Circularly polarized luminescent material and preparation method thereof, and circularly polarized organic light-emitting diode

Abstract

The invention discloses a circular polarization luminescent material and a preparation method thereof, and a circular polarization organic light-emitting diode, the circular polarization luminescent material comprises a compound represented by a general formula (I): # imgabs0 #, in which R1 is # imgabs1 # or # imgabs2 #; x is OTf, Cl, Br, I, TFSI or PF6; r2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene. According to the circularly polarized light-emitting material, the circularly polarized light-emitting performance of the material is jointly improved through the synergistic effect among the chiral binaphthalene structure, the pyridine ring, the substituent group of the pyridine ring and the formed supramolecular structure or fractal structure.

Description

Technical Field

[0001] The invention belongs to the technical field of development of organic light-emitting molecules, and relates to a circularly polarized light-emitting material and a preparation method thereof, and a circularly polarized organic light-emitting diode. Background Art

[0002] Circularly polarized light is a special type of polarized light, whose electric field vector rotates clockwise or counterclockwise in the direction of the light source, which is called right-handed or left-handed polarized light, respectively. Circularly polarized luminescence (CPL) refers to the phenomenon that a chiral luminescent body produces unequal left-handed and right-handed polarized light under excitation. Therefore, circularly polarized organic light-emitting diodes (CP-OLEDs) based on circularly polarized light are widely used in anti-counterfeiting and encryption, healthy eye protection, optical data storage, chiral sensing, liquid crystal and three-dimensional display technology, etc. because they can emit light with circular polarization characteristics.

[0003] Generally speaking, circularly polarized light is obtained by filtering ordinary non-polarized light through a series of filters, such as linear polarizers, quarter-wave plates, etc. However, this method requires a complex device structure and causes a lot of energy loss. Therefore, it is of great significance to develop chiral luminescent materials that can directly emit circularly polarized light. Typical circularly polarized luminescent materials contain two main parts: a chiral part and a luminescent part. The two parts are connected by covalent bonds or intermolecular assembly. Axial chirality usually refers to a molecule containing two pairs of chemical groups that are arranged in a non-planar manner around the chiral axis. Such molecules are non-superimposable on their mirror images, which means that they cannot be overlapped by simple translation and rotation. The chiral axis is usually determined by a chemical bond that is constrained by the steric hindrance of the group and cannot rotate freely. The binaphthyl molecule is formed by two naphthalene molecules connected by a single bond at the 1-position. Due to the large plane of naphthalene, the two naphthalene rings cannot be coplanar due to the steric hindrance effect, but are staggered with each other, and the planes they are in have a certain angle. This structure makes binaphthyl usually exhibit axial chirality. In addition, the luminescence asymmetry factor of binaphthyl molecules is large, the synthesis is relatively simple, and they have circularly polarized luminescence properties. However, the luminescence properties of binaphthyl molecules are poor, which limits their wide application. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a circularly polarized luminescent material and a preparation method thereof, and a circularly polarized organic light emitting diode, thereby solving the technical problem that the circularly polarized light luminescence performance of binaphthyl molecules in the prior art is poor.

[0005] The present invention is achieved through the following technical solutions: A circularly polarized luminescent material, comprising a compound represented by general formula (I):

[0006] Among them, R1 is or ; X = OTf, Cl, Br, I, TFSI, PF6; R2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene.

[0007] The above-mentioned method for preparing a circularly polarized luminescent material comprises the following steps: S1: 1-bromo-3-hydroxynaphthalene and dihydroxy-bis-tetramethylethylenediamine copper chloride were dissolved in dichloromethane, and then the system was placed in an oxygen atmosphere and stirred for reaction to obtain R / S-BINDL; S2: After splitting the R / S-BINDL, dissolving the split BINDL, ethyl bromide, sodium iodide and potassium carbonate in acetone and subjecting them to reflux reaction to obtain R-BINDB or S-BINDB; S3: After mixing the R-BINDB or S-BINDB with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium, 1,4-dioxane is added under an argon atmosphere for reflux reaction to obtain R-BINPY or S-BINPY; or after mixing the R-BINDB or S-BINDB with 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, triethylamine is added under an argon atmosphere for reflux reaction to obtain R-BINAPY or S-BINAPY; S4: reacting the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodide, halogenated benzyl, halogenated methylnaphthalene, halogenated methylanthracene, halogenated methylbenzopyrene, halogenated methylpyrene, halogenated methylphenanthrene or halogenated methylperylene to obtain the circularly polarized luminescent material.

[0008] Preferably, in step S1, the molar ratio of 1-bromo-3-hydroxynaphthalene to dihydroxy-bis-tetramethylethylenediamine copper chloride is 1:(0.008-0.02).

[0009] Preferably, in step S1, the reaction is stirred for 14 to 24 hours.

[0010] Preferably, in step S2, the molar ratio of the separated BINDL, ethyl bromide, sodium iodide and potassium carbonate is 1:(4-8):(0.1-0.2):(4-8); in step S2, the temperature of the reflux reaction is 60-75°C, and the time is 20-50h.

[0011] Preferably, in step S3, the molar ratio of the R-BINDB or S-BINDB to pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium is 1:(2-6):(4-8):(0.03-0.1), and the temperature of the reflux reaction of the R-BINDB or S-BINDB with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium and 1,4-dioxane is 105-125° C., and the time is 12-24 h.

[0012] Preferably, in step S3, the molar ratio of the R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 1:(2-5):(0.08-0.15):(0.03-0.05), and the reflux reaction temperature of the R-BINDB or S-BINDB with 4-ethynylpyridine, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride and triethylamine is 95-115° C., and the time is 8-18 h.

[0013] Preferably, in step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to methyl trifluoromethanesulfonate is 1:(2-6), the reaction temperature is room temperature, and the reaction time is 12-24 h.

[0014] Preferably, in step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to diphenyltrifluoromethanesulfonic acid iodide is 1:(2-6), the reaction temperature is 80-110° C., and the reaction time is 6-12 h.

[0015] A circularly polarized organic light emitting diode comprises the circularly polarized light emitting material mentioned above.

[0016] Compared with the prior art, the present invention has the following beneficial technical effects: The present invention discloses a circularly polarized luminescent material, comprising a compound represented by general formula (I): , where R1 is or ; X = OTf, Cl, Br, I, TFSI, PF6; R2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene. The core structure of the circularly polarized luminescent material is a chiral binaphthyl structure or a chiral binaphthyl structure with an alkynyl group, and a pyridine ring or a substituted pyridine ring is bonded to the binaphthyl structure. First, in the molecule, the binaphthyl structure itself has chiral properties and can produce circularly polarized light. The difference in chiral configuration between the excited state and the ground state will lead to the emission of circularly polarized light; secondly, the introduction of the pyridine ring or the substituted pyridine ring changes the electronic structure inside the molecule. These substituents form a larger conjugated plane inside the molecule, which makes the movement of electrons in the molecule freer. The high degree of conjugation is conducive to the delocalization and transmission of electrons in the molecule, thereby effectively reducing the molecular energy gap. A smaller molecular energy gap means that the electron The pyridine ring and its substituents are more easily excited, so they are more likely to respond under external stimuli, which is more conducive to the improvement of luminescence performance. At the same time, the pyridine ring and its substituents, as intermediates for energy transfer, can also promote the transfer of energy from the excited state to the luminescent state, thereby improving the luminescence efficiency. In addition, the pyridine ring or substituted pyridine ring bonded to the chiral binaphthyl structure can form a supramolecular structure through intermolecular interactions (including hydrogen bonds and π-π stacking, etc.). In this process, the chirality is transferred from the chiral binaphthyl structure to the pyridine ring and its substituents, and then further to the entire supramolecular structure, thereby realizing multi-level amplification of the chirality, and finally forming a two-dimensional chiral fractal structure, which can significantly amplify the chiral signal and circularly polarized luminescence performance. Therefore, in the present invention, the synergistic effect between the chiral binaphthyl structure, the pyridine ring and its substituents, and the formed supramolecular structure or fractal structure jointly improves the circularly polarized luminescence performance of the material.

[0017] Furthermore, the present invention also discloses a method for preparing the circularly polarized luminescent material. In the method, 1-bromo-3-hydroxynaphthalene is first used as a raw material, and oxidative coupling is performed under the action of an organic catalyst dihydroxy-bis-tetramethylethylenediamine copper chloride, and a chiral center is introduced to obtain R / S-BINDL, that is, a mixture of R-BINDL and S-BINDL. Then, the R / S-BINDL is chirally split, reacted with bromoethane after the split, an ethyl group is introduced, and the alkylation is performed, which can increase the stability of the binaphthyl molecule and reduce the occurrence of side reactions in the next coupling reaction. R-BINDB or S-BINDB is generated, and then R-BINDB or S-BINDB is reacted with pyridine-4-boronic acid in the presence of tetrakistriphenylphosphine palladium to generate R-BINPY or S-BINPY through a Suzuki coupling reaction, or R-BINDB or S-BINDB is reacted with 4-ethynylpyridine in the presence of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride to generate R-BINAPY or S-BINAPY through a Sonogashira coupling reaction, wherein different coupling reactions are used. Different pyridine groups (pyridin-4-yl or 4-ethynylpyridine) should be introduced into the binaphthyl viologen molecule to increase the conjugation degree and functionality of the molecule, and finally R-BINPY, S-BINPY, R-BINAPY or S-BINAPY react with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodide, benzyl bromide, bromomethylnaphthalene, bromomethylanthracene, bromomethylbenzopyrene, bromomethylpyrene, bromomethylphenanthrene or bromomethylperylene to replace the nitrogen atom on the pyridine ring, so that the chiral binaphthylpyridine becomes a cationic viologen derivative with electrochemical properties. The preparation method of the circularly polarized luminescent material has a clear synthesis route, efficient product chirality control, mild reaction conditions, strong product diversity and functionality, a large conjugated structure, and good circularly polarized luminescence performance.

[0018] Furthermore, another inventive point of the present invention is that in step S1, the molar ratio of 1-bromo-3-hydroxynaphthalene and dihydroxy-bis-tetramethylethylenediamine copper chloride is 1:(0.008-0.02). First, by controlling the molar ratio of the two reactants, the reaction conditions can be optimized, so that the formation of the target product (R / S-BINDL) is more favorable. The lower amount of dihydroxy-bis-tetramethylethylenediamine copper chloride can reduce the occurrence of side reactions and improve the selectivity of the reaction, thereby obtaining a higher purity target product. In addition, although the chiral separation is mainly carried out in the subsequent steps, the reaction conditions in step S1 will also affect the initial formation of the chiral product. The appropriate molar ratio helps to form a certain proportion of chiral intermediates at the beginning of the reaction, providing a more favorable basis for the subsequent chiral separation. In addition, the ratio of reactants will have a significant effect on the reaction rate. By adjusting the molar ratio, the optimal balance between reaction rate and yield can be determined. Too low a catalyst dosage will result in a slow reaction rate, while too high a dosage will induce unnecessary side reactions. Therefore, setting the molar ratio range helps to obtain a higher yield while ensuring reaction efficiency.

[0019] Furthermore, another inventive point of the present invention is that in step S1, the reaction is stirred for 14 to 24 hours. First, the length of time for the stirring reaction is the key to ensure sufficient contact and reaction between the reactants. The time range of 14 to 24 hours allows the reactants to be fully mixed in the solution, and through the collision and interaction between molecules, the reaction gradually reaches an equilibrium state. This can ensure that the production of the target product (R / S-BINDL) is maximized while reducing the residue of unreacted raw materials. A sufficiently long reaction time helps to reduce the occurrence of side reactions. By extending the reaction time, the main reaction can be made more thorough, thereby improving the purity and yield of the target product. In addition, appropriately extending the reaction time helps to stabilize the formation and accumulation of chiral intermediates, providing a more favorable basis for subsequent chiral separation.

[0020] Furthermore, another inventive point of the present invention is that in step S2, the molar ratio of the split BINDL, ethyl bromide, sodium iodide and potassium carbonate is 1:(4~8):(0.1~0.2):(4~8); in step S2, the temperature of the reflux reaction is 60~75°C, and the time is 20~50h. First, the appropriate molar ratio ensures effective collision and reaction between the reactants. Ethyl bromide is used as an alkylating agent, and its excessive use can promote the alkylation reaction of BINDL and improve the generation rate and yield of the target product. At the same time, sodium iodide is used as a catalyst or promoter, and its appropriate addition can accelerate the reaction process. Potassium carbonate is used as a base, and its dosage must also be controlled within a certain range to maintain the acid-base balance of the reaction system and promote the smooth progress of the reaction. By accurately controlling the molar ratio of the reactants, the generation of by-products can be reduced and the selectivity of the target product can be improved. This helps to simplify the subsequent purification steps and reduce production costs. The long reflux reaction (20-50h) allows enough time for the reactants to fully interact and transform, thus ensuring that the reaction is as complete as possible, which helps to reduce the residue of unreacted raw materials and improve the purity of the product. In addition, the reflux reaction temperature is 70°C, which can speed up the reaction rate while reducing the occurrence of side reactions and improving the reaction yield.

[0021] Furthermore, another inventive point of the present invention is that in step S3, the molar ratio of the R-BINDB or S-BINDB to pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium is 1:(2~6):(4~8):(0.03~0.1), and the temperature of the reflux reaction of the R-BINDB or S-BINDB with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium and 1,4-dioxane is 105~125°C, and the time is 12~24h. First, by accurately controlling the molar ratio of the reactants, the conditions of the Suzuki coupling reaction can be optimized, so that the formation of the target product (i.e., the product of the coupling of R-BINDB or S-BINDB with pyridine-4-boric acid) is more favorable. An appropriate excess of pyridine-4-boric acid can promote the coupling reaction. As a base, the amount of potassium carbonate should also be controlled within a certain range to maintain the acid-base balance of the reaction system and promote the smooth progress of the reaction. Tetrakistriphenylphosphine palladium is used as a catalyst, and its dosage is small but its role is critical. The right amount of catalyst can significantly increase the reaction rate and yield. Accurate control of the reaction conditions and the dosage of the reactants can reduce the formation of by-products, thereby improving the purity of the target product, which is very important for simplifying the subsequent purification steps and controlling the quality of the final product. The long reflux reaction (12~24h) allows enough time for the reactants to fully interact and transform, thereby ensuring that the reaction is as complete as possible. This helps to reduce the residue of unreacted raw materials and increase the yield of the product. In addition, the reflux reaction temperature is 115℃, which can speed up the reaction rate while reducing the occurrence of side reactions and improving the reaction yield.

[0022] Furthermore, another inventive point of the present invention is that in step S3, the molar ratio of the R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 1:(2-5):(0.08-0.15):(0.03-0.05), and the R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 1:(2-5):(0.08-0.15):(0.03-0.05). The temperature of the reflux reaction of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride and triethylamine is 95-115°C, and the time is 8-18h. First, by precisely controlling the molar ratio of the reactants, especially the amount of the catalyst [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride and cuprous iodide, the efficiency of the Sonogashira coupling reaction can be significantly improved. These two catalysts play a key role in the reaction, promoting the coupling between alkynes and halogenated hydrocarbons to generate target products containing triple bonds. Appropriate reactant molar ratios and reaction times can ensure that the reaction is as complete as possible, reduce the residue of unreacted raw materials, and thus improve the yield and purity of the product. By precisely controlling the reaction conditions and the amount of reactants, the occurrence of unnecessary side reactions can be reduced. In addition, the temperature of the reflux reaction here is 95-115°C, which can accelerate the reaction rate while reducing the occurrence of side reactions and improve the reaction yield.

[0023] Further, another inventive point of the present invention is that in step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to methyl trifluoromethanesulfonate is 1: (2-6), the reaction temperature is room temperature, and the reaction time is 12-24 hours. First, the reaction is carried out at room temperature, avoiding the risk of side reactions and product decomposition caused by high temperature. The room temperature reaction conditions are milder, which is conducive to maintaining the stability and activity of the product, and also reduces the requirements and energy consumption of experimental equipment. By accurately controlling the molar ratio of the reactants, effective collision and reaction between the reactants can be ensured. Methyl trifluoromethanesulfonate is used as an esterification agent, and its appropriate excess can promote the esterification reaction and improve the generation rate and yield of the target product. The long-term reaction (12-24 hours) at room temperature allows the reactants to have enough time to fully interact and transform, thereby helping to reduce the generation of by-products and improve the purity and selectivity of the target product.

[0024] Further, another inventive point of the present invention is that in step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to diphenyl trifluoromethanesulfonic acid iodine is 1: (2-6), the reaction temperature is 80-110° C., and the reaction time is 4-12 hours. The higher reaction temperature can significantly increase the molecular motion speed of the reactants and increase the collision frequency between them, thereby accelerating the reaction rate. In the appropriate temperature range, the interaction between the reactants is more sufficient, which is conducive to the formation of the target product. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0026] Figure 1 Schematic diagram of the reaction process of synthesizing circularly polarized luminescent materials in the present invention; Figure 2 The circularly polarized luminescent material prepared in Example 3 of the present invention, i.e., the ultraviolet-visible absorption spectrum of chiral right-handed binaphthylphenyl viologen after reduction with metallic zinc and sodium; Figure 3 The circularly polarized luminescent material prepared in Example 4 of the present invention, i.e., the ultraviolet-visible absorption spectrum of chiral left-handed binaphthylphenyl viologen after reduction with metallic zinc and sodium; Figure 4 The cyclic voltammetry curve of the circularly polarized luminescent material prepared in Example 3 of the present invention, i.e., chiral right-handed binaphthylphenyl viologen; Figure 5 The cyclic voltammetry curve of the circularly polarized luminescent material prepared in Example 4 of the present invention, i.e., chiral left-handed binaphthylphenyl viologen; Figure 6 This is an electron paramagnetic resonance spectrum of the circularly polarized luminescent material prepared in Example 3 of the present invention, namely, chiral right-handed binaphthylphenyl viologen; Figure 7 This is an electron paramagnetic resonance spectrum of the circularly polarized luminescent material prepared in Example 4 of the present invention, namely, chiral left-handed binaphthylphenyl viologen; Figure 8 The circularly polarized luminescent material prepared in Examples 3 and 4 of the present invention, i.e., the fluorescence spectrum of chiral right-handed / left-handed binaphthylphenyl viologen; Fig. 9 The circular dichroism spectra of the circularly polarized luminescent material prepared in Examples 3 and 4 of the present invention, i.e., chiral right-handed / left-handed binaphthylphenyl viologen; Fig.10The circularly polarized luminescence test results of the circularly polarized luminescent materials prepared in Examples 3 and 4 of the present invention, i.e., chiral right-handed / left-handed binaphthylphenyl viologen; Fig.11 : is a luminescence asymmetry factor diagram of the circularly polarized luminescent material prepared in Examples 3 and 4 of the present invention, namely, chiral right-handed / left-handed binaphthylphenyl viologen; Fig.12 The circularly polarized luminescent material prepared in Example 3 of the present invention, namely, SEM images of chiral right-handed binaphthylphenyl viologen at different magnifications. DETAILED DESCRIPTION

[0027] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0028] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0029] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0030] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0031] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0032] The present invention provides a circularly polarized luminescent material, characterized in that it comprises a compound represented by general formula (I): ; Among them, R1 is or ; X = OTf, Cl, Br, I, TFSI or PF6; R2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene.

[0033] In addition, the present invention also discloses a preparation method of the above-mentioned circularly polarized luminescent material, the raw materials are 1-bromo-3-hydroxynaphthalene, dihydroxy-bis-tetramethylethylenediamine copper chloride, potassium carbonate, sodium iodide, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium, ethyl bromide, 4-ethynylpyridine. Pyridine-4-boric acid, tetrakistriphenylphosphine palladium, potassium carbonate, anhydrous copper acetate, diphenyltrifluoromethanesulfonic acid iodine, trifluoromethanesulfonic acid methyl ester, and the method comprises the following steps: (1): Synthesis of 4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL) 1-bromo-3-hydroxynaphthalene and dihydroxy-bis-tetramethylethylenediamine copper chloride are dissolved in dichloromethane, wherein the molar ratio of 1-bromo-3-hydroxynaphthalene to dihydroxy-bis-tetramethylethylenediamine copper chloride is 1:(0.008-0.02), and then the system is placed in an oxygen atmosphere and stirred for reaction for 14-24 hours. After the reaction is complete, the reaction mixture is concentrated under reduced pressure and then subjected to silica gel column chromatography, using gradient chromatography (dichloromethane: petroleum ether=1:2, dichloromethane) to obtain a light yellow solid, namely R / S-BINDL, which is a mixture of R-BINDL and S-BINDL.

[0034] (2): Chiral separation 5 g of 4,4'-dibromo-2,2-dihydroxy-1,1'-binaphthyl was split by a chiral company to obtain R-BINDL or S-BINDL, wherein the chiral company was Daicel Pharmaceutical Chiral Technology Co., Ltd.

[0035] (3): Synthesis of intermediate R / S-4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (R-BINDB or S-BINDB) Dissolve the separated BINDL (R-BINDB or S-BINDB), ethyl bromide, sodium iodide and potassium carbonate in acetone, and reflux for reaction at 60-75°C for 20-50h, wherein the molar ratio of R-BINDB or S-BINDB to ethyl bromide, sodium iodide and potassium carbonate is 1:(4-8):(0.1-0.2):(4-8), filter the reaction mixture after cooling, concentrate the filtrate under reduced pressure, add acetone to recrystallize and purify the reaction mixture to obtain a light yellow solid, namely R-BINDB or S-BINDB; (4): Synthesis of intermediate chiral 4,4′-bipyridine-2,2′-dioxy-1,1′-binaphthyl (R-BINPY or S-BINPY) or chiral alkynylbinaphthylpyridine (R-BINAPY or S-BINAPY) The R-BINDB or S-BINDB is mixed with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium, wherein the molar ratio of the R-BINDB or S-BINDB to pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium is 1:(2-6):(4-8):(0.03-0.1), 1,4-dioxane is added under an argon atmosphere, and the mixture is refluxed at a temperature of 105-125° C. for 12-24 hours. The resulting solution is subjected to reduced pressure rotary evaporation, water is added to the reaction mixture and stirred, the aqueous layer is extracted three times with dichloromethane, the organic layer is separated, the residual water is dried with sodium sulfate, the filtrate is filtered and concentrated under reduced pressure, and the solid is purified by column chromatography (V 石油醚 :V 乙酸乙酯 =10:1, V 5%三乙胺 ; V 石油醚 :V 乙酸乙酯 =5:1, V 5%三乙胺 ) to obtain a white solid, namely R or S-4,4′-bipyridine-2,2′-dioxy-1,1′-binaphthyl (R-BINPY or S-BINPY); Or after the R-BINDB or S-BINDB is mixed with 4-ethynylpyridine, cuprous iodide, and [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, the molar ratio of the R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide, and [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride is 1:(2-5):(0.08-0.15):(0.03-0.05), triethylamine is added under an argon atmosphere, and the mixture is refluxed at a temperature of 95-115° C. for 8-18 hours. After the reaction is completed, water is added to the reaction mixture and stirred, the aqueous layer is extracted with dichloromethane, the organic layer is separated, the residual water is dried with sodium sulfate, the dried mixture is concentrated under reduced pressure, and the residue is purified by column chromatography (V 二氯甲烷 :V 甲醇 =10:1) purification to obtain chiral alkynyl binaphthylpyridine, i.e. R-BINAPY or S-BINAPY; (5): Modification of nitrogen atoms on pyridine The circularly polarized luminescent material is prepared by reacting the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodide, halogenated benzyl, halogenated methylnaphthalene, halogenated methylanthracene, halogenated methylbenzopyrene, halogenated methylpyrene, halogenated methylphenanthrene or halogenated methylperylene at room temperature, wherein the halogen in the halogenated compound is chlorine, bromine or iodine.

[0036] Specific: Under argon environment, R-BINPY, S-BINPY, R-BINAPY or S-BINAPY and methyl trifluoromethanesulfonate are dissolved in dichloromethane, wherein the molar ratio of R-BINPY or S-BINPY to methyl trifluoromethanesulfonate is 1:(2-6). The solution is stirred at room temperature for 6-24 hours, and the reaction mixture is washed 3-5 times with dichloromethane solution. After drying, a yellow solid is obtained, which is chiral binaphthylmethyl viologen, i.e., R-BINMeV, S-BINMeV, R-BINAMeV or S-BINAMeV.

[0037] Under argon environment, R-BINPY, S-BINPY, R-BINAPY or S-BINAPY, diphenyl trifluoromethanesulfonic acid iodide and cupric acetate are dissolved in N,N-dimethylformamide solution, the reaction solution is stirred at 80-110 °C for 6-24 hours, the reaction mixture is washed three times with a mixed solution of acetone, chloroform and ether, and dried to obtain a yellow solid, which is chiral binaphthyl viologen, namely R-BINPhV, S-BINPhV, R-BINAPhV or S-BINAPhV.

[0038] In addition, the obtained product can be subjected to ion exchange to obtain a product whose anion is TFSI or PF6.

[0039] At the same time, the present invention also discloses a circularly polarized organic light-emitting diode, which contains the circularly polarized light-emitting material. The structure of the circularly polarized organic light-emitting diode is specifically: anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode, wherein the circularly polarized light-emitting material is used as the light-emitting layer, has a higher light-emitting asymmetry factor, and can obtain a high-performance OLED.

[0040] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0041] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0042] Example 1 Preparation of R-BINMeV (1) Synthesis of 4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL) Dissolve 1-bromo-3-hydroxynaphthalene (4 g, 18 mmol) in dichloromethane (80 mL) and add dihydroxy-bis-tetramethylethylenediamine copper chloride (Cl(OH)TMEDA) (42 mg, 0.18 mmol). Place the system under oxygen atmosphere and stir at room temperature for 16 h. After the reaction is complete, the reaction mixture is concentrated under reduced pressure and then subjected to silica gel column chromatography. Using gradient chromatography ( V 二氯甲烷 : V 石油醚 =1:2, dichloromethane), to obtain 1.75 g of light yellow solid with a yield of 43%, to obtain 4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL), i.e., a mixture of R-BINDL and S-BINDL.

[0043] (2) Chiral separation Take 4,4'-dibromo-2,2-dihydroxy-1,1'-binaphthyl and have it split by a chiral company to obtain right-handed or left-handed 4,4'-dibromo-2,2-dihydroxy-1,1'-binaphthyl (R-BINDL or S-BINDL).

[0044] Compound BINDL: 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.5 Hz, 2H), 7.75 (s,2H), 7.49 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H),5.04 (s, 2H). (3) Synthesis of intermediate R-4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (R-BINDB) R-BINDL (1 g, 2.25 mmol), ethyl bromide (1 mL, 13.5 mmol), sodium iodide (0.054 g, 0.36 mg), and potassium carbonate (1.56 g, 11.25 mmol) were added to a round-bottom flask and dissolved in acetone solution. The mixture was refluxed for 30 h. After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The concentrated solid was added with acetone for recrystallization and purification to obtain 0.5 g of light yellow solid, i.e., R-BINDB, with a yield of about 50%.

[0045] Compound R-BINDB: 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.5 Hz, 2H), 7.75(s, 2H), 7.49 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.4 Hz,2H), 5.04 (s, 2H). Compound S-BINDB: 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.5 Hz, 2H), 7.75(s, 2H), 7.49 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.4 Hz,2H), 5.04 (s, 2H). (4) Synthesis of the intermediate chiral 4,4′-bipyridine-2,2′-dioxy-1,1′-binaphthyl (R-BINPY) R-BINDB (0.32 g, 0.62 mmol), pyridine-4-boric acid (0.23 g, 1.86 mmol), and potassium carbonate (0.43 g, 3.10 mmol) were added to a round-bottom flask. Subsequently, argon was introduced into the flask. In an argon atmosphere, Pd(PPh3)4 (45.0 mg, 0.039 mmol), 1,4-dioxane (12.5 mL), and deionized water (1.26 mL) were added thereto, and the mixture was heated under reflux for 16 h. After the reaction was completed, the reaction solution was subjected to reduced pressure rotary evaporation. The solid reaction mixture after spin drying was added with 30 mL of water and stirred. The aqueous layer was extracted three times with 30 mL of dichloromethane. The organic layer was separated, and the residual water was dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure. The obtained solid was purified by column chromatography (petroleum ether: ethyl acetate = 10:1, 5% triethylamine → petroleum ether: ethyl acetate = 5:1, 5% triethylamine) to obtain a white solid, i.e., chiral dextrorotatory 4,4´-bipyridine-2,2´-dioxy-1,1´-binaphthyl (R-BINPY). The yield was 0.25 g, and the yield was about 80%.

[0046] Compound R-BINPY: 1 H NMR (400 MHz, CDCl3) δ 8.81 (d, J = 5.0 Hz, 4H), 7.84(d, J = 8.1 Hz, 2H), 7.64 (d, J = 5.7 Hz, 4H), 7.37 (s, 2H), 7.32 (ddd, J = 17.2,9.3, 3.6 Hz, 6H), 4.12 (qd, J = 7.0, 2.1 Hz, 4H), 1.12 (t, J = 7.0 Hz, 6H). (5) Synthesis of chiral right-handed binaphthylmethyl viologen (R-BINMeV) Under argon atmosphere, R-BINPY (0.1 g, 0.2 mmol) was added to a round-bottom flask, and dichloromethane (5 mL) was added. The reaction solution was stirred at 0 ° C, and methyl trifluoromethanesulfonate (0.05 L, 0.44 mmol) was added dropwise. After the addition, the reaction solution was stirred at room temperature for 15 h. After the reaction was completed, the reaction mixture was washed three times with dichloromethane (5 mL) to wash away the unmethylated chiral binaphthylpyridine and methyl trifluoromethanesulfonate. After drying, a yellow solid was obtained, which was chiral right-handed binaphthylmethyl viologen (R-BINMeV). Yield: 0.09 g, with a yield of about 90%.

[0047] Compound R-BINMeV: melting point: 201-203 ℃. 1 H NMR (400 MHz, DMSO) δ 9.18 (d, J =6.0 Hz, 4H), 8.51 (d, J = 5.9 Hz, 4H), 7.86 (d, J = 8.3 Hz, 2H), 7.76 (s, 2H), 7.42 (dt, J = 15.0, 7.1 Hz, 4H), 7.11 (d, J = 8.3 Hz, 2H), 4.47 (s, 6H), 4.22 (d, J = 6.9 Hz, 4H), 1.07 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ 155.43,155.23, 145.41, 135.31, 133.80, 128.73, 127.19, 125.39, 125.23, 125.13,124.56, 121.30, 117.44, 64.50, 47.51, 14.71. 19 F NMR (376 MHz, DMSO) δ -77.7. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]263.13375; found: 263.13047. Example 2 This example is the preparation of chiral left-handed binaphthylmethyl viologen (S-BINMeV). The difference from Example 1 is that steps (3) to (5) are specifically as follows: (3) Synthesis of the intermediate S-4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthyl (S-BINDB) S-BINDL (1 g, 2.25 mmol), ethyl bromide (1 mL, 13.5 mmol), sodium iodide (0.054 g, 0.36 mg), and potassium carbonate (1.56 g, 11.25 mmol) were added to a round-bottom flask and dissolved in acetone solution. The mixture was refluxed for 30 h. After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The concentrated solid was added with acetone for recrystallization and purification to obtain 0.5 g of light yellow solid, namely S-BINDB, with a yield of about 50%.

[0048] (4) Synthesis of the intermediate chiral 4,4′-bipyridine-2,2′-dioxy-1,1′-binaphthyl (S-BINPY) S-BINDB (0.32 g, 0.62 mmol), pyridine-4-boric acid (0.23 g, 1.86 mmol), and potassium carbonate (0.43 g, 3.10 mmol) were added to a round-bottom flask. Subsequently, argon was introduced into the flask. In an argon atmosphere, Pd(PPh3)4 (45.0 mg, 0.039 mmol), 1,4-dioxane (12.5 mL), and deionized water (1.26 mL) were added thereto, and the mixture was heated under reflux for 16 h. After the reaction was completed, the reaction solution was subjected to reduced pressure rotary evaporation. The solid reaction mixture after spin drying was added with 30 mL of water and stirred. The aqueous layer was extracted three times with 30 mL of dichloromethane. The organic layer was separated, and the residual water was dried over anhydrous sodium sulfate. The filtrate was filtered and concentrated under reduced pressure. The obtained solid was purified by column chromatography (petroleum ether: ethyl acetate = 10:1, 5% triethylamine → petroleum ether: ethyl acetate = 5:1, 5% triethylamine) to obtain a white solid, which was chiral left-4,4´-bipyridine-2,2´-dioxy-1,1´-binaphthyl (S-BINPY). The yield was 0.25 g, and the yield was about 80%.

[0049] Compound S-BINPY: 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.5 Hz, 2H), 7.75(s, 2H), 7.49 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.4 Hz,2H), 5.04 (s, 2H). (5) Synthesis of chiral left-handed binaphthylmethyl viologen (S-BINMeV) Under argon atmosphere, S-BINPY (0.1 g, 0.2 mmol) was added to a round-bottom flask, and dichloromethane (5 mL) was added. The reaction solution was stirred at 0 °C, and methyl trifluoromethanesulfonate (0.05 L, 0.44 mmol) was added dropwise. After the addition, the reaction solution was stirred at room temperature for 15 h. After the reaction, the reaction mixture was washed three times with dichloromethane (5 mL) to remove the unmethylated chiral binaphthylpyridine and methyl trifluoromethanesulfonate. After drying, a yellow solid was obtained, which was chiral left-handed binaphthylmethyl viologen (S-BINMeV), with a yield of 0.09 g and a yield of about 90%.

[0050] Compound S-BINMeV: melting point: 201-203 °C, 1 H NMR (400 MHz, DMSO) δ 9.18 (d, J =6.2 Hz, 4H), 8.51 (d, J = 6.1 Hz, 4H), 7.86 (d, J = 8.6 Hz, 2H), 7.76 (s, 2H), 7.42 (dt, J = 14.9, 7.2 Hz, 4H), 7.11 (d, J = 8.5 Hz, 2H), 4.47 (s, 6H), 4.27 –4.15 (m, 4H), 1.08 (t, J = 7.0 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ 155.42, 153.23,145.40, 135.31, 133.80, 128.73, 127.18, 125.39, 125.23, 125.13, 124.56,121.30, 117.43, 64.50, 47.51, 14.71. 19 F NMR (376 MHz, DMSO) δ -77.76. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]263.13299; found: 263.13047. The structural formula of the product obtained in Example 1 and Example 2 is:

[0051] Example 3 This example is the preparation of chiral right-handed binaphthylphenyl viologen (R-BINPhV). The difference from Example 1 is that step (5) is specifically as follows: (5) Under argon atmosphere, R-BINPY (0.1 g, 0.2 mmol), diphenyl trifluoromethanesulfonic acid iodide (0.27 mg, 0.6 mmol), and copper acetate (1.63 mg, 0.01 mmol) were added to a round-bottom flask, and DMF (5 mL) was added thereto. The reaction solution was stirred at 100 °C for 8 h. After the reaction was completed, DMF was removed by vacuum pump at 80 °C, and the solid reaction mixture was washed with acetone, chloroform, and ether (V Et2O :VCHCl3 :V Acetone = 1:1:1, 5 mL) mixed solution was washed three times to remove the unreacted chiral binaphthylpyridine and diphenyltrifluoromethanesulfonic acid iodide. After drying, a yellow solid was obtained, which was chiral right-handed binaphthylphenyl viologen (R-BINPhV). The yield was 0.09 g, and the yield was about 90%.

[0052] Compound R-BINPhV: Melting point: greater than 300 ℃. 1 H NMR (400 MHz, DMSO) δ 9.54 (d, J =6.4 Hz, 4H), 8.69 (d, J = 6.3 Hz, 4H), 8.01 (d, J = 7.9 Hz, 6H), 7.89 – 7.78 (m,8H), 7.47 (dt, J = 15.0, 6.7 Hz, 6H), 7.17 (d, J = 8.5 Hz, 2H), 4.27 (d, J = 6.2Hz, 4H), 1.12 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ 156.90, 153.28,144.61, 142.56, 135.18, 133.86, 131.32, 130.37, 129.05, 127.30, 125.47,125.34, 125.23, 124.77, 121.60, 117.63, 64.51, 14.73. 19 F NMR (376 MHz, DMSO) δ-77.6. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]325.14960; found:325.14612. Example 4 This example is the preparation of chiral left-handed binaphthylphenyl viologen (S-BINPhV). The difference from Example 3 is that S-BINPY is used for the reaction. Other steps are the same. The obtained product is chiral left-handed binaphthylphenyl viologen, namely S-BINPhV.

[0053] Compound S-BINPhV: Melting point: greater than 300 ℃. 1H NMR (400 MHz, DMSO) δ 9.54 (d, J =6.4 Hz, 4H), 8.69 (d, J = 6.4 Hz, 4H), 8.01 (d, J = 7.9 Hz, 6H), 7.83 (dd, J =16.9, 9.6 Hz, 8H), 7.47 (dt, J = 15.3, 7.2 Hz, 6H), 7.17 (d, J = 8.6 Hz, 2H),4.27 (dd, J = 11.6, 6.7 Hz, 4H), 1.12 (t, J = 7.0 Hz, 6H). 13 C NMR (151 MHz, DMSO)δ 156.90, 153.28, 144.61, 142.56, 135.17, 133.86, 131.32, 130.37, 129.05,127.30, 125.47, 125.34, 125.22, 124.77, 121.60, 117.63, 64.51, 14.73. 19 F NMR (376 MHz, DMSO) δ -77.6. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]325.14898; found: 325.14612. The structural formula of the product obtained in Example 3 and Example 4 is:

[0054] Example 5 This example is the preparation of chiral dextrorotatory alkynyl binaphthylmethyl viologen (R-BINAMeV). The difference from Example 1 is that steps (4) to (5) are specifically as follows: (4): Synthesis of the intermediate chiral 4,4′-bipyridine-2,2′-dioxy-1,1′-alkynylbinaphthyl (R-BINAPY) R-BINDB (0.249 g, 0.5 mmol), 4-ethynylpyridine (0.130 g, 1.25mmol), cuprous iodide (10 mg, 0.05 mmol), [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (15 mg, 0.02 mol) were added to a round-bottom flask. Triethylamine (10 mL) was added under argon atmosphere and heated to reflux for 8 h. After the reaction was completed, 30 mL of water was added to the reaction mixture and stirred. The aqueous layer was extracted three times with dichloromethane, the organic layer was separated, the residual water was dried with sodium sulfate, the filtrate was concentrated under reduced pressure after filtration, and the solid was purified by column chromatography (dichloromethane: methanol = 10:1) to obtain 53 mg of white solid, i.e., R-BINAPY, with a yield of 80%.

[0055] (5): Preparation of chiral right-rotating alkynylbinaphthylmethyl viologen (R-BINAMeV) Under argon atmosphere, R-BINAPY (0.08 g, 0.15 mmol) was added to a round-bottom flask, and dichloromethane (5 mL) was added. The reaction solution was stirred at 0 ° C, and methyl trifluoromethanesulfonate (0.037 L, 0.32 mmol) was added dropwise. After the addition, the reaction solution was stirred at room temperature for 15 h. After the reaction was completed, the reaction mixture was washed three times with dichloromethane (5 mL) to wash away the unmethylated chiral binaphthylpyridine and methyl trifluoromethanesulfonate. After drying, a yellow solid was obtained, which was chiral right-handed / left-handed binaphthylmethyl viologen (R-BINAMeV). Yield: 0.06 g, with a yield of about 75%.

[0056] Compound R-BINAPY: 1 H NMR (400 MHz, DMSO) δ 8.73 (d, J = 6.0 Hz, 4H), 8.41(d, J = 8.4 Hz, 2H), 7.97 (s, 2H), 7.75 (dd, J = 4.4, 1.6 Hz, 4H), 7.54 (s, 2H), 7.38 (s, 2H), 7.04 (d, J = 8.5 Hz, 2H), 4.16 (dd, J = 7.0, 2.5 Hz, 4H), 1.03 (t, J = 7.0 Hz, 6H). Compound R-BINAMeV: Melting point: greater than 300 ℃. 1 H NMR (400 MHz, DMSO) δ 9.08 (d, J=6.8 Hz, 4H), 8.48 (dd, J = 10.5, 7.8 Hz, 6H), 8.10 (s, 2H), 7.61 – 7.54 (m,2H), 7.45 – 7.39 (m, 2H), 7.06 (d, J = 8.6 Hz, 2H), 4.37 (s, 6H), 4.22 – 4.13(m, 4H), 1.03 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ 153.23, 145.68,138.19, 133.10, 129.06, 128.49, 127.77, 125.76, 125.62, 125.26, 123.00,121.04, 118.90, 99.88, 90.51, 64.67, 47.82, 14.62. 19 F NMR (376 MHz, DMSO) δ -77.77. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]287.13386; found:287.13047. Example 6 This example is the preparation of chiral left-handed alkynyl binaphthylmethyl viologen (S-BINAMeV). The difference from Example 1 is that steps (4) to (5) are specifically as follows: (4): Synthesis of the intermediate chiral 4,4′-bipyridine-2,2′-dioxy-1,1′-alkynylbinaphthyl (S-BINAPY) S-BINDB (0.249 g, 0.5 mmol), 4-ethynylpyridine (0.130 g, 1.25mmol), cuprous iodide (10 mg, 0.05 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (15 mg, 0.02 mol) were added to a round-bottom flask. Triethylamine (10 mL) was added under argon atmosphere and heated to reflux for 8 h. After the reaction was completed, 30 mL of water was added to the reaction mixture and stirred. The aqueous layer was extracted three times with dichloromethane, the organic layer was separated, the residual water was dried with sodium sulfate, the filtrate was concentrated under reduced pressure after filtration, and the solid was purified by column chromatography (V 二氯甲烷 :V 甲醇 =10:1) to obtain 53 mg of white solid, namely S-BINAPY, with a yield of 80%.

[0057] (5): Under argon atmosphere, S-BINAPY (0.08 g, 0.15 mmol) was added to a round-bottom flask and dichloromethane (5 mL) was added. The reaction solution was stirred at 0°C and methyl trifluoromethanesulfonate (0.037 L, 0.32 mmol) was added dropwise. After the addition, the reaction solution was stirred at room temperature for 15 h. After the reaction, the reaction mixture was washed three times with dichloromethane (5 mL) to remove the unmethylated chiral binaphthylpyridine and methyl trifluoromethanesulfonate. After drying, a yellow solid was obtained, which was chiral left-handed binaphthylmethyl viologen (S-BINAMeV). Yield: 0.06 g, with a yield of about 75%.

[0058] Compound S-BINAMeV: Melting point: greater than 300 ℃. 1 H NMR (400 MHz, DMSO) δ 9.08 (d, J =6.8 Hz, 4H), 8.48 (dd, J = 10.5, 7.7 Hz, 6H), 8.10 (s, 2H), 7.60 – 7.56 (m,2H), 7.41 (d, J = 7.2 Hz, 2H), 7.06 (d, J = 8.6 Hz, 2H), 4.37 (s, 6H), 4.21 –4.14 (m, 4H), 1.03 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ 153.23, 145.68,138.19, 133.10, 129.06, 128.49, 127.77, 125.76, 125.62, 125.26, 123.00,121.04, 118.90, 99.88, 90.51, 64.67, 47.82, 14.62. 19 F NMR (376 MHz, DMSO) δ -77.77. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]287.13372; found:287.13047. Example 7 This example is the preparation of chiral right-handed alkynylbinaphthylphenyl viologen (R-BINAPhV), and the difference from Example 5 is step (5), which is specifically: (5): Under argon atmosphere, R-BINAPY (0.08 g, 0.15 mmol), diphenyl trifluoromethanesulfonic acid iodide (0.065 g, 0.44 mmol), and copper acetate (1.37 mg, 0.007 mmol) were added to a round-bottom flask, and DMF (5 mL) was added thereto. The reaction solution was stirred at 100 °C for 8 h. After the reaction was completed, DMF was removed by vacuum pump at 80 °C, and the solid reaction mixture was washed with acetone, chloroform, and ether (V Et2O :V CHCl3 :V Acetone = 1:1:1, 5 mL) mixed solution was washed three times to remove the unreacted chiral binaphthylpyridine and diphenyltrifluoromethanesulfonic acid iodide. After drying, a yellow solid was obtained, which was chiral right-handed binaphthylphenyl viologen (R-BINAPhV). The yield was 0.06 g, and the yield was about 75%.

[0059] Compound R-BINAPY: 1 H NMR (400 MHz, DMSO) δ 8.73 (d, J = 6.0 Hz, 4H), 8.41(d, J = 8.4 Hz, 2H), 7.97 (s, 2H), 7.75 (dd, J = 4.4, 1.6 Hz, 4H), 7.54 (s, 2H), 7.38 (s, 2H), 7.04 (d, J = 8.5 Hz, 2H), 4.16 (dd, J = 7.0, 2.5 Hz, 4H), 1.03 (t, J = 7.0 Hz, 6H). Compound R-BINAPhV: melting point: 182 -184 ℃. 1 H NMR (400 MHz, DMSO) δ 8.73 (d, J =6.0 Hz, 4H), 8.41 (d, J = 8.4 Hz, 2H), 7.97 (s, 2H), 7.74 (d, J = 6.0 Hz, 4H),7.55 – 7.51 (m, 2H), 7.37 (t, J = 7.7 Hz, 2H), 7.04 (d, J = 8.6 Hz, 2H), 4.16(dd, J= 7.0, 2.5 Hz, 4H), 1.02 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ153.28, 144.77, 142.51, 139.66, 133.11, 131.33, 130.25, 129.39, 128.59,127.85, 125.75, 124.65, 123.34, 121.74, 121.39, 118.93, 101.89, 90.87, 64.73,14.64. 19 F NMR (376 MHz, DMSO) δ -77.77. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]349.14879; found: 349.14612. Example 8 This example is the preparation of chiral left-handed alkynylbinaphthylphenyl viologen (S-BINAPhV). The difference from Example 7 is that S-BINAPY reaction is used, and the product obtained is chiral left-handed alkynylbinaphthylphenyl viologen (S-BINPhV).

[0060] Compound S-BINAPY: 1 H NMR (400 MHz, DMSO) δ 8.73 (d, J = 6.0 Hz, 4H), 8.41(d, J = 8.4 Hz, 2H), 7.97 (s, 2H), 7.74 (d, J = 6.0 Hz, 4H), 7.55 – 7.51 (m, 2H), 7.37 (t, J = 7.7 Hz, 2H), 7.04 (d, J = 8.6 Hz, 2H), 4.16 (dd, J = 7.0, 2.5 Hz, 4H),1.02 (t, J = 6.9 Hz, 6H). Compound S-BINAPhV: melting point: 182-184 ℃. 1 H NMR (400 MHz, DMSO) δ 8.73 (d, J =6.0 Hz, 4H), 8.41 (d,J = 8.4 Hz, 2H), 7.97 (s, 2H), 7.74 (d, J = 6.0 Hz, 4H),7.55 – 7.51 (m, 2H), 7.37 (t, J = 7.7 Hz, 2H), 7.04 (d, J = 8.6 Hz, 2H), 4.16(dd, J = 7.0, 2.5 Hz, 4H), 1.02 (t, J = 6.9 Hz, 6H). 13 C NMR (151 MHz, DMSO) δ153.28, 144.76, 142.50, 139.66, 133.11, 131.32, 130.24, 129.38, 128.59,127.85, 125.74, 125.28, 124.65, 123.34, 121.39, 118.92, 101.89, 90.87, 64.72,14.64. 19 F NMR (376 MHz, DMSO) δ -77.77. HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]349.14890; found: 349.14612. The structural formula of the product obtained in Example 7 and Example 8 is:

[0061] Figure 2 The UV-visible absorption spectrum of the chiral right-handed binaphthyl phenyl viologen prepared in Example 3 of the present invention after reduction with metallic zinc and sodium; Figure 3 The figure is the UV-visible absorption spectrum of the chiral left-handed binaphthyl phenyl viologen prepared in Example 4 of the present invention after reduction with metallic zinc and sodium. As can be seen from the figure, after zinc reduction, the color of the chiral right-handed binaphthyl phenyl viologen and the chiral left-handed binaphthyl phenyl viologen solution basically did not change. After sodium reduction, the solution color changed from orange to yellow, and the peak at a wavelength of 600-700 nm increased, indicating that the color of the chiral right-handed / left-handed binaphthyl phenyl viologen changed after being reduced to different states. This property makes the compound have potential important application value in the fields of optoelectronics and sensors.

[0062] Figure 4 The cyclic voltammetry curve of the chiral right-handed binaphthyl phenyl viologen prepared in Example 3 of the present invention is shown in FIG. Figure 5 This is the cyclic voltammetry curve of the chiral left-handed binaphthylphenyl viologen prepared in Example 4 of the present invention. It can be seen from the figure that after the introduction of phenyl on pyridine, the chiral right-handed / left-handed binaphthylphenyl viologen has the electrochemical characteristics of the viologen molecule, and has a set of redox peaks by applying voltage. At the same time, the electrochemical data measured at different scan rates show that the two molecules have good stability.

[0063] Figure 6 This is the electron paramagnetic resonance spectrum of the chiral right-handed binaphthylphenyl viologen prepared in Example 3 of the present invention, Figure 7 This is an electron paramagnetic resonance spectrum of the chiral left-handed binaphthyl phenyl viologen prepared in Example 4 of the present invention. It can be seen from the figure that free radicals are generated in the chiral right-handed / left-handed binaphthyl phenyl viologen after adding sodium.

[0064] Figure 8 3 is the fluorescence spectrum of the chiral right-handed / left-handed binaphthyl phenyl viologen prepared in Examples 3-4 of the present invention. As can be seen from the figure, the chiral right-handed / left-handed binaphthyl phenyl viologen molecules have good fluorescence emission performance at around 600nm.

[0065] Fig. 9 The circular dichroism spectrum of the chiral right-handed / left-handed binaphthyl phenyl viologen prepared in Examples 3-4 of the present invention is a spectral technique used to detect the difference in absorption of left-handed and right-handed circularly polarized light by chiral molecules within a specific wavelength range. This difference reflects the optically selective absorption of light by chiral molecules, which is a unique optical property of chiral molecules. It can be seen from the figure that the chiral right-handed / left-handed binaphthyl phenyl viologen has a strong absorption at 270-400 nm. This wavelength range corresponds to the electronic transition of certain chromophores in the molecule, such as π-π Transition or n-π Transition. For molecules such as binaphthyl phenyl viologen, the absorption peak is related to the conjugated system, substituents and the structure of the chiral center in the molecule. Chiral right-handed and left-handed binaphthyl phenyl viologens show strong absorption peaks and significant chiral optical activity in the circular dichroism spectrum.

[0066] Fig.10 The circularly polarized luminescence test results of the chiral right-handed / left-handed binaphthylphenyl viologen prepared in Examples 3 and 4 of the present invention are shown in FIG. Fig.11The luminescence asymmetry factor diagram of the chiral right-handed / left-handed binaphthyl phenyl viologen prepared in Examples 3 to 4 of the present invention is shown. The size of the luminescence asymmetry factor directly reflects the strength of the circular polarization directionality of the chiral molecule during the luminescence process. A higher g-factor value means that the luminophore can more effectively emit light in a single circular polarization direction, which has important application value in the fields of optical sensing, information storage, and display technology. It can be seen from the figure that the chiral right-handed / left-handed binaphthyl phenyl viologen has good circularly polarized luminescence characteristics, and the luminescence asymmetry factor can reach up to 0.01, making the chiral viologen molecule potentially applicable in circularly polarized light-emitting devices, chiral recognition sensors, and optical switches.

[0067] Fig.12 The circularly polarized luminescent material prepared in Example 3 of the present invention, i.e., the SEM images of chiral right-handed binaphthyl phenyl viologen at different magnifications, wherein the scale of (a) is 100 μm, and the scale of (b) is 30 μm. It can be seen from the figures that the circularly polarized luminescent material prepared in the present invention has an obvious chiral fractal structure after stacking, has a chiral amplification effect, and exhibits controllable self-assembly, which is mainly attributed to the large amount of π-π stacking and hydrogen bonding interactions between molecules, which produce this chiral fractal structure assembly, greatly improving the circularly polarized luminescence performance of the binaphthyl molecules.

[0068] Example 9 The product compound whose anion is Cl, Br or I is placed in a saturated aqueous solution of LiTFSI, stirred overnight, and the solid part is washed 3 to 5 times by centrifugation with water to obtain the anion TFSI - of viologen molecules.

[0069] Example 10 The product with an anion of Cl, Br or I is placed in a saturated aqueous solution of NH4PF6, stirred overnight, and the solid part is washed 3 to 5 times by centrifugation with water to obtain a product with an anion of PF6 - of viologen molecules.

[0070] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A circularly polarized luminescent material, characterized in that: Including compounds represented by general formula (I): Among them, R1 is or ; X = OTf, Cl, Br, I, TFSI or PF6; R2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene.

2. The method for preparing a circularly polarized luminescent material according to claim 1, characterized in that: The following steps are involved: S1: 1-bromo-3-hydroxynaphthalene and dihydroxy-bis-tetramethylethylenediamine copper chloride were dissolved in dichloromethane, and then the system was placed in an oxygen atmosphere and stirred for reaction to obtain R / S-BINDL; S2: After splitting the R / S-BINDL, dissolving the split BINDL, ethyl bromide, sodium iodide and potassium carbonate in acetone and subjecting them to reflux reaction to obtain R-BINDB or S-BINDB; S3: After mixing the R-BINDB or S-BINDB with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium, 1,4-dioxane is added under an argon atmosphere for reflux reaction to obtain R-BINPY or S-BINPY; or after mixing the R-BINDB or S-BINDB with 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, triethylamine is added under an argon atmosphere for reflux reaction to obtain R-BINAPY or S-BINAPY; S4: reacting the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodide, halogenated benzyl, halogenated methylnaphthalene, halogenated methylanthracene, halogenated methylbenzopyrene, halogenated methylpyrene, halogenated methylphenanthrene or halogenated methylperylene to obtain the circularly polarized luminescent material.

3. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S1, the molar ratio of 1-bromo-3-hydroxynaphthalene to dihydroxy-bis-tetramethylethylenediamine copper chloride is 1:(0.008-0.02).

4. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S1, the reaction is stirred for 14 to 24 hours.

5. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S2, the molar ratio of the separated BINDL, ethyl bromide, sodium iodide and potassium carbonate is 1:(4-8):(0.1-0.2):(4-8); in step S2, the temperature of the reflux reaction is 60-75° C., and the time is 20-50 h.

6. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S3, the molar ratio of the R-BINDB or S-BINDB to pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium is 1:(2-6):(4-8):(0.03-0.1), and the temperature of the reflux reaction of the R-BINDB or S-BINDB with pyridine-4-boric acid, potassium carbonate and tetrakistriphenylphosphine palladium and 1,4-dioxane is 105-125° C., and the time is 12-24 h.

7. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S3, the molar ratio of the R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 1:(2-5):(0.08-0.15):(0.03-0.05), and the reflux reaction temperature of the R-BINDB or S-BINDB and 4-ethynylpyridine, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride and triethylamine is 95-115° C. for 8-18 h.

8. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to methyl trifluoromethanesulfonate is 1:(2-6), the reaction temperature is room temperature, and the reaction time is 12-24 hours.

9. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that: In step S4, the molar ratio of R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to diphenyltrifluoromethanesulfonic acid iodide is 1:(2-6), the reaction temperature is 80-110° C., and the reaction time is 6-12 h.

10. A circularly polarized organic light emitting diode, characterized in that: Contains the circularly polarized luminescent material as described in claim 1.

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