Binaphthylamine derivative with chiral macrocycle as well as preparation method and application of binaphthylamine derivative

Abstract

The invention relates to the technical field of organic luminescence, and discloses a binaphthylamine derivative with a chiral macrocycle and a preparation method and application thereof. According to the organic compound based on the binaphthylamine derivative with the chiral large ring, a binaphthylamine-containing group serves as a donor structure and is connected with different receptors, a series of D-A-D-A ring structure molecules are synthesized, and the organic compound has the high quantum yield and circular polarization property and can be used for preparing the chiral large ring-containing binaphthylamine derivative with the chiral large ring. The compound can be used in the fields of preparation of efficient organic electroluminescent devices, 3D display and advanced display technology, information security and anti-counterfeiting, biosensing and bioimaging, optical storage and information processing and the like.

Description

Technical Field

[0001] The present application relates to the technical field of organic light-emitting materials, and in particular to a dinaphthylamine derivative having a chiral macrocycle, a preparation method thereof, and an application thereof. Background Art

[0002] Circularly polarized luminescence (CPL) materials can produce left-handed or right-handed circularly polarized light with varying intensities upon stimulated emission. This phenomenon arises from the inherent difference in the radiative rates of the two circularly polarized light transitions of the chiral centers (molecules or structures) in the excited state. This difference in chiral luminescence intensity is typically quantified by the asymmetry factor (glum = 2(IL-IR) / (IL+IR)). CPL materials hold unique application prospects in 3D displays (without glasses), dual-channel optical information storage, advanced anti-counterfeiting, and asymmetric synthesis.

[0003] However, the current core challenge lies in how to synergistically optimize material properties: that is, to obtain a significantly enhanced |glum| value while achieving high luminescence quantum efficiency, which is crucial for promoting its practical application.

[0004] Patent application content

[0005] To overcome the problems existing in the above-mentioned prior art, the primary purpose of this application is to provide a binaphthylamine derivative with a chiral macrocycle. This binaphthylamine derivative with a chiral macrocycle can increase the circularly polarized luminescence asymmetry factor of an organic system while maintaining high luminescence efficiency.

[0006] Another object of the present application is to provide a method for preparing the above-mentioned binaphthylamine derivative having a chiral macrocycle.

[0007] Another object of the present application is to provide applications of the above-mentioned binaphthylamine derivatives having a chiral macrocycle.

[0008] The above-mentioned purpose of this application is achieved through the following technical solutions:

[0009] A chiral macrocyclic binaphthylamine derivative can be used as a circularly polarized luminescent material, characterized in that it has a molecular structure shown in the following formula (1) or (2):

[0010]

[0011] Wherein, R1 is independently selected from one of phenyl and tert-butyl, and R2 and R3 are independently selected from any one of pyrimidine derivatives, triazine derivatives, benzophenone derivatives, and diphenyl sulfone derivatives.

[0012] Preferably, the R1 to R3 substituents in the present application are selected from any one of 1 to 13 below:

[0013]

[0014] The present application also provides a method for preparing the above-mentioned binaphthylamine derivative having a chiral macrocycle, comprising the following steps:

[0015] S1. Preparation of intermediate product R / S-2

[0016] Under an inert gas atmosphere, [1,1'-binaphthyl]-2,2'-diamine, 4-tert-butylbromobenzene, palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine and sodium tert-butoxide were dispersed in a two-necked flask containing toluene and reacted at 110°C for 12 hours. After the reaction, the solvent was dried and the crude product was further purified to obtain the intermediate product R / S-2.

[0017] S2. Preparation of intermediate product R / S-3 or R / S-3'

[0018] Under an inert gas atmosphere, the intermediate product R / S-2 obtained in step S1, 4,4'-dibromodiphenyl sulfone or 4,4'-dibromobenzophenone, palladium acetate, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and sodium tert-butoxide are dispersed in a two-necked flask containing toluene and reacted at 110° C. for 6 hours. After the reaction is completed, the solvent is dried and the crude product is further purified to obtain the intermediate product R / S-3 or R / S-3';

[0019] S3. Preparation of target product A21 or A23

[0020] Under an inert gas atmosphere, the intermediate product R / S-3 or R / S-3' obtained in step S2 is dispersed with 4,4'-dibromodiphenyl sulfone or 4,4'-dibromobenzophenone, palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide in a two-necked flask containing toluene. The mixture is reacted at 110°C for 12 hours. After the reaction, the solvent is dried and the resulting crude product is further purified to obtain the target product A21 or A23.

[0021] Preferably, the crude product in steps S1, S2 and S3 is further purified by column chromatography.

[0022] More preferably, the detergent used in the column chromatography purification in step S1 is petroleum ether: dichloromethane in a volume ratio of 2:1.

[0023] More preferably, the detergent used in the column chromatography purification in step S2 is petroleum ether: dichloromethane in a volume ratio of 4:1.

[0024] Preferably, the inert gas atmosphere in steps S1, S2 and S3 is a nitrogen atmosphere.

[0025] The present application also provides the use of the above-mentioned binaphthylamine derivatives with chiral macrocycles as luminescent materials, luminescent devices or smart materials.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] The binaphthylamine derivative provided in the present application is based on the binaphthylamine derivative as the parent core, has a pure blue light emission spectrum characteristic and a high quantum yield, meets the photoelectric performance requirements of organic electroluminescent devices, and can also increase the circularly polarized luminescence asymmetry factor of the organic system, with a maximum value exceeding 1×10 -3 . BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Compound A21 prepared in Example 1 of the present application 1 HMNR diagram;

[0029] Figure 2 Compound A23 prepared in Example 2 of the present application 1 HMNR diagram;

[0030] Figure 3 The UV absorption and emission patterns of compound A21 prepared in Example 1 of the present application;

[0031] Figure 4 These are the ultraviolet absorption and emission patterns of compound A23 prepared in Example 2 of the present application.

[0032] Figure 5 Fluorescence quantum yield of compound A21 prepared in Example 1 of the present application

[0033] Figure 6 Fluorescence quantum yield of compound A23 prepared in Example 2 of this application

[0034] Figure 7 Photoluminescence asymmetry factor diagram of compound A21 prepared in Example 1 of the present application

[0035] Figure 8 Photoluminescence asymmetry factor diagram of compound A23 prepared in Example 2 of the present application DETAILED DESCRIPTION

[0036] The embodiments of the present application will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0037] It should be noted that:

[0038] In this application, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0039] In this application, unless otherwise specified, percentages (%) or parts refer to percentages or parts by weight relative to the composition.

[0040] In this application, unless otherwise specified, the components involved or their preferred components can be combined with each other to form a new technical solution.

[0041] In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any combination of real numbers between a and b, where a and b are both real numbers.

[0042] The "ranges" disclosed in this application are in the form of lower limits and upper limits, which can be one or more lower limits, and one or more upper limits, respectively.

[0043] In this application, unless otherwise stated, each reaction or operation step can be carried out sequentially or in a sequential manner. Preferably, the reaction method herein is carried out sequentially.

[0044] Unless otherwise indicated, the professional and scientific terms used herein are the same as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to this application.

[0045] The present application provides a chiral macrocycle with a binaphthylamine derivative as a donor, which can be used as a circularly polarized luminescent material and has a molecular structure shown in the following formula (1) or formula (2):

[0046]

[0047] Wherein, R1 is independently selected from one of phenyl and tert-butyl, and R2 and R3 are independently selected from any one of pyrimidine derivatives, triazine derivatives, benzophenone derivatives, and diphenyl sulfone derivatives.

[0048] The present application provides a dinaphthylamine derivative, which is an organic compound based on the dinaphthylamine derivative. It uses a dinaphthylamine group as a donor structure and connects different receptors to synthesize a series of DADA ring structure molecules. It has the emission spectrum characteristics of pure blue light, high quantum yield and circularly polarized light properties, and can be used to prepare high-efficiency organic electroluminescent devices and increase the circularly polarized luminescence asymmetry factor of the organic system.

[0049] In some preferred embodiments, the substituents R1 to R3 in the present application are selected from any one of 1 to 13 below:

[0050]

[0051] In some more preferred embodiments, the binaphthylamine derivatives having a chiral macrocycle described in formula (1) and formula (2) may preferably be any one of the following compounds A1 to A50:

[0052]

[0053]

[0054]

[0055] In some more preferred embodiments, the binaphthylamine derivatives having a chiral macrocycle described in formula (1) and formula (2) have one of the following molecular structural formulas:

[0056]

[0057] The present application also provides a method for preparing the above-mentioned binaphthylamine derivative having a chiral macrocycle, comprising the following steps:

[0058] S1. Preparation of intermediate product R / S-2

[0059] Under an inert gas atmosphere, [1,1'-binaphthyl]-2,2'-diamine, 4-tert-butylbromobenzene, palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine (BINAP) and sodium tert-butoxide were dispersed in a two-necked flask containing toluene and reacted at 110° C. for 12 hours. After the reaction, the solvent was dried and the crude product was further purified to obtain the intermediate product R / S-2. The chemical reaction equation involved in the preparation process is as follows:

[0060]

[0061] S2. Preparation of intermediate product R / S-3 (or R / S-3')

[0062] Under an inert gas atmosphere, the intermediate product R / S-2 obtained in step S1, 4,4'-dibromodiphenyl sulfone (or 4,4'-dibromobenzophenone), palladium acetate, tri-tert-butylphosphine and sodium tert-butoxide were dispersed in a two-necked flask containing toluene and reacted at 110° C. for 6 hours. After the reaction, the solvent was dried and the crude product was further purified to obtain the intermediate product R / S-3 (or R / S-3'). The chemical reaction equation involved in the preparation process is as follows:

[0063]

[0064]

[0065] S3. Preparation of target product A21 (or A23)

[0066] Under an inert gas atmosphere, the intermediate product R / S-3 (or R / S-3') obtained in step S3, 4,4'-dibromodiphenyl sulfone (or 4,4'-dibromobenzophenone), palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide were dispersed in a two-necked flask containing toluene and reacted at 110°C for 12 hours. After the reaction, the solvent was dried and the resulting crude product was further purified to obtain the target product A21 (or A23). The chemical reaction equation involved in this preparation process is as follows:

[0067]

[0068] In some preferred embodiments, the crude product in steps S1, S2, and S3 is further purified by column chromatography.

[0069] In some more preferred embodiments, the detergent used in the column chromatography purification in step S1 is petroleum ether: dichloromethane in a volume ratio of 2:1.

[0070] In some more preferred embodiments, the detergent used in the column chromatography purification in step S2 is petroleum ether: dichloromethane in a volume ratio of 4:1.

[0071] In some preferred embodiments, the inert gas atmosphere in steps S1, S2 and S3 is a nitrogen atmosphere.

[0072] The following will describe in detail the preparation methods of the binaphthylamine derivatives of formula (1) or (2) having a chiral macrocycle, taking the compounds A21 and A23 as examples.

[0073] Example 1

[0074] S1. The preparation method of intermediate product R / S-2 is as follows:

[0075] Under nitrogen, [1,1'-binaphthyl]-2,2'-diamine R / S-1 (2.2 g, 5 mmol, 1 eq), 4-tert-butylbromobenzene (2.035704 g, 11 mmol, 2.2 eq), palladium acetate (Pd(OCCH)) (22.5 mg, 0.1 mmol, 0.02 eq), 1,1-binaphthyl-2,2-bis(diphenylphosphine) (BINAP) (62.3 mg, 0.1 mmol, 0.02 eq), and sodium tert-butoxide (NaOtBu) (1.4 g, 15 mmol, 3 eq) were dispersed in a two-necked flask containing 30 mL of toluene. The mixture was reacted at 110°C for 12 hours. After completion of the reaction, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (volume ratio 2:1). The intermediate R / S-2 was obtained in a yield of 3.5 g (85%). The chemical reaction equation in this preparation step is as follows:

[0076]

[0077] S2. Preparation of intermediate product R / S-3

[0078] Under a nitrogen atmosphere, the intermediate product R / S-2 (2.20 g, 4 mmol, 1 eq), 4,4'-dibromobenzophenone (0.680 g, 2 mmol, 0.5 eq), palladium acetate (Pd(O2CCH3)2) (17.9 mg, 0.08 mmol, 0.02 eq), 1,1-binaphthyl-2,2-bisdiphenylphosphine (BINAP) (50 mg, 0.08 mmol, 0.02 eq) and sodium tert-butoxide (NaOtBu) (1.176 g, 12 mmol, 3 eq) were dispersed in a 30 mL toluene two-necked flask. The reaction was carried out at 110 ° C for 6 hours. After the reaction was completed, the solvent was dried and the crude product was further purified by column chromatography using petroleum ether: dichloromethane (volume ratio 4:1). The intermediate product R / S-3 was obtained with a yield of 2.04 g (yield 80%). The chemical reaction equation in this preparation step is as follows:

[0079]

[0080] S3. Preparation of target product A23

[0081] Under nitrogen, intermediate R / S-3 (2.55 g, 2 mmol, 1 eq), 4,4'-dibromobenzophenone (0.680 g, 2 mmol, 1 eq), palladium acetate (Pd(O2CCH3)2) (22.5 mg, 0.1 mmol, 0.05 eq), tri-tert-butylphosphine (40 mg, 0.2 mmol, 0.1 eq), and sodium tert-butoxide (NaOtBu) (0.576 g, 6 mmol, 3 eq) were dispersed in a two-necked flask containing 30 mL of toluene. The mixture was reacted at 110°C for 4 hours. After completion of the reaction, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (5:1 by volume). The final product A23 was obtained in a yield of 2.41 g (83%).

[0082] The chemical reaction equation in this preparation step is as follows:

[0083]

[0084] Example 2

[0085] S1. Preparation of intermediate product R / S-2

[0086] Under nitrogen, [1,1'-binaphthyl]-2,2'-diamine R / S-1 (2.2 g, 5 mmol, 1 eq), 4-tert-butylbromobenzene (2.035704 g, 11 mmol, 2.2 eq), palladium acetate (Pd(O2CCH3)2) (22.5 mg, 0.1 mmol, 0.02 eq), 1,1-binaphthyl-2,2-bis(diphenylphosphine) (BINAP) (62.3 mg, 0.1 mmol, 0.02 eq), and sodium tert-butoxide (NaOtBu) (1.4 g, 15 mmol, 3 eq) were dispersed in a two-necked flask containing 30 mL of toluene. The mixture was reacted at 110°C for 12 hours. After completion of the reaction, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (volume ratio 2:1). The intermediate product R / S-2 was obtained in an amount of 3.5 g (yield 85%). The chemical reaction equation in this preparation step is as follows:

[0087]

[0088] S2. Preparation of intermediate product R / S-3'

[0089] Under a nitrogen atmosphere, the intermediate product R / S-2 (2.20 g, 4 mmol, 1 eq), 4,4'-dibromodiphenyl sulfone (0.75 g, 2 mmol, 0.5 eq), palladium acetate (Pd(O2CCH3)2) (17.9 mg, 0.08 mmol, 0.02 eq), 1,1-binaphthyl-2,2-bisdiphenylphosphine (BINAP) (50 mg, 0.08 mmol, 0.02 eq) and sodium tert-butoxide (NaOtBu) (1.176 g, 12 mmol, 3 eq) were dispersed in a 30 mL toluene two-necked flask. The reaction was carried out at 110 ° C for 6 hours. After the reaction was completed, the solvent was dried and the crude product was further purified by column chromatography using petroleum ether: dichloromethane (volume ratio 4:1). The intermediate product R / S-3 was obtained with a yield of 2.1 g (yield 80%). The chemical reaction equation in this preparation step is as follows:

[0090]

[0091] S3. Preparation of target product A21

[0092] Under a nitrogen atmosphere, intermediate R / S-3 (2.62 g, 2 mmol, 1 eq), 4,4'-dibromodiphenyl sulfone (0.75 g, 2 mmol, 1 eq), palladium acetate (Pd(O2CCH3)2) (22.5 mg, 0.1 mmol, 0.05 eq), tri-tert-butyl phosphine (40 mg, 0.2 mmol, 0.1 eq), and sodium tert-butoxide (NaOtBu) (0.576 g, 6 mmol, 3 eq) were dispersed in a 30 mL toluene two-necked flask. The mixture was reacted at 110°C for 4 hours. After completion of the reaction, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (volume ratio 5:1). The final product A21 was obtained in a yield of 2.21 g (72.3%).

[0093] The chemical reaction equation in this preparation step is as follows:

[0094]

[0095] Characterization and performance testing

[0096] The chiral macrocycles A23 and A21 of the binaphthylamine derivatives prepared in Examples 1 and 2 were characterized and tested for their properties. Figures 1 to 8 shown.

[0097] The test method is as follows:

[0098] Compound structure detection: using a Bruker 400 MHz superconducting nuclear magnetic resonance spectrometer, the solvent is deuterated chloroform; UV absorption spectroscopy detection: using a Shimadzu UV-visible spectrophotometer UV-2700, the scanning range is 300-450 nm;

[0099] Emission spectrum detection: A steady-state / transient fluorescence spectrometer (FLS980) was used with an excitation wavelength of 365 nm and a test temperature of 300 K.

[0100] The test results are as follows:

[0101] from Figure 1 It can be seen that the characteristic wave number (ppm) of compound A21 prepared in Example 1 is 1 H NMR (400 MHz, Chloroform-d) δ 7.96 (dd, J = 7.5, 1.3 Hz, 4H), 7.93–7.89 (m, 4H), 7.88–7.83 (m, 12H), 7.43 (td, J = 7.3, 1.3 Hz, 4H), 7.36–7.30 (m, 8H), 7.23–7.16 (m, 16H), 6.93–6.88 (m, 8H), 1.34 (s, 36H). The peaks in the proton magnetic resonance molecular spectrum corresponded one-to-one with the target product, and the quantity was reasonable. This indicates that Example 1 prepared the chiral macrocyclic compound 21, a binaphthylamine derivative, with a single structure and high purity.

[0102] from Figure 2 It can be seen that the characteristic wave number (ppm) of compound A23 prepared in Example 2 is 1 H NMR (400 MHz, Chloroform-d) δ 7.96 (dd, J = 7.5, 1.4 Hz, 4H), 7.93–7.89 (m, 4H), 7.70 (d, J = 6.8 Hz, 4H), 7.52–7.47 (m, 8H), 7.46–7.41 (m, 8H), 7.36 (d, J = 1.3 Hz, 1H), 7.34 (dd, J = 7.0, 1.5 Hz, 11H), 7.20–7.15 (m, 8H), 7.03–6.98 (m, 8H), 1.34 (s, 36H). The peaks in the proton magnetic resonance molecular spectrum corresponded one-to-one with the target product, and the number was reasonable. This indicates that Example 2 prepared the chiral macrocyclic compound A23, a binaphthylamine derivative, with a single structure and high purity.

[0103] Figure 3 、 4 The UV absorption and emission patterns of compounds A23 and A21 prepared in Examples 1 and 2 of the present application are shown in FIG. Figure 3 、 4It can be seen that the ultraviolet absorption peaks of compounds A21 and A23 prepared in the present application are mainly at wavelengths of 350 nm and 375 nm, respectively; while the fluorescence emission peaks of compounds A21 and A23 are at 446 nm and 432 nm, respectively.

[0104] Figure 5 、 6 This is a graph of the photoluminescence quantum yield of compounds A21 and A23 prepared in Examples 1 and 2 of the present application before deoxygenation. Figure 5 、 6 It can be seen that the photoluminescence quantum yields of A21 and 23 prepared in the present application before deoxygenation reached 40.49% and 85.15%, respectively, which have high quantum yields and can be used to make more efficient circularly polarized light-emitting devices.

[0105] Figure 7 、 8 The CPL spectra of compounds A21 and A23 prepared in Examples 1 and 2 of the present application are shown in FIG. Figure 7 、 8 It can be seen that the photoluminescence asymmetry factor of A21 and A23 compounds exceeds 1×10 -3 .

[0106] In addition to compounds A21 and A23, the chiral macrocycles of the binaphthylamine derivatives in this application have circularly polarized properties because they are structurally similar to compounds A21 / A23. They are compounds with binaphthylamine derivatives as donors, connected to stabilizing groups and acceptor groups with electron-withdrawing capabilities. Therefore, through similar preparation methods and the same characterization and testing methods, it can be seen that these binaphthylamine derivative compounds all have circularly polarized properties.

[0107] The dinaphthylamine derivatives in this application are molecules with axial chirality, while benzophenone or diphenyl sulfone can serve as chiral centers or chiral inducing elements. When the two are combined, a stronger chiral center or chiral environment is generated, thereby enhancing the CPL signal. Benzophenone or diphenyl sulfone can serve as electron acceptors, while the amino group of dinaphthylamine can serve as electron donors. This structural design can promote an efficient ICT process, which is generally associated with enhanced luminescence efficiency and CPL activity. The introduction of benzophenone or diphenyl sulfone will expand the conjugated system of the dinaphthylamine derivatives, which helps to adjust the luminescence properties, such as emission wavelength and luminescence efficiency. In addition, the ring structure of the dinaphthylamine derivative bound to the acceptor may form a more rigid molecular structure, which helps to reduce non-radiative transitions and improve luminescence efficiency.

[0108] The present application provides a class of chiral macrocycles with binaphthylamine derivatives as donors, as well as their preparation methods and applications. Organic compounds based on binaphthylamine derivatives use binaphthylamine groups as donor structures and connect different receptors to synthesize a series of DADA closed-ring structure molecules with high quantum yield and circularly polarized light properties, which can be used to prepare high-efficiency organic electroluminescent devices.

[0109] At the same time, the present application realizes the controllable preparation of binaphthylamine derivatives; the preparation cost is low, the raw material sources are wide, large-scale production can be achieved, and it has broad commercial prospects.

[0110] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with an embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0111] Although several embodiments of the present application have been shown and described, those skilled in the art will appreciate that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and purpose of the present application, and that the scope of the present application is defined by the claims and their equivalents.

Claims

1. A binaphthylamine derivative having a chiral macrocycle, which can be used as a circularly polarized luminescent material, characterized in that: It has a molecular structure as shown in formula (1) or (2): Wherein, R1 is independently selected from one of phenyl and tert-butyl, and R2 and R3 are independently selected from any one of pyrimidine derivatives, triazine derivatives, benzophenone derivatives, and diphenyl sulfone derivatives.

2. The binaphthylamine derivative having a chiral macrocycle according to claim 1, characterized in that: The R1 to R3 substituents are selected from any one of 1 to 13 below 3. The binaphthylamine derivative having a chiral macrocycle according to claim 1, characterized in that: Has one of the following molecular structures:

4. The binaphthylamine derivative having a chiral macrocycle according to claim 3, characterized in that: Has one of the following molecular structures:

5. The method for preparing the binaphthylamine derivative having a chiral macrocycle according to claim 4, characterized in that: The steps include: S1. Preparation of intermediate product R / S-2 Under an inert gas atmosphere, [1,1'-binaphthyl]-2,2'-diamine, 4-tert-butylbromobenzene, palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine and sodium tert-butoxide were dispersed in a two-necked flask containing toluene and reacted at 110°C for 12 hours. After the reaction, the solvent was dried and the crude product was further purified to obtain the intermediate product R / S-2. S2. Preparation of intermediate product R / S-3 or R / S-3' Under an inert gas atmosphere, the intermediate product R / S-2 obtained in step S1, 4,4'-dibromodiphenyl sulfone or 4,4'-dibromobenzophenone, palladium acetate, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and sodium tert-butoxide are dispersed in a two-necked flask containing toluene and reacted at 110° C. for 6 hours. After the reaction is completed, the solvent is dried and the crude product is further purified to obtain the intermediate product R / S-3 or R / S-3'; S3. Preparation of target product A21 or A23 Under an inert gas atmosphere, the intermediate product R / S-3 or R / S-3' obtained in step S2 is dispersed with 4,4'-dibromodiphenyl sulfone or 4,4'-dibromobenzophenone, palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide in a two-necked flask containing toluene. The mixture is reacted at 110°C for 12 hours. After the reaction, the solvent is dried and the resulting crude product is further purified to obtain the target product A21 or A23.

6. The method for preparing a benzothiadiazole derivative according to claim 5, wherein: The crude product in steps S1, S2 and S3 is further purified by column chromatography.

7. The method for preparing a benzothiadiazole derivative according to claim 6, wherein: The detergent used in the column chromatography purification in step S1 is petroleum ether: dichloromethane in a volume ratio of 2:

1.

8. The method for preparing a benzothiadiazole derivative according to claim 6, wherein: The washing solvent used in the column chromatography purification in step S2 is petroleum ether: dichloromethane in a volume ratio of 4:

1.

9. The method for preparing a benzothiadiazole derivative according to claim 5, wherein: The inert gas atmosphere in steps S1, S2 and S3 is a nitrogen atmosphere.

10. Use of the binaphthylamine derivative having a chiral macrocycle according to claim 1 as a luminescent material, a luminescent device or a smart material.

Images