A circularly polarized light-emitting material, a preparation method thereof, and a circularly polarized organic light-emitting diode

Abstract

The application discloses a circularly polarized luminescent material and a preparation method thereof, and a circularly polarized organic light-emitting diode. The circularly polarized luminescent material comprises a compound shown in a general formula (I): wherein R1 is or ; X is OTf, Cl, Br, I, TFSI or PF6; and R2 is any one of a methyl group, a phenyl group, a benzyl group, a methylnaphthalene group, a methylanthracene group, a methylbenzopyrene group, a methylpyrene group, a methylphenanthrene group and a methylperylene group. The circularly polarized luminescent material improves the circularly polarized luminescent performance of the material through the synergistic effect among a chiral binaphthyl structure, a pyridine ring and a substituent group thereof, and a supermolecular structure or a fractal structure formed.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic light-emitting molecule development, and relates to a circularly polarized light-emitting material, a preparation method thereof, and a circularly polarized organic light-emitting diode. BACKGROUND

[0002] Circularly polarized light is a special kind of polarized light, and the electric field vector thereof rotates clockwise or counterclockwise in the direction of the light source, and is called right-handed or left-handed polarized light, respectively. Circularly polarized light emission (CPL) refers to the phenomenon that a chiral light-emitting body produces unequal left-handed and right-handed polarized light under excitation. Therefore, the circularly polarized organic light-emitting diode (CP-OLED) based on circularly polarized light is widely used in the fields of anti-counterfeiting and encryption, health eye protection, optical data storage, chiral sensing, liquid crystal and three-dimensional display technology, etc. due to its ability to emit light with circularly polarized characteristics.

[0003] Generally, the method for obtaining circularly polarized light is to filter ordinary non-polarized light through a series of filters such as linear polarizers, 1 / 4 wave plates, etc. However, this method requires a complex device structure and causes a large amount of energy loss. Therefore, it is of great significance to develop chiral light-emitting materials capable of directly emitting circularly polarized light. Typical circularly polarized light-emitting materials contain two main parts: a chiral part and a light-emitting 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 not superimposable on their mirror images, which means they cannot be coincided by simple translation and rotation. The chiral axis is usually determined by chemical bonds that cannot rotate freely due to steric hindrance of the groups. Binaphthyl molecules are formed by connecting two naphthalene molecules at the 1-position through a single bond. Due to the large plane of naphthalene, the two naphthalene rings cannot be coplanar due to steric hindrance, but are staggered with each other, and the planes thereof have a certain angle. This structure makes binaphthyl usually exhibit axial chirality. In addition, binaphthyl molecules have a large light-emitting asymmetry factor, are relatively simple to synthesize, and have circularly polarized light-emitting performance. However, the light-emitting performance of binaphthyl molecules is poor, which limits their wide application. SUMMARY

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

[0005] The present application is realized by the following technical solutions:

[0006] A circularly polarized light-emitting material comprises a compound represented by general formula (I):

[0007]

[0008] wherein 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.

[0009] The preparation method of the circularly polarized luminescent material comprises the following steps:

[0010] S1: 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethyldiethylene diamine copper are dissolved in dichloromethane, and then the system is stirred and reacted under an oxygen atmosphere to obtain R / S-BINDL;

[0011] S2: After the R / S-BINDL is separated, the separated BINDL, bromoethane, sodium iodide and potassium carbonate are dissolved in acetone and refluxed to obtain R-BINDB or S-BINDB;

[0012] S3: The R-BINDB or S-BINDB is mixed with pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine palladium, and then refluxed under an argon atmosphere by adding 1,4-dioxane to obtain R-BINPY or S-BINPY, or the R-BINDB or S-BINDB is mixed with 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium, and then refluxed under an argon atmosphere by adding triethylamine to obtain R-BINAPY or S-BINAPY;

[0013] S4: The R-BINPY, S-BINPY, R-BINAPY or S-BINAPY is reacted with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodine, halogenated benzyl, halogenated methylnaphthalene, halogenated methylanthracene, halogenated methylbenzopyrene, halogenated methylpyrene, halogenated methylphenanthrene or halogenated methylperylene to obtain the circularly polarized luminescent material.

[0014] Preferably, in step S1, the molar ratio of the 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethyldiethylene diamine copper is 1:(0.008-0.02).

[0015] Preferably, in step S1, the stirring reaction is performed for 14-24 hours.

[0016] Preferably, in step S2, the molar ratio of the split BINDL, bromoethane, 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℃, and the time is 20-50h.

[0017] Preferably, in step S3, the molar ratio of the R-BINDB or S-BINDB, pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine 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, pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine palladium with 1,4-dioxane is 105-125℃, and the time is 12-24h.

[0018] Preferably, in step S3, the molar ratio of the R-BINDB or S-BINDB, 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium is 1:(2-5):(0.08-0.15):(0.03-0.05), and the temperature of the reflux reaction of the R-BINDB or S-BINDB, 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium with triethylamine is 95-115℃, and the time is 8-18h.

[0019] Preferably, in step S4, the molar ratio of the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY and methyl trifluoromethanesulfonate is 1:(2-6), the reaction temperature is room temperature, and the reaction time is 12-24h.

[0020] Preferably, in step S4, the molar ratio of the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY and diphenyl triflate is 1:(2-6), the reaction temperature is 80-110℃, and the reaction time is 6-12h.

[0021] A circularly polarized organic light-emitting diode comprises the circularly polarized light-emitting material described above.

[0022] Compared with the prior art, the application has the following beneficial technical effects:

[0023] The application discloses a circularly polarized light-emitting material, which comprises a compound shown in general formula (I):

[0024] wherein 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 alkyne group, and a pyridine ring or a substituted pyridine ring is bonded to the binaphthyl structure. Firstly, in the molecule, the binaphthyl structure itself has chiral characteristics and can produce circularly polarized light. The difference in chiral configuration between the excited state and the ground state of the binaphthyl structure will cause 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 large conjugated plane inside the molecule, making the movement of electrons inside the molecule more free. High conjugation degree is conducive to the delocalization and transmission of electrons inside the molecule, thereby effectively reducing the molecular energy gap. Smaller molecular energy gap means that electrons are more easily excited, so it is easier to respond under external stimulation, which is more conducive to improving the luminescent performance. At the same time, the pyridine ring and its substituents can also promote the transfer of energy from the excited state to the luminescent state as intermediates of energy transfer, thereby improving the luminescent efficiency. In addition, the pyridine ring or the substituted pyridine ring bonded to the chiral binaphthyl structure can form a supramolecular structure through intermolecular interactions (including hydrogen bonds and pi-pi stacking, etc.). In this process, chirality is transmitted from the chiral binaphthyl structure to the pyridine ring and its substituents, and further to the entire supramolecular structure, realizing multi-level amplification of chirality, and finally forming a two-dimensional chiral fractal structure that can significantly amplify the chiral signal and the circularly polarized luminescent performance. Therefore, in the present application, the synergistic effect between the chiral binaphthyl structure, the pyridine ring and its substituents, and the supramolecular structure or fractal structure formed thereby, collectively improves the circularly polarized luminescent performance of the material.

[0025] Further, the application also discloses a preparation method of the circularly polarized luminescent material, which comprises the following steps: firstly, using 1-bromo-3-hydroxynaphthalene as raw material, and performing oxidative coupling under the action of an organic catalyst, i.e., chlorinated dihydroxy-bistetramethyl ethylene diamine copper, so as to introduce a chiral center and obtain R / S-BINDL, i.e., a mixture of R-BINDL and S-BINDL; then performing chiral separation on the R / S-BINDL, and performing reaction on the separated R-BINDL or S-BINDL with bromoethane so as to introduce an ethyl group and perform alkylation, 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; then, R-BINDB or S-BINDB is subjected to a Suzuki coupling reaction with pyridine-4-boric acid under the catalysis of tetraphenylphosphonium palladium so as to generate R-BINPY or S-BINPY, or R-BINDB or S-BINDB is subjected to a Sonogashira coupling reaction with 4-ethynylpyridine under the catalysis of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium so as to generate R-BINAPY or S-BINAPY, wherein different coupling reactions are used to introduce different pyridine groups (pyridine-4-yl or 4-ethynylpyridine) into the binaphthyl viologen molecule, so as to increase the conjugation degree and functionality of the molecule; finally, R-BINPY, S-BINPY, R-BINAPY or S-BINAPY is reacted with methyl trifluoromethanesulfonate, diphenyl trifluoromethanesulfonic acid iodine, benzyl bromide, bromomethylnaphthalene, bromomethylanthracene, bromomethylbenzopyrene, bromomethylpyrene, bromomethylphenanthrene or bromomethylperylene, so as to substitute the nitrogen atom on the pyridine ring, so that the chiral binaphthyl pyridine becomes a cationic viologen derivative with electrochemical properties. The preparation method of the circularly polarized luminescent material has the advantages of clear synthesis route, high efficiency of chiral control of product, mild reaction condition, strong product diversity and functionality, large conjugated structure, and good circularly polarized luminescent performance.

[0026] Further, another inventive point of the present application is that in step S1, the molar ratio of 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethyldiethylene diamine copper is 1:(0.008~0.02). First, by controlling the molar ratio of the two reactants, the reaction conditions can be optimized, making the generation of the target product (R / S-BINDL) more favorable. Lower use of chlorinated dihydroxy-bistetramethyldiethylene diamine copper can reduce the occurrence of side reactions and improve the selectivity of the reaction, thereby obtaining a target product with higher purity. In addition, although chiral resolution mainly occurs in subsequent steps, the reaction conditions in step S1 also affect the preliminary formation of chiral products. Appropriate molar ratio helps to form a certain proportion of chiral intermediates at the initial stage of the reaction, providing a more favorable basis for subsequent chiral resolution. In addition, the proportion of reactants has a significant impact on the reaction rate. By adjusting the molar ratio, the optimal balance point between reaction rate and yield can be determined. Too low catalyst dosage will result in too slow reaction rate, while too high dosage will trigger unnecessary side reactions. Therefore, the setting of this molar ratio range helps to ensure reaction efficiency while obtaining higher yield.

[0027] Further, another inventive point of the present application is that in step S1, the molar ratio of 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethyldiethylene diamine copper is 1:(0.008~0.02). First, by controlling the molar ratio of the two reactants, the reaction conditions can be optimized, making the generation of the target product (R / S-BINDL) more favorable. Lower use of chlorinated dihydroxy-bistetramethyldiethylene diamine copper can reduce the occurrence of side reactions and improve the selectivity of the reaction, thereby obtaining a target product with higher purity. In addition, although chiral resolution mainly occurs in subsequent steps, the reaction conditions in step S1 also affect the preliminary formation of chiral products. Appropriate molar ratio helps to form a certain proportion of chiral intermediates at the initial stage of the reaction, providing a more favorable basis for subsequent chiral resolution. In addition, the proportion of reactants has a significant impact on the reaction rate. By adjusting the molar ratio, the optimal balance point between reaction rate and yield can be determined. Too low catalyst dosage will result in too slow reaction rate, while too high dosage will trigger unnecessary side reactions. Therefore, the setting of this molar ratio range helps to ensure reaction efficiency while obtaining higher yield.

[0028] Further, another inventive point of the present application is that in step S2, the molar ratio of the split BINDL, bromoethane, 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. Bromoethane, as an alkylating agent, can promote the alkylation of BINDL and improve the generation rate and yield of the target product. At the same time, the appropriate amount of sodium iodide as a catalyst or promoter can accelerate the reaction process. The amount of potassium carbonate as a base also needs to 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 step and reduce production costs. The long reflux reaction time (20-50h) allows sufficient time for the reactants to interact and transform, thereby 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 of 70°C can accelerate the reaction rate while reducing the occurrence of side reactions and improving the reaction yield.

[0029] Further, another inventive point of the present application is that in step S3, the molar ratio of the R-BINDB or S-BINDB, pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine 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, pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine palladium with 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 to make the generation of the target product (i.e. the product of the coupling of R-BINDB or S-BINDB with pyridine-4-boronic acid) more favorable. Appropriate excess of pyridine-4-boronic acid can promote the coupling reaction, and the amount of potassium carbonate as a base also needs to be controlled within a certain range to maintain the acid-base balance of the reaction system and promote the smooth progress of the reaction. Tetrakis triphenylphosphine palladium as a catalyst, although in small amount, plays a key role, and an appropriate amount of catalyst can significantly improve the reaction rate and yield. Accurate control of reaction conditions and the amount of reactants can reduce the generation of by-products, thereby improving the purity of the target product, which is very important for the simplification of the subsequent purification step and the quality control of the final product. The long reflux reaction time (12-24h) allows sufficient time for the reactants to interact and transform, thereby ensuring that the reaction is as complete as possible. This helps to reduce the residue of unreacted raw materials and improve the yield of the product. In addition, the reflux reaction temperature of 115°C can accelerate the reaction rate while reducing the occurrence of side reactions and improving the reaction yield.

[0030] Further, another inventive point of the present application is that in step S3, the molar ratio of R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium is 1:(2-5):(0.08-0.15):(0.03-0.05), and the temperature of reflux reaction of R-BINDB or S-BINDB with 4-ethynylpyridine, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium and triethylamine is 95-115°C, and the time is 8-18h. Firstly, by precisely controlling the molar ratio of reactants, especially the amount of catalysts [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium and cuprous iodide, the efficiency of Sonogashira coupling reaction can be significantly improved. These two catalysts play a key role in the reaction, promoting the coupling between alkyne and halogenated hydrocarbon to generate the target product containing a triple bond. The appropriate molar ratio of reactants and reaction time can ensure that the reaction is as complete as possible, reducing the residue of unreacted raw materials, thereby improving 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 is 95-115°C, which can accelerate the reaction rate while reducing the occurrence of side reactions and improve the reaction yield.

[0031] Further, another inventive point of the present application 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), and the reaction temperature is room temperature, and the reaction time is 12-24h. Firstly, the reaction is carried out at room temperature, which avoids the risk of side reactions and product decomposition caused by high temperature, and the room temperature reaction condition is more mild, which is conducive to maintaining the stability and activity of the product, and also reduces the requirements for experimental equipment and energy consumption. By precisely controlling the molar ratio of reactants, the effective collision and reaction between reactants can be ensured, and methyl trifluoromethanesulfonate as an esterification reagent can promote the esterification reaction, improve the generation rate and yield of the target product. Long-time reaction (12-24h) at room temperature allows sufficient time for the reactants to interact and transform, which helps to reduce the generation of by-products and improve the purity and selectivity of the target product.

[0032] Further, another inventive point of the present application is that in step S4, the molar ratio of the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY to diphenyl iodine triflate is 1:(2-6), the reaction temperature is 80-110°C, and the reaction time is 4-12h. Higher reaction temperature can significantly increase the molecular motion speed of the reactants, increase the collision frequency between them, and thus speed up the reaction rate. In the appropriate temperature range, the interaction between the reactants is more sufficient, which is beneficial to the generation of the target product. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor.

[0034] Figure 1 Reaction process diagram for synthesizing circularly polarized luminescent material in the present application;

[0035] Figure 2 UV-visible absorption spectrum of the circularly polarized luminescent material prepared in Example 3 of the present application, i.e. chiral right-handed binaphthyl phenyl viologen after reduction by zinc and sodium;

[0036] Figure 3 UV-visible absorption spectrum of the circularly polarized luminescent material prepared in Example 4 of the present application, i.e. chiral left-handed binaphthyl phenyl viologen after reduction by zinc and sodium;

[0037] Figure 4 Cyclic voltammetry curve of the circularly polarized luminescent material prepared in Example 3 of the present application, i.e. chiral right-handed binaphthyl phenyl viologen;

[0038] Figure 5 Cyclic voltammetry curve of the circularly polarized luminescent material prepared in Example 4 of the present application, i.e. chiral left-handed binaphthyl phenyl viologen;

[0039] Figure 6 Electron paramagnetic resonance spectrum of the circularly polarized luminescent material prepared in Example 3 of the present application, i.e. chiral right-handed binaphthyl phenyl viologen;

[0040] Figure 7 Electron paramagnetic resonance spectrum of the circularly polarized luminescent material prepared in Example 4 of the present application, i.e. chiral left-handed binaphthyl phenyl viologen;

[0041] Figure 8 Fluorescence spectrum of the circularly polarized luminescent material prepared in Examples 3-4 of the present application, i.e. chiral right-handed / left-handed binaphthyl phenyl viologen;

[0042] Figure 9 Circular dichroism spectra of the circularly polarized luminescent material prepared in Example 3~4 of the present application, i.e. chiral dextro- / levo- binaphthyl phenyl viologen;

[0043] Figure 10 Circularly polarized luminescence test results of the circularly polarized luminescent material prepared in Example 3~4 of the present application, i.e. chiral dextro- / levo- binaphthyl phenyl viologen;

[0044] Figure 11 Emission asymmetry factor diagrams of the circularly polarized luminescent material prepared in Example 3~4 of the present application, i.e. chiral dextro- / levo- binaphthyl phenyl viologen;

[0045] Figure 12 SEM diagrams of the circularly polarized luminescent material prepared in Example 3 of the present application, i.e. chiral dextro- binaphthyl phenyl viologen at different magnifications. DETAILED DESCRIPTION

[0046] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have the usual meanings understood by those skilled in the art of the present application, and in the event of a conflict, the definitions in the present specification shall prevail.

[0047] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, i.e. the present application can be practiced without regard to any particular theory or mechanism.

[0048] Herein, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0049] Herein, unless otherwise specified, “comprise”, “include”, “contain”, “have” or similar words encompass the meaning of “consist of” and “consist essentially of”, e.g. “A comprises a” encompasses the meaning of “A comprises a and other” and “A comprises only a”.

[0050] Herein, for the sake of brevity, all possible combinations of the technical features in each embodiment or example are not described. Therefore, as long as the combinations of the technical features do not contradict each other, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope of the present specification.

[0051] The application provides a circularly polarized luminescent material characterized by comprising a compound shown in a general formula (I):

[0052] ;

[0053] wherein R1 is or ; X = OTf, Cl, Br, I, TFSI or PF6; and R2 is any one of methyl, phenyl, benzyl, methylnaphthalene, methylanthracene, methylbenzopyrene, methylpyrene, methylphenanthrene and methylperylene.

[0054] In addition, the application further discloses a preparation method of the circularly polarized luminescent material, raw materials are 1-bromo-3-hydroxynaphthalene, chlorinated dihydroxy-bistetramethylylethylenediamine copper, potassium carbonate, sodium iodide, cuprous iodide, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, bromoethane, pyridine-4-boronic acid, tetrakis(triphenylphosphine)palladium, potassium carbonate, anhydrous copper acetate, diphenyl iodine triflate, methyl trifluoromethanesulfonate, and the method comprises the following steps:

[0055] (1) synthesis of 4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthalene (R / S-BINDL)

[0056] 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethylylethylenediamine copper are dissolved in dichloromethane, the molar ratio of 1-bromo-3-hydroxynaphthalene and chlorinated dihydroxy-bistetramethylylethylenediamine copper is 1: (0.008-0.02), then the system is stirred under an oxygen atmosphere for 14-24 hours, after the reaction is completed, the reaction mixture is concentrated under reduced pressure, and then silica gel column chromatography is carried out, gradient chromatography (dichloromethane: petroleum ether = 1:2, dichloromethane) is adopted, and light yellow solid, namely R / S-BINDL, is obtained, the R / S-BINDL is a mixture of R-BINDL and S-BINDL.

[0057] (2) chiral resolution

[0058] 5 g of 4,4'-dibromo-2,2-dihydroxy-1,1'-binaphthalene is resolved by a chiral company to obtain R-BINDL or S-BINDL, wherein the chiral company is a large race Lu pharmaceutical chiral technology limited company.

[0059] (3) synthesis of intermediate R / S-4,4'-dibromo-2,2'-diethoxy-1,1'-binaphthalene (R-BINDB or S-BINDB)

[0060] The split BINDL (R-BINDB or S-BINDB), bromoethane, sodium iodide and potassium carbonate are dissolved in acetone, and refluxed at 60-75°C for 20-50h, wherein the molar ratio of R-BINDB or S-BINDB to bromoethane, sodium iodide and potassium carbonate is 1: (4-8): (0.1-0.2): (4-8), and after cooling, the reaction mixture is filtered, and the filtrate is concentrated under reduced pressure, and the reaction mixture is recrystallized by adding acetone to purify, to obtain a light yellow solid, i.e. R-BINDB or S-BINDB;

[0061] (4): synthesis of intermediate chiral 4,4'-bipyridine-2,2'-dioxy-1,1'-binaphthyl (R-BINPY or S-BINPY) or chiral alkynyl binaphthyl pyridine (R-BINAPY or S-BINAPY)

[0062] The R-BINDB or S-BINDB is mixed with pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine palladium, wherein the molar ratio of R-BINDB or S-BINDB to pyridine-4-boronic acid, potassium carbonate and tetrakis triphenylphosphine palladium is 1: (2-6): (4-8): (0.03-0.1), 1,4-dioxane is added under argon atmosphere, and refluxed at 105-125°C for 12-24h, the reaction solution is rotary evaporated under reduced pressure, the reaction mixture is stirred with water, the water layer is extracted with dichloromethane for three times, the residual water of the organic layer is dried with sodium sulfate, the filtrate is 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, i.e. R or S-4,4'-bipyridine-2,2'-dioxy-1,1'-binaphthyl (R-BINPY or S-BINPY);

[0063] or the R-BINDB or S-BINDB is mixed with 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, wherein the molar ratio of R-BINDB or S-BINDB to 4-ethynylpyridine, cuprous iodide and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium is 1: (2-5): (0.08-0.15): (0.03-0.05), triethylamine is added under argon atmosphere, and refluxed at 95-115°C for 8-18h, after the reaction is completed, the reaction mixture is stirred with water, the water layer is extracted with dichloromethane, the organic layer is separated, the residual water is dried with sodium sulfate, and 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) to obtain chiral alkynyl binaphthyl pyridine, i.e. R-BINAPY or S-BINAPY;

[0064] (5): modification of the nitrogen atom on the pyridine

[0065] The R-BINPY, S-BINPY, R-BINAPY or S-BINAPY is reacted with methyl trifluoromethanesulfonate, diphenyl iodonium triflate, halobenzyl, halomethyl naphthalene, halomethyl anthracene, halomethyl benzopyrene, halomethyl pyrene, halomethyl phenanthrene or halomethyl perylene at room temperature to obtain the circularly polarized luminescent material. The halogen in the halogenated compound is chlorine, bromine or iodine.

[0066] Specifically:

[0067] Under an argon atmosphere, the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY is dissolved in dichloromethane with methyl trifluoromethanesulfonate, and the molar ratio of the R-BINPY or S-BINPY to the methyl trifluoromethanesulfonate is 1:(2-6). The solution is stirred at room temperature for 6-24 hours, and the reaction mixture is washed with a dichloromethane solution for 3-5 times. After drying, a yellow solid is obtained, which is chiral binaphthyl methyl viologen, i.e. R-BINMeV, S-BINMeV, R-BINAMeV or S-BINAMeV.

[0068] Under an argon atmosphere, the R-BINPY, S-BINPY, R-BINAPY or S-BINAPY is dissolved in N,N-dimethylformamide solution with diphenyl iodonium triflate and copper acetate, and the reaction solution is stirred at 80-110 ℃ for 6-24 hours. The reaction mixture is washed with a mixed solution of acetone, chloroform and diethyl ether for 3 times, and a yellow solid is obtained after drying, which is chiral binaphthyl phenyl viologen, i.e. R-BINPhV, S-BINPhV, R-BINAPhV or S-BINAPhV.

[0069] In addition, the obtained product can be ion exchanged to obtain a product with TFSI or PF6 as an anion.

[0070] Meanwhile, the application also discloses a circularly polarized organic light-emitting diode comprising the circularly polarized luminescent material. The structure of the circularly polarized organic light-emitting diode is as follows: anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode, wherein the circularly polarized luminescent material is used as the light-emitting layer, has a high light-emitting asymmetry factor, and can obtain a high-performance OLED.

[0071] The application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the application but not to limit the scope of the application. Furthermore, it should be understood that after reading the content of the application, those skilled in the art can make various modifications or changes to the application, and these equivalent forms also fall within the scope defined by the appended claims.

[0072] The following examples use the apparatuses and devices that are conventional in the art. The experimental methods in the following examples, if not specified, are usually carried out according to the conventional conditions, or according to the conditions suggested by the manufacturers. The following examples use various raw materials, unless otherwise specified, and the conventional commercially available products are used, and the specifications are conventional specifications in the art. In the specification of the application and the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0073] Example 1

[0074] Preparation of R-BINMeV

[0075] (1) Synthesis of 4,4' dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL)

[0076] Dissolve 1-bromo-3-hydroxynaphthalene (4 g, 18 mmol) in dichloromethane (80 mL) and add chloro-dihydroxy-bistetramethylenediamine copper (Cl(OH) TMEDA) (42 mg, 0.18 mmol). Stir the system under an oxygen atmosphere at room temperature for 16 h. After the reaction is complete, concentrate the reaction mixture under reduced pressure, and then perform silica gel column chromatography using gradient elution (hexane: dichloromethane = 1:2, dichloromethane), to obtain 1.75 g of a light yellow solid, at a yield of 43%, to prepare 4,4' dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL), which is a mixture of R-BINDL and S-BINDL. V 二氯甲烷 : V 石油醚 =1:2, dichloromethane), to obtain 1.75 g of a light yellow solid, at a yield of 43%, to prepare 4,4' dibromo-2,2'-diethoxy-1,1'-binaphthyl (R / S-BINDL), which is a mixture of R-BINDL and S-BINDL.

[0077] (2) Chiral resolution

[0078] Resolve 4,4' dibromo-2,2-dihydroxy-1,1'-binaphthyl by chiral resolution to obtain dextrorotatory or levorotatory-4,4' dibromo-2,2-dihydroxy-1,1'-binaphthyl (R-BINDL or S-BINDL).

[0079] Compound BINDL: 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J= 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 8.4 Hz, 2H),5.04 (s, 2H).

[0080] (3) Synthesis of intermediate R-4,4' dibromo-2,2'-diethoxy-1,1'- binaphthyl (R-BINDB)

[0081] Into a round bottom flask was added R-BINDL (1 g, 2.25 mmol), bromoethane (1 mL, 13.5 mmol), sodium iodide (0.054 g, 0.36 mg), potassium carbonate (1.56 g, 11.25 mmol) dissolved in acetone and the reaction was refluxed for 30 h. After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The solid obtained after concentration was recrystallized from acetone to obtain 0.5 g of pale yellow solid, R-BINDB, in about 50% yield.

[0082] 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), 7.36 (t, J = 8.4 Hz,2H), 5.04 (s, 2H).

[0083] 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), 7.36 (t, J = 8.4 Hz,2H), 5.04 (s, 2H).

[0084] (4) Synthesis of intermediate chiral 4,4'-dipyridine-2,2'-dioxy-1,1'- binaphthyl (R-BINPY)

[0085] To a round bottom flask was added R-BINDB (0.32 g, 0.62 mmol), pyridine-4- boronic acid (0.23 g, 1.86 mmol), potassium carbonate (0.43 g, 3.10 mmol). Subsequently, the flask was purged with argon. To this was added Pd(PPh3)4(45.0 mg, 0.039 mmol), 1,4-dioxane (12.5 mL) and deionized water (1.26 mL) under argon atmosphere and heated to reflux for 16 h. After the reaction was completed, the reaction was concentrated under reduced pressure. The solid reaction mixture was stirred with 30 mL of water and the aqueous layer was extracted with 30 mL of dichloromethane three times. The organic layer was separated and the residual water was dried over anhydrous sodium sulfate. The filtrate was concentrated under reduced pressure and the resulting 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 right-handed-4,4'-bipyridine-2,2'-dioxide-1,1'-binaphthyl (R-BINPY), yield: 0.25 g, about 80% yield.

[0086] 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).

[0087] (5) Synthesis of chiral right-handed binaphthyl methyl viologen (R-BINMeV)

[0088] R-BINPY (0.1 g, 0.2 mmol) was added to a round bottom flask under argon atmosphere, dichloromethane (5 mL) was added. The reaction was stirred at 0 °C, methyl trifluoromethanesulfonate (0.05 L, 0.44 mmol) was added dropwise. After the addition was complete, the reaction was stirred at room temperature for 15 h. After the reaction was complete, the reaction mixture was washed with dichloromethane (5 mL) three times to wash away the un-methylated chiral BINOL and methyl triflate. The yellow solid was obtained after drying, which was chiral R-BINMeV. Yield: 0.09 g, about 90% yield.

[0089] Compound R-BINMeV: Melting point: 201-203 °C. 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. High resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]263.13375; found: 263.13047.

[0090] Example 2

[0091] The present example is the preparation of chiral left-handed binaphthyl methyl viologen (S-BINMeV). Different from example 1, steps (3)-(5) are as follows:

[0092] (3) Synthesis of intermediate S-4,4’-dibromo-2,2’-diethoxy-1,1’-binaphthyl (S-BINDB)

[0093] Into a round bottom flask was added S-BINDL (1 g, 2.25 mmol), bromoethane (1 mL, 13.5 mmol), sodium iodide (0.054 g, 0.36 mg), potassium carbonate (1.56 g, 11.25 mmol) and dissolved in acetone solution. The reaction was refluxed for 30 h. After cooling, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The concentrated solid was recrystallized in acetone to obtain 0.5 g of light yellow solid, S-BINDB, with a yield of about 50%.

[0094] (4) Synthesis of intermediate chiral 4,4’-dipyridin-2,2’-dioxy-1,1’-binaphthyl (S-BINPY)

[0095] Into a round bottom flask was added S-BINDB (0.32 g, 0.62 mmol), pyridine-4-boronic acid (0.23 g, 1.86 mmol), potassium carbonate (0.43 g, 3.10 mmol). Subsequently, the flask was purged with argon. In an argon environment, 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 reaction was heated and refluxed for 16 h. After the reaction was completed, the reaction solution was rotary evaporated under reduced pressure. The solid reaction mixture after rotary evaporation was stirred with 30 mL of water, and the water layer was extracted with 30 mL of dichloromethane three times. The organic layer was separated, and the residual water was dried with anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and 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-handed-4,4´-dipyridin-2,2´-dioxy-1,1´-binaphthyl (S-BINPY), with a yield of 0.25 g and a yield of about 80%.

[0096] 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).

[0097] (5) Synthesis of chiral levorotatory binaphthyl methyl viologen (S-BINMeV)

[0098] Under argon atmosphere, S-BINPY (0.1 g, 0.2 mmol) was added into a round bottom flask, dichloromethane (5 mL) was added. The reaction solution was stirred at 0 ℃, methyl trifluoromethanesulfonate (0.05 L, 0.44 mmol) was added dropwise. After the dropwise addition was completed, the reaction solution was stirred at room temperature for 15 h. After the reaction was completed, the reaction mixture was washed with dichloromethane (5 mL) three times to wash away the unmethylated chiral binaphthyl pyridine and methyl trifluoromethanesulfonate. After drying, a yellow solid was obtained, which was chiral levorotatory binaphthyl methyl viologen (S-BINMeV), yield: 0.09 g, yield about 90%.

[0099] Compound S-BINMeV: Melting point: 201-203 ℃, 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. High resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+]263.13299; found: 263.13047.

[0100] The product prepared in Example 1 and Example 2 has the following structural formula:

[0101]

[0102] Example 3

[0103] This example is the preparation of chiral right-handed BINPhV, which is different from Example 1 in that step (5) is as follows:

[0104] (5) Under argon environment, R-BINPY (0.1 g, 0.2 mmol), diphenyl triflate (0.27 mg, 0.6 mmol), 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, the DMF was removed by vacuum pump at 80 °C, and the solid reaction mixture was washed with a mixed solution of acetone, chloroform and diethyl ether (V Et2O :V CHCl3 :V Acetone = 1:1:1, 5 mL) three times to wash away the unreacted chiral BINPY, diphenyl triflate. After drying, a yellow solid was obtained, which was chiral right-handed BINPhV, with a yield of about 90%.

[0105] Compound R-BINPhV: Melting point: greater than 300 °C. 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 = 6.2 Hz, 4H), 1.12 (t, J = 6.9 Hz, 6H). 13C 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. High resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ] 325.14960; found: 325.14612.

[0106] Example 4

[0107] This example is the preparation of chiral levorotatory binaphthyl phenyl viologen (S-BINPhV), which is different from Example 3 in that S-BINPY is used for reaction, and other conditions are the same. The product prepared is chiral levorotatory binaphthyl phenyl viologen, i.e. S-BINPhV.

[0108] Compound S-BINPhV: melting point: greater than 300 °C. 1 H 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). 13C 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. High resolution mass spectral data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]325.14898; found: 325.14612.

[0109] The product prepared in Example 3 and Example 4 has the following structural formula:

[0110]

[0111] Example 5

[0112] This example is the preparation of chiral right acetylenyl binaphthyl methyl viologen (R-BINAMeV), which is different from Example 1 in that steps (4)~(5) are as follows:

[0113] (4): Synthesis of intermediate chiral 4,4'-dipyridine-2,2'-dioxy-1,1'-acetylenyl binaphthyl (R-BINAPY)

[0114] Into a round bottom flask was added R-BINDB (0.249 g, 0.5 mmol), 4-ethynylpyridine (0.130 g, 1.25 mmol), cuprous iodide (10 mg, 0.05 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (15 mg, 0.02 mol), and triethylamine (10 mL) under argon atmosphere, and heated to reflux for 8 h. After the reaction was completed, the reaction mixture was stirred with 30 mL of water, and the aqueous layer was extracted with dichloromethane three times, and the organic layer was separated, and the residual water was dried with sodium sulfate, and the filtrate was concentrated under reduced pressure, 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%.

[0115] (5): Preparation of chiral right acetylenyl binaphthyl methyl viologen (R-BINAMeV)

[0116] R-BINAPY (0.08 g, 0.15 mmol) was added to a round bottom flask under argon atmosphere and dichloromethane (5 mL) was added. The reaction was stirred at 0 °C and methyl triflate (0.037 L, 0.32 mmol) was added dropwise. After the addition was complete, the reaction was stirred at room temperature for 15 h. After the reaction was complete, the reaction mixture was washed with dichloromethane (5 mL) three times to wash away the un-methylated chiral BINAPY and methyl triflate. The yellow solid was obtained after drying, which was chiral R- / S-BINAMeV. Yield: 0.06 g, about 75% yield.

[0117] 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).

[0118] Compound R-BINAMeV: Melting point: greater than 300 °C. 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). 13C 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. High resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]287.13386; found:287.13047.

[0119] Example 6

[0120] This example is the preparation of chiral levorotatory acetylenyl binaphthyl methyl viologen (S-BINAMeV), which is different from Example 1 in that steps (4)~(5) are as follows:

[0121] (4): Synthesis of intermediate chiral 4,4'-dipyridine-2,2'-dioxy-1,1'- acetylenyl binaphthyl (S-BINAPY)

[0122] Into a round bottom flask was added S-BINDB (0.249 g, 0.5 mmol), 4- ethynylpyridine (0.130 g, 1.25 mmol), cuprous iodide (10 mg, 0.05 mmol), [1,1'- bis(diphenylphosphino)ferrocene]dichloropalladium (15 mg, 0.02 mol), under argon atmosphere, added triethylamine (10 mL), heated to reflux for 8 h. After the reaction was completed, the reaction mixture was added to 30 mL of water and stirred, the aqueous layer was extracted with dichloromethane three times, the organic layer was separated, the residual water was dried with sodium sulfate, and the filtrate was concentrated under reduced pressure, 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, which was S-BINAPY, with a yield of 80%.

[0123] (5): In an argon environment, S-BINAPY (0.08 g, 0.15 mmol) was added to a round bottom flask, and dichloromethane (5 mL) was added. The reaction was stirred at 0 °C, and methyl trifluoromethanesulfonate (0.037 L, 0.32 mmol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature for 15 h. After the reaction was completed, the reaction mixture was washed with dichloromethane (5 mL) three times to wash away the unmethylated chiral binaphthyl methyl viologen and methyl triflate. After drying, a yellow solid was obtained, which was chiral levorotatory binaphthyl methyl viologen (S-BINAMeV). Yield: 0.06 g, yield about 75%.

[0124] Compound S-BINAMeV: Melting point: greater than 300 °C. 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. High resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]287.13372; found:287.13047.

[0125] Example 7

[0126] This example is the preparation of chiral right acetylenic binaphthyl phenyl viologen (R-BINAPhV), which is different from example 5 in step (5), which is as follows:

[0127] (5): Under argon atmosphere, R-BINAPY (0.08 g, 0.15 mmol), diphenyl triflate (0.065 g, 0.44 mmol), copper acetate (1.37 mg, 0.007 mmol) were added into a round bottom flask, DMF (5 mL) was added into the flask, the reaction solution was stirred at 100 °C for 8 h. After the reaction was completed, the DMF was removed by vacuum pump at 80 °C, the solid reaction mixture was washed with a mixture of acetone, chloroform, diethyl ether (V Et2O :V CHCl3 :V Acetone = 1:1:1, 5 mL) three times to wash away the unreacted chiral binaphthyl pyridine, diphenyl triflate. After drying, a yellow solid was obtained, which was chiral right binaphthyl phenyl viologen (R-BINAPhV), yield: 0.06 g, yield about 75%.

[0128] 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).

[0129] Compound R-BINAPhV: Melting point: 182 - 184 °C. 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. High-resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]349.14879; found: 349.14612.

[0130] Example 8

[0131] This example describes the preparation of chiral levo-alkynyl-binaphthol violetin (S-BINAPhV). Unlike Example 7, the S-BINAPY reaction was used, and the product obtained was chiral levo-alkynyl-binaphthol violetin (S-BINPhV).

[0132] 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).

[0133] 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. High-resolution mass spectrometry data: HRMS calcd for C 36 H 34 N2O2 2+ [M 2+ ]349.14890; found: 349.14612.

[0134] The structural formulas of the products obtained in Examples 7 and 8 are as follows:

[0135]

[0136] Figure 2 The UV-Vis absorption spectrum of the chiral dextrorotatory naphthalenephenyl viologen prepared in Example 3 of this invention after reduction with zinc and sodium is shown. Figure 3The UV-visible absorption spectrum of the chiral left-handed binaphthyl phenyl viologen prepared in Example 4 after reduction by metal zinc and sodium is shown in the figure. As can be seen from the figure, after reduction by zinc, the color of the chiral right-handed binaphthyl phenyl viologen and the chiral left-handed binaphthyl phenyl viologen solution has no change, and after reduction by sodium, the color of the solution changes from orange to yellow, and the peak at 600-700 nm is increased, indicating that the color of the chiral right-handed / left-handed binaphthyl phenyl viologen changes after being reduced to different states, which makes the compound have potential important application value in the field of optoelectronics, sensors and the like.

[0137] Figure 4 The cyclic voltammogram of the chiral right-handed binaphthyl phenyl viologen prepared in Example 3 is shown in the figure. Figure 5 The cyclic voltammogram of the chiral left-handed binaphthyl phenyl viologen prepared in Example 4 is shown in the figure. As can be seen from the figure, after introducing a phenyl group on pyridine, the chiral right-handed / left-handed binaphthyl phenyl viologen has the electrochemical characteristics of viologen molecules, and has a set of redox peaks by applying voltage, and the electrochemical data measured at different scan rates show that the two molecules have good stability.

[0138] Figure 6 The electron paramagnetic resonance spectrum of the chiral right-handed binaphthyl phenyl viologen prepared in Example 3 is shown in the figure. Figure 7 The electron paramagnetic resonance spectrum of the chiral left-handed binaphthyl phenyl viologen prepared in Example 4 is shown in the figure. As can be seen from the figure, after sodium is added, the chiral right-handed / left-handed binaphthyl phenyl viologen has free radicals.

[0139] Figure 8 The fluorescence spectrum of the chiral right-handed / left-handed binaphthyl phenyl viologen prepared in Examples 3-4 is shown in the figure. As can be seen from the figure, the chiral right-handed / left-handed binaphthyl phenyl viologen molecules have good fluorescence emission performance at about 600 nm.

[0140] Figure 9 The circular dichroism spectrum of the chiral right-handed / left-handed binaphthyl phenyl viologen prepared in Examples 3-4 is shown in the figure. Circular dichroism is a spectroscopic technique for detecting the difference in absorption of left-handed and right-handed circularly polarized light in a specific wavelength range. This difference reflects the optical rotation of chiral molecules, which is a unique optical property of chiral molecules. As can be seen from the figure, the chiral right-handed / left-handed binaphthyl phenyl viologen has strong absorption at 270-400, which corresponds to the electronic transition of some chromophores in the molecule, such as π-π transition. For molecules such as binaphthyl phenyl viologen, the absorption peak is related to the conjugated system in the molecule, the substituent group and the structure of the chiral center. The chiral right-handed and left-handed binaphthyl phenyl viologen exhibits strong absorption peaks and significant chiral optical activity in the circular dichroism spectrum. Transition or n-π

[0141] Figure 10 ​Circularly polarized luminescence test results of the chiral dextrorotatory / levorotatory binaphthyl phenyl viologen prepared in embodiments 3~4 of the present application, Figure 11 The luminescence asymmetric factor graph of the chiral dextrorotatory / levorotatory binaphthyl phenyl viologen prepared in embodiments 3~4 of the present application, the size of the luminescence asymmetric factor directly reflects the strength of the directionality of the chiral molecule in the luminescence process. Higher g-factor value means that the luminescent body can more effectively emit light of a single circular polarization direction, which has important application value in the fields of optical sensing, information storage, display technology, etc. As can be seen from the figure, the chiral dextrorotatory / levorotatory binaphthyl phenyl viologen has good circularly polarized luminescence characteristics, and the luminescence asymmetric factor can reach 0.01 at the highest, making the chiral viologen molecule have potential applications in circularly polarized luminescence devices, chiral recognition sensors, and optical switches.

[0142] Figure 12 The SEM graph of the circularly polarized luminescence material prepared in embodiment 3 of the present application, i.e. the chiral dextrorotatory binaphthyl phenyl viologen, under different magnifications, wherein the scale of (a) is 100 μm and the scale of (b) is 30 μm. As can be seen from the figure, the circularly polarized luminescence material prepared by the present application has a clear chiral fractal structure after stacking, has a chiral amplification effect, and exhibits controllable self-assembly, which is mainly due to the large number of π-π stacking and hydrogen bonding interactions between molecules, resulting in such chiral fractal structure assembly, greatly improving the circularly polarized luminescence performance of the binaphthyl molecule.

[0143] Embodiment 9

[0144] The compound with anion Cl, Br or I of the product is placed in a saturated LiTFSI aqueous solution, stirred overnight, and the solid part is washed with water by centrifugation for 3~5 times to prepare a viologen molecule with anion TFSI - .

[0145] Embodiment 10

[0146] The compound with anion Cl, Br or I of the product is placed in a saturated NH4PF6 aqueous solution, stirred overnight, and the solid part is washed with water by centrifugation for 3~5 times to prepare a viologen molecule with anion PF6 - .

[0147] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered within the protection scope of the present application.

[0148] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A circularly polarized luminescent material, characterized in that, Including compounds represented by general formula (I): ， Where R1 is X = OTf; R2 is phenyl; the compound represented by the general formula (I) is dextrorotatory naphthylphenyl viologen or levorotatory naphthylphenyl viologen.

2. The method for preparing a circularly polarized luminescent material as described in claim 1, characterized in that, Includes the following steps: S1: 1-Bromo-3-hydroxynaphthalene and dihydroxy-bis(tetramethylethylenediamine)copper chloride were dissolved in dichloromethane, and then the system was stirred and reacted under an oxygen atmosphere to prepare R / S-BINDL. The structural formula of the R / S-BINDL is: ； S2: After the R / S-BINDL is split, the split BINDL, bromoethane, sodium iodide and potassium carbonate are dissolved in acetone and refluxed to obtain R-BINDB or S-BINDB. The structural formula of R-BINDB or S-BINDB is as follows: ； S3: R-BINDB or S-BINDB is mixed with pyridine-4-boronic acid, potassium carbonate and tetra-triphenylphosphine palladium, and then 1,4-dioxane is added under argon atmosphere and refluxed to obtain R-BINPY or S-BINPY. The structural formula of R-BINPY or S-BINPY is: ； S4: The R-BINPY or S-BINPY is reacted with diphenyltrifluoromethanesulfonic acid iodine to prepare 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 and copper dihydroxy-bis(tetramethylethylenediamine)diamine 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 14-24 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, bromoethane, sodium iodide and potassium carbonate is 1:(4~8):(0.1~0.2):(4~8); in step S2, the reflux reaction temperature is 60~75℃ and the time is 20~50h.

6. The method for preparing a circularly polarized luminescent material according to claim 2, characterized in that, In step S3, the molar ratio of R-BINDB or S-BINDB to pyridine-4-boronic acid, potassium carbonate, and tetratriphenylphosphine palladium is 1:(2~6):(4~8):(0.03~0.1).

7. 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 or S-BINPY to diphenyltrifluoromethanesulfonic acid iodine is 1:(2~6), the reaction temperature is 80~110℃, and the reaction time is 6~12h.

8. A circularly polarized organic light-emitting diode, characterized in that, It includes the circularly polarized luminescent material as described in claim 1.

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