-like structure shrinks and packs more tightly as the solvent further evaporates, and a new belt structure is formed in the deeper layer. Finally, as a tertiary structure, the belt-like structure adopts a helical packing, and when the solvent completely evaporates, a fibrous structure with a specific handedness is formed. The helical packing can be attributed to the chirality transfer from the helical phase of the PAA / MA blocks to the thermodynamically stable supramolecular structure. The stepwise structural evolution observed in the hierarchical supramolecular co-assembly mechanism is caused by the molecular chirality of the MA component, the structural chirality of the PAA / MA chains, and the co-assembly promoted by thermal annealing and gradual solvent evaporation.

[0157] 2-5. Optimization of multiple parameters affecting the evolution of chiral supramolecular structures.

[0158] Several parameters influencing the evolution of chiral supramolecular fiber-like structures obtained through co-assembly of achiral polymers and R / S-MA were discovered. Using star-shaped PAA homopolymers (e.g., sample 4 in Table 1), in contrast to star-shaped BCPs, irregular structures were formed due to the absence of phase separation caused by the chemical incompatibility between the PAA and PS blocks (Fig. 21a). Accordingly, low supramolecular chirality with a g-factor of 0.005 was observed (Fig. 21d). To further understand the effect of the volume fraction of polymer blocks on chiral supramolecular co-assembly, as summarized in Table 1, the molecular weights of the PAA blocks were the same (100 kg mol -1 ), star-shaped PAA-b-PS diblock copolymers with various molecular weights for the PS block were synthesized. In particular, the g-factor spectra of the composite films obtained by thermal annealing for 24 h showed that the g-factor decreased as the volume fraction of the PS block increased (Fig. 21 e and f). In addition, the morphology obtained after 24 h annealing of Sample 2 or 3, which had a higher or highest volume fraction of the PS block (Fig. 21 b and c), appeared to be similar to that observed in Sample 1, which had a shorter thermal annealing time (Fig. 16 a to c, Fig. 17 a to c, Fig. 18 a to c). These results suggest that as the volume fraction of the PS block increases, assemblies that are dynamically trapped are formed without reaching a thermodynamically stable state even after long-term thermal annealing.

[0159] In addition to the volume ratio, the concentration of the polymer composite consisting of star-shaped PAA-b-PS (e.g., sample 1 in Table 1) and R-MA used for coating and thermal annealing was controlled. The g-factor spectrum was 2.5 mg mL -1The highest level of supramolecular chirality was achieved at a concentration of 2.5 mg mL (Fig. 22). -1 The decrease in g-factor values ​​observed at higher or lower concentrations may be due to the morphological characteristics of the composite film. In Fig. 23a, 1.0 mg mL -1 At a concentration of 5.0 mg mL, the composite film exhibits a fibrous structure without a distinct handedness, indicating weak supramolecular chirality. On the other hand, at a concentration of 5.0 mg mL, -1 As the concentration increased, the obtained form after 24 hours of annealing reached the optimum concentration of 2.5 mg mL after 8 hours of thermal annealing. -1 , which showed similar morphologies to those observed in (Fig. 23c and Figs. 17a to c). This result indicates that high concentration hinders the evolution of thermodynamic chiral supramolecular structures. Consequently, it was demonstrated that not only the thermal annealing time but also the volume ratio of polymer blocks and the solution concentration can affect the thermodynamics and kinetics of chiral supramolecular co-assembly.

[0160] Sample number M n,PAA (kg·mol -1 )M n,PS (kg·mol -1 ) Volume ratio of PS block g-factor 11001900.655+0.038(S), -0.031(R) 21002500.714±0.017 (R / S) 31003200.762±0.01 (R / S) 41000.005 (R / S)

[0161] 2-6. Full-color CPL emission of achiral dye molecules through chiral supramolecular assembly

[0162] To fabricate CPL-active hybrid films, various achiral fluorescent dye molecules, specifically, 1-pyrenecarboxylic acid (PCA), Oregon Green 488 (OG), and Rhodamine (RhB), were introduced into chiral supramolecular co-assemblies comprising star-shaped PAA-b-PS and R / S-MA, followed by a thermal annealing process. Here, PCA, OG, and RhB serve as blue, green, and red fluorescent dye molecules, respectively. All of the dye molecules share the common characteristic of possessing a carboxylic acid group. This characteristic is essential for their effective participation in the co-assembly process, primarily through hydrogen bonding interactions with the PAA block. FTIR spectral analyses of PAA-b-PS / MA, the dye molecules, and the hybrid films formed by incorporating the dyes into PAA-b-PS / MA provide evidence of hydrogen bonding interactions via [OH…O] linkages (Figures 24a to 24c). The FTIR spectrum shows clear shifts, broadening and splitting of the characteristic vibrational bands associated with the carbonyl and hydroxyl groups, indicating that hydrogen bonding interactions have occurred between the carboxylic acid groups of the dye and the MA and PAA blocks.

[0163] In the hybrid film incorporated with PCA molecules, the absorption spectrum exhibited two distinct peaks located at approximately 360 nm and approximately 410 nm (Fig. 25a). The shorter wavelength peak corresponds to the π-π* transition of the pyrene chromophore, and the longer peak may be attributed to the aggregated state of PCA molecules induced through intermolecular interactions such as hydrogen bonding and π-π stacking. In particular, the CD spectrum exhibited distinct CD peaks in a broad wavelength range from 330 nm to 800 nm. These peaks are consistent with the two absorption peaks identified above. In addition, the CD spectrum exhibited a mirror-symmetric CD response, which is due to the molecular chirality of the additive used in the co-assembly process. An interesting observation is that the maximum g-factor at 430 nm was 2.6 × 10 -2 is as high as (a in Fig. 26). When OG molecules were incorporated into the hybrid film, the absorption band attributed to the π-π* transition of the OG chromophore was detected at approximately 470 nm (b in Fig. 25). For the RhB-integrated hybrid film, the absorption peak arising from the π-π* transition was observed at 565 nm (c in Fig. 25). It is noteworthy that band splitting was observed in both OG-integrated and RhB-integrated samples. This phenomenon is attributed to aggregation mediated by intermolecular interactions that may alter the energy levels available for electronic transitions. The CD spectra for both OG-integrated and RhB-integrated hybrid films exhibited mirror-image characteristic CD signals aligned along their respective absorption bands. The maximum g-factor was 7.0 × 10 for the OG-integrated and RhB-integrated hybrid films, respectively. -3 and 3.0×10 -2(b and c in Fig. 26). It should be noted that no chirality transfer to the dye molecules occurs in the absence of the thermal annealing process, as evidenced by the absence of CD reactions. This result indicates that chirality cannot be conferred to achiral dye molecules solely through hydrogen bonding interactions. Instead, the chiral arrangement of dye molecules through the co-assembly process induced by thermal annealing is essential for the chirality transfer to the achiral dye molecules. Consequently, these collective observations demonstrate that chirality was successfully transferred to the achiral dye molecules through the co-assembly process.

[0164] Next, the inventors investigated the CPL emission of hybrid films incorporating various dyes. The hybrid film incorporating PCA molecules exhibited blue CPL emission centered at about 450 nm (Fig. 27a). On the other hand, the hybrid films incorporating OG and RhB molecules exhibited green and red CPL emissions at about 550 nm and 625 nm, respectively (Fig. 27b and c). The handedness of the CPL emission is consistent with the geometric handedness of the chiral supramolecular structure. The luminescence dissymmetry factor (g) calculated using Eq. (4) lum ) plays an important parameter role in quantifying the size of CPL. In the above equation, I L represents the strength of left-handed CPL, and I R exhibits the strength of right-handed CPL. Surprisingly, CPL-active hybrid films containing PCA, OG, and RhB molecules exhibited excellent g of 0.11, 0.03, and 0.09, respectively. lumThe values ​​were shown in Fig. 27d to f. In addition, the hybrid films exhibited higher QY values ​​of 29.2%, 16%, and 12.4% for PCA, OG, and RhB, respectively, compared to the pure dye films. In the pure dye films, the emission was completely quenched after annealing due to the aggregation-caused quenching (ACQ) effect. However, in the hybrid films formed via co-assembly, the interaction between the PAA block and the dye molecules hindered the intermolecular interactions and electron exchange, ultimately alleviating the ACQ effect. The CPL performance achieved via star-shaped BCP-based supramolecular co-assembly was compared with that of chiral supramolecular materials composed of achiral dye molecules and other polymers (Table 2). This comparison helps to highlight the effectiveness of our strategy in enabling efficient chirality transfer to achiral dye molecules, resulting in high CPL activity. Altogether, these results demonstrate that the supramolecular chiral co-assembly of star-shaped BCPs, R / S-MA, and achiral dye molecules not only exhibits remarkable CPL-activating behavior but also exhibits high luminescence efficiency in the solid state. Furthermore, this study demonstrates the generalizability of this strategy when functional groups capable of participating in the co-assembly process via hydrogen bonding are present, demonstrating the potential for incorporating a wide range of achiral dye molecules for CPL emission.

[0165] [Formula 4]

[0166]

[0167] The morphology of the CPL-active hybrid films obtained by incorporating PCA, OG, and RhB molecules was characterized using SEM. SEM images of the hybrid films containing PCA and OG molecules show the formation of supramolecular fibers and morphological structures exhibiting a pronounced handedness (Figures 28a and b and 29a and b). This is consistent with the supramolecular structures obtained through the co-assembly of star-shaped BCP and R / S-MA in the absence of dye molecules. In Figure 28a, the presence of PCA crystalline aggregates was also observed. However, when RhB molecules were introduced into the co-assembly process (Figure 30a and b), the resulting structures resembled the supramolecular morphology of star-shaped BCP / S-MA obtained after 3 h of thermal annealing (Figures 15a to c). This finding suggests that the presence of bulky dye molecules hinders the achievement of a thermodynamically stable state. This interference is attributed to the interaction between the PAA block and the RhB molecule, which hinders the mobility of the polymer chains and the evolution of chiral supramolecular structures.

[0168] Chiral induction agent system g lum QY (%)Chiral additiveAchiral poly(1,4-butadiene)-b-poly(ethylene oxide) (PBd-b-PEO) + L / D-tartaric acid + PCA2.3×10 -2 -Comparative Example Chiral polymer nanofiber (a-pinene derived) Chiral polymer nanofiber + 5-(dimethylamino)-N-(prop-2-yn-1-yl)naphthalene-1-sulfonamide 2.5×10 -2 -Comparison Example: Chiral polyisocyanide-based supramolecular polymer + achiral fluorescent dyes ~3×10 -2-Comparative example chiral additive 1) PBd-b-PEO + D- / L-dibenzoyl TA + PCA 2) PBd-b-PEO + R / S-MA + 9-anthracenecarboxylic acid 1) 1.0×10 -2 2) 3.0×10 -2 1) 28%2) -Comparative Example Chiral Block Copolymer Polystyrene-b-poly(L-lactide) + six-carboxylate group modified hexathiobenzene compound 0.8×10 -2 -Comparison Example: Chiral polymer Chiral binaphthyl polymer + pyrene-naphthalimide dye 5.6×10 -2 38.8% Comparison Example Chiral Additive Polyaniline helical microfiber + R / S-camphorsulfonic acid + tetraphenylethylene ~2.5×10 -2 -Comparison Example: Chiral polyacetylene-based polymer + 9,10-bis(phenylethynyl)anthracene 4.2×10 -2 38.8% Comparison Example Chiral AdditiveRacemic polyacetylene + chiral α-pinene + green fluorescein (X18)9.0×10 -2 -Comparative Example Chiral Additive Stat-like PAA-b-PS + R / S-MA + PCA / OG / RhB 1) 0.11 2) 0.03 3) 0.09 1) 29.2% 2) 16.0% 3) 12.4% Example

[0169] 2.7 Fabrication of circularly polarized light-emitting materials based on perovskite nanocrystals

[0170] 1) First, star-shaped PAA-b-PS (5 mg) and R / S-mandelic acid were added to 1 mL of a mixed solvent of dimethylformamide and toluene (volume ratio = 1:1) and stirred vigorously at room temperature for 2 days (molar ratio of AA monomer to mandelic acid = 1:2).

[0171] 2) Simultaneously, star-shaped PAA-b-PS (5 mg) was added to 1 mL of dimethylformamide and stirred vigorously at room temperature for 1 day, then perovskite precursors CsBr and PbBr2 (molar ratio of perovskite precursor and AA monomer = 2:1) were added and stirred vigorously at room temperature for more than 5 days to obtain a mixed solution. Then, 100 uL of the mixed solution was dropped into 5 mL of toluene to form perovskite nanocrystals on the PAA core, n-hexane was added to precipitate, and the precipitate was dissolved in toluene.

[0172] 3) The star-shaped PAA-b-PS obtained in 1) and the solution containing R / S-mandelic acid; and the CsPbBr3 nanocrystal solution formed in the star-shaped PAA-b-PS obtained in 2) were mixed by stirring, uniformly applied to a substrate, and then heat-treated at 60°C for 1 hour.

[0173] Referring to Figures 31a and b, the hybrid film incorporating CsPbBr3 nanocrystals exhibited green CPL emission centered at approximately 510 nm. The handedness of the CPL is controlled by the handedness of the supramolecular chiral structure, which is determined by the molecular chirality of mandelic acid. A high luminescence asymmetry factor of up to 0.027 was observed, confirming that the chiral supramolecular structure technology of the present invention imparts chirality transfer and CPL activity not only to fluorescent dye molecules but also to perovskite nanocrystals.

[0174] 3. Conclusion

[0175] In conclusion, the present invention introduces an efficient and simple strategy for fabricating chiral, fibrous supramolecular structures. This approach involves the co-assembly of achiral star-shaped PAA-b-PS and R / S-MA with 21 polymer arms. Both the AA repeating unit and MA possess multiple hydrogen-bonding moieties, which promote strong noncovalent interactions between BCP and MA within the flexible environment provided by the covalently bound unimolecular micelle. This results in a pronounced supramolecular chirality, as evidenced by a high g-factor of 0.038. Furthermore, we provide an in-depth exploration of the mechanism driving the formation of these chiral supramolecular structures through time-dependent CD results and morphological changes. Our results reveal a hierarchical progression of the structures, transitioning from chiral star-shaped BCPs to belt-like nanostructures and ultimately evolving into fibrous microstructures with specific handedness. Furthermore, by incorporating various achiral fluorescent dye molecules into the chiral supramolecular co-assemblies, we were able to obtain a g-factor of up to 0.11. lum Full-color CPL-active films were successfully fabricated. Enhanced QY values ​​were achieved compared to pure dye films by mitigating aggregation-induced fluorescence quenching and thermal decomposition of dye molecules through effective encapsulation within star-shaped BCPs via hydrogen bonding. Ultimately, the present invention introduces a novel supramolecular co-assembly strategy that utilizes star-shaped BCPs as building blocks for constructing complex chiral supramolecular structures and high-performance CPL-active hybrid films. This exemplifies the broad applicability and superiority of the strategy developed in the present invention, highlighting its promising prospects for future applications in related technical fields.

[0176] The above description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0177] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. An achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral supramolecular higher-order structure comprising a chiral additive, The above polyacrylic acid and the above chiral additive interact non-covalently, The handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive. Chiral supramolecular higher-order structures.

2. In paragraph 1, A chiral supramolecular higher-order structure wherein the above shell block polymer is a hydrophobic polymer.

3. In paragraph 2, A chiral supramolecular higher-order structure, wherein the hydrophobic polymer comprises at least one selected from polystyrene, polyethylene, polypropylene, polybutadiene, polyaniline, polythiophene, poly(phenylene vinylene), and derivatives thereof.

4. In paragraph 1, A chiral supramolecular higher-order structure, wherein the chiral additive comprises at least one selected from mandelic acid, tartaric acid, aspartic acid, tyrosine, ibuprofen, and hydroxymandelic acid.

5. In paragraph 1, The above-mentioned achiral star-shaped block copolymer is a chiral supramolecular higher-order structure having a star-shaped structure including a plurality of arms extending from the core block polymer.

6. In paragraph 1, A chiral supramolecular higher-order structure, wherein the volume ratio of the core block polymer and the shell block polymer is 1:1 to 1:

4.

7. In paragraph 1, The above chiral supramolecular higher-order structure is a chiral supramolecular higher-order structure that forms a helical fiber-shaped structure.

8. In paragraph 1, A chiral supramolecular higher-order structure, wherein the asymmetry factor value of the above chiral supramolecular higher-order structure is 0.03 or more.

9. Chiral supramolecular higher-order structure according to paragraph 1; and achiral fluorescent substance A circularly polarized light emitting structure comprising: The circular polarization direction of the circularly polarized light-emitting structure is determined according to the handedness of the chiral supramolecular higher-order structure. Circular polarizing light emitting structure.

10. In paragraph 9, The above achiral fluorescent substance is a dye compound comprising at least one selected from 1-pyrenecarboxylic acid, Oregon Green 488, rhodamine, anthracene-9-carboxylic acid, terephthalic acid, naphthalene dicarboxylic acid, coumarin-6-carboxylic acid, 7-hydroxy-4-methylcoumarin-3-carboxylic acid, and naphthalene-1,8-dicarboxylic acid; a semiconductor compound comprising at least one selected from CdS, CdSe, and PbS; a perovskite nanocrystal compound comprising at least one selected from CsPbX3 (cesium lead halide) and MAPbX3 (methylammonium lead halide); Or a circularly polarized light-emitting structure comprising at least one upconversion nanoparticle selected from NaYF4:Yb, Er (ytterbium (Yb) and erbium (Er) doped sodium yttrium fluoride (NaYF4)) and NaYF4:Yb, Tm (Yb and thulium (Tm) doped NaYF4).

11. In paragraph 9, A circularly polarized light-emitting structure, wherein the luminescence asymmetry factor value of the above circularly polarized light-emitting structure is 0.03 or more.

12. Preparing a mixed solution comprising an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a chiral additive, and a solvent; Stirring the above mixed solution; and Applying the above stirred mixed solution and performing thermal annealing A method for producing a chiral supramolecular higher-order structure, comprising: The above polyacrylic acid and the above chiral additive interact non-covalently, The handedness of the chiral supramolecular higher-order structure is determined according to the chirality of the chiral additive. Method for preparing chiral supramolecular higher-order structures.

13. In paragraph 12, A method for producing a chiral supramolecular higher-order structure, wherein the solvent comprises at least one selected from dimethylformamide, toluene, tetrahydrofuran, ethyl acetate, 1,4-dioxane, dimethyl sulfoxide, acetonitrile, acetone, ethanol, and methanol.

14. In paragraph 12, A method for producing a chiral supramolecular higher-order structure, wherein the molar ratio of the acrylic acid repeating unit of the polyacrylic acid and the chiral additive is 1:1 to 1:

3.

15. In paragraph 12, A method for producing a chiral supramolecular higher-order structure, wherein the above thermal annealing is performed in a temperature range of 50°C to 70°C.

16. In paragraph 12, A method for producing a chiral supramolecular higher-order structure, wherein the above thermal annealing is performed for 1 hour to 48 hours.

17. In paragraph 12, A method for producing a chiral supramolecular higher-order structure, wherein the volume ratio of the core block polymer and the shell block polymer is 1:1 to 1:

4.

18. In paragraph 12, The concentration of the above mixed solution is 1 mg·mL -1 Exceeding 10 mg mL -1 A method for producing a chiral supramolecular higher-order structure.

19. In paragraph 12, Before performing the above thermal annealing, A method for producing a chiral supramolecular higher-order structure, further comprising adding an achiral fluorescent agent to the stirred mixed solution and stirring.

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