Benzothiadiazole cyclic derivative as well as preparation method and application thereof
By designing the DADA structure of a benzothiadiazole cyclic derivative, the problems of red light emission and charge distribution regulation in the prior art were solved, and the photoelectric performance of the high-efficiency organic electroluminescent device was improved.
Patent Information
- Application Number
- CN202510981884.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2025-06-30
- Filing Date
- 2025-07-16
- Publication Date
- 2025-11-14
AI Technical Summary
In the existing technology, aromatic π-conjugated molecular materials are difficult to emit in the red light region, and the intramolecular charge distribution is difficult to control to meet the photoelectric performance requirements of organic electroluminescent devices.
We designed and synthesized benzothiadiazole cyclic derivatives with a DADA structure, using benzothiadiazole as an acceptor to connect donor structures such as triphenylamine, forming materials with red light emission spectral characteristics.
It achieves emission in the red light region, improves the photoelectric performance of organic electroluminescent devices, and possesses high quantum yield and high luminous efficiency.
Smart Images
Figure CN120943845A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of organic light-emitting materials technology, specifically to a benzothiadiazole cyclic derivative, its preparation method, and its application. Background Technology
[0002] π-conjugated systems have been extensively studied for device development. Aromatic π-conjugated optoelectronic materials, as an important type, possess excellent optoelectronic properties. Aromatic π-conjugated molecules can be applied to devices such as field-effect transistors and light-emitting diodes. Large π-conjugated (DADA) cyclic molecular materials have achieved significant development. The optical and electronic properties of the molecules can be modulated by changes in their molecular structure. Donor-acceptor-donor-acceptor (DADA) conjugated compounds exhibit low band gaps and broad optical absorption spectra, with intramolecular charge shifting from electron-rich donors to electron-deficient acceptor units.
[0003] Therefore, altering the molecular structure of DADA to control the distribution of charge within the molecule and thus modulate its optical properties has always been an important research direction in this field.
[0004] Patent application content
[0005] To overcome the problems existing in the prior art, the primary objective of this application is to provide a benzothiadiazole cyclic derivative. This benzothiadiazole cyclic derivative can redshift the emission wavelength to the red light region.
[0006] Another object of this application is to provide a method for preparing the above-mentioned benzothiadiazole cyclic derivative.
[0007] Another objective of this application is to provide the application of the above-mentioned benzothiadiazole cyclic derivatives.
[0008] The above-mentioned objectives of this application are achieved through the following technical solutions:
[0009] A benzothiadiazole cyclic derivative, which can be used as a luminescent material, is characterized by having a molecular structure as shown in formula (1) or formula (2):
[0010]
[0011]
[0012] Among them, R1 to R3 are benzene substituents or heteroatom benzene ring substituents.
[0013] Preferably, when R1 to R3 represent substituents, each substituent is individually selected from a benzene ring and its derivatives or from various heterocyclic derivatives.
[0014] More preferably, the atoms in the above-mentioned ring structure contain hydrogen atoms, deuterium atoms, or substituents.
[0015] Preferably, the R1 to R3 substituents in this application are selected from any one of the following from I to XXIV:
[0016]
[0017] This application also provides a method for preparing the above-mentioned benzothiadiazole cyclic derivative, comprising the following steps:
[0018] S1. Preparation of intermediate product A1-1 or A197-1
[0019] Under an inert gas atmosphere, N1,N3-diphenylphenyl-1,3-diamine (or N1,N3-bis([1,1′-biphenyl]-4-yl)-1,3-phenylenediamine), ditert-butyl dicarbonate, and 4-dimethylaminopyridine were reacted in a 30 mL tetrahydrofuran double-necked flask at 78 °C for 12 hours. After the reaction was completed, the solvent was evaporated. The crude product was further purified to obtain intermediate product A1-1 or A197-1.
[0020] S2. Preparation of intermediate product A1-2 or A197-2
[0021] Under an inert gas atmosphere, the intermediate product A1-1, 4,7-dibromo-2,1,3-benzothiadiazole (or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine, and sodium tert-butoxide obtained in step S1 were dispersed in a 30 mL toluene double-necked flask and reacted at 100 °C for 12 hours. After the reaction was completed, the crude product obtained after evaporating the solvent was further purified to obtain the target product A1-2 or A197-2.
[0022] S3. Preparation of intermediate product A1-3 or A197-3
[0023] Under an inert gas atmosphere, the intermediate product A1-2 obtained in step S2 was reacted in a solution of trifluoroacetic acid and dichloromethane at a volume ratio of 3:1 for 6 hours. The crude product was further purified to obtain intermediate product A1-3 or A197-3.
[0024] S4. Preparation of the target product A1 or A197
[0025] Under an inert gas atmosphere, A1-3,4,7-dibromo-2,1,3-benzothiadiazole (or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide were dispersed in a 30 mL toluene double-necked flask and reacted at 60 °C for 24 hours. After the reaction was completed, the crude product obtained by evaporating the solvent was further purified to obtain the target product A1 or A197.
[0026] Preferably, the crude product in steps S1, S2 and S4 is further purified by column chromatography, while in step S3 it is purified by washing and extraction.
[0027] More preferably, the washing agent used in step S1 column chromatography purification is petroleum ether: dichloromethane in a volume ratio of 5:1.
[0028] More preferably, the washing agent used in step S2, column chromatography purification, is petroleum ether:dichloromethane in a volume ratio of 6:1.
[0029] This application also provides the application of the above-mentioned benzothiadiazole cyclic derivatives as luminescent materials, luminescent devices or smart materials.
[0030] Compared with the prior art, the beneficial effects of this application are:
[0031] The provided benzothiadiazole cyclic derivative uses benzothiadiazole as an acceptor and has red light emission spectrum characteristics, which meets the photoelectric performance requirements of organic electroluminescent devices. Attached Figure Description
[0032] Figure 1 The 1H MNR chromatogram of compound A1 prepared in Example 1 of this application;
[0033] Figure 2 The 1H MNR chromatogram of compound A197 prepared in Example 2 of this application;
[0034] Figure 3 The ultraviolet absorption spectra of compounds A1 and A197 prepared in Examples 1 and 2 of this application are shown.
[0035] Figure 4 The PL emission patterns of compounds A1 and A197 prepared in Examples 1 and 2 of this application are shown.
[0036] Figure 5 This is a photoluminescence quantum yield diagram of compound A1 prepared in Example 1 of this application before deoxygenation;
[0037] Figure 6 Photoluminescence quantum yield diagram of compound A197 prepared in Example 2 of this application before deoxygenation. Detailed Implementation
[0038] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.
[0039] It should be noted that:
[0040] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.
[0041] In this application, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.
[0042] Unless otherwise specified, the components or preferred components involved in this application may be combined to form new technical solutions.
[0043] In this application, unless otherwise stated, the numerical range "a~b" is a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers.
[0044] The “scope” disclosed in this application may be in the form of a lower limit and an upper limit, and may be one or more lower limits and one or more upper limits, respectively.
[0045] In this application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.
[0046] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this application.
[0047] This application provides a benzothiadiazole cyclic derivative that can be used as a luminescent material, having the molecular structure shown in formula (1) or formula (2) below:
[0048]
[0049] Among them, R1 to R3 are benzene substituents or heteroatom benzene ring substituents.
[0050] The benzothiadiazole cyclic derivatives provided in this application are based on organic compounds containing triphenylamine and other groups as donor structures, which are linked to benzothiadiazole derivative acceptors with different structures to synthesize a series of DADA cyclic molecules. These molecules have red light emission spectrum characteristics and high quantum yield, and can be used to prepare high-efficiency organic electroluminescent devices.
[0051] In some preferred embodiments, when R1 to R3 represent substituents, each is independently selected from benzene rings and their derivatives or benzene ring derivatives containing heteroatoms.
[0052] In some preferred embodiments, the atoms of the further ring structure have hydrogen atoms, deuterium atoms, or substituents.
[0053] In some preferred embodiments, the substituent is selected from any one of the following: I to XXIV:
[0054]
[0055] In some preferred embodiments, the benzothiadiazole cyclic derivative of formula (1) may preferably be any one of the following compounds A1 to A306:
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067]
[0068]
[0069]
[0070] This application also provides a method for preparing the above-mentioned benzothiadiazole cyclic derivative, comprising the following steps:
[0071] S1. Preparation of intermediate product A1-1 or A197-1
[0072] Under an inert gas atmosphere, N1,N3-diphenylphenyl-1,3-diamine (or N1,N3-bis([1,1′-biphenyl]-4-yl)-1,3-phenylenediamine), di-tert-butyl dicarbonate, and 4-dimethylaminopyridine were reacted in a 30 mL tetrahydrofuran double-necked flask at 78 °C for 12 hours. After the reaction was completed, the solvent was evaporated, and the crude product was further purified to obtain intermediate product A1-1 or A197-1.
[0073] S2. Preparation of intermediate product A1-2 or A197-2
[0074] Under an inert gas atmosphere, the intermediate product A1-1 or A197-1 obtained in step S1, 4,7-dibromo-2,1,3-benzothiadiazole (or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine, and sodium tert-butoxide were dispersed in a 30 mL toluene double-necked flask and reacted at 100 °C for 12 hours. After the reaction was completed, the crude product obtained after evaporating the solvent was further purified to obtain the target product A1-2 or A197-2.
[0075] S3. Preparation of intermediate product A1-2 or A197-2
[0076] Under an inert gas atmosphere, the intermediate product A1-2 or A197-2 obtained in step S2 was reacted in a solution of trifluoroacetic acid and dichloromethane at a volume ratio of 3:1 for 6 hours. The crude product was further purified to obtain intermediate product A1-3 or A197-3.
[0077] S4. Preparation of the target product A1 or A197
[0078] Under an inert gas atmosphere, A1-3 or A197-3, 4,7-dibromo-2,1,3-benzothiadiazole or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, tri-tert-butylphosphine and sodium tert-butoxide were dispersed in a 30 mL toluene double-necked flask and reacted at 60 °C for 24 hours. After the reaction was completed, the crude product obtained by evaporating the solvent was further purified to obtain the target product A1 or A197.
[0079] In some preferred embodiments, the crude product in steps S1, S2, and S4 is further purified by column chromatography, while in step S3 it is purified by washing and extraction.
[0080] The following will describe in detail the preparation methods of compounds A1 and A197, which are cyclic derivatives of benzothiadiazole, represented by formula (1) or formula (2).
[0081] S1. The preparation method of intermediate product A1-1 is as follows:
[0082] Under a nitrogen atmosphere, N1,N3-diphenylphenyl-1,3-diamine (2.6 g, 10 mmol, 1 eq), di-tert-butyl dicarbonate (3.27 g, 15 mmol, 1.5 eq), and 4-dimethylaminopyridine (245 mg, 2 mmol, 0.2 eq) were dispersed in a 30 mL tetrahydrofuran (THF) double-necked flask. The reaction was carried out at 78 °C for 12 h. After the reaction was complete, the solvent was evaporated, and the crude product was further purified by recrystallization using petroleum ether:dichloromethane (v / v 5:1) to give intermediate A1-1, with a yield of 3.06 g (85% yield).
[0083] The chemical reaction equations for this preparation step are as follows:
[0084]
[0085] S2. Preparation of intermediate product A1-2
[0086] Under a nitrogen atmosphere, intermediate A1-1 (7.2 g, 20 mmol, 2 eq), 4,7-dibromo-2,1,3-benzothiadiazole (2.94 g, 10 mmol, 1 eq), palladium acetate (Pd(OAc)2) (112 mg, 0.5 mmol, 0.05 eq), 1,1-binaphthyl-2,2-bis(diphenylphosphine) (BINAP) (311 mg, 0.5 mmol, 0.05 eq), and sodium tert-butoxide (NaOtBu) (2.88 g, 30 mmol, 3 eq) were dispersed in a 30 mL tetrahydrofuran (THF) double-necked flask. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (6:1 v / v). Intermediate A1-2 was obtained, with a yield of 7.08 g (83%).
[0087] The chemical reaction equations for this preparation step are as follows:
[0088]
[0089] S3. Preparation of intermediate product A1-3
[0090] Under a nitrogen atmosphere, intermediate A1-2 (8.53 g, 10 mmol, 1 eq) and trifluoroacetic acid (5.7 g, 50 mmol, 1.5 eq) were dispersed in a 15 mL dichloromethane (DCM) double-necked flask. The reaction was carried out at 25 °C for 6 hours. After the reaction was completed, the pH was adjusted to weakly alkaline by adding saturated sodium bicarbonate solution, followed by extraction with dichloromethane. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to give intermediate A1-3, with a yield of 6.2 g (95% yield).
[0091]
[0092] S4. Preparation of target product A1
[0093] Under a nitrogen atmosphere, Al-3 (6.52 g, 10 mmol, 1 eq), 4,7-dibromo-2,1,3-benzothiadiazole (2.94 g, 10 mmol, 1 eq), palladium acetate (Pd(OAc)2) (112 mg, 0.5 mmol, 0.05 eq), tri-tert-butylphosphine (202 mg, 1 mmol, 0.1 eq), and sodium tert-butoxide (NaOtBu) (2.88 g, 30 mmol, 3 eq) were dispersed in a 30 mL toluene (Toluene) double-necked flask. The reaction was carried out at 60 °C for 24 hours. After the reaction was completed, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (v / v 8:1).
[0094] Product A1 was obtained, with a yield of 6.5g (yield 83%).
[0095]
[0096] Example 2
[0097] S1. The preparation method of intermediate product A197-1 is as follows:
[0098] Under a nitrogen atmosphere, N1,N3-bis([1,1′-biphenyl]-4-yl)-1,3-phenylenediamine (4.12 g, 10 mmol, 1 eq), di-tert-butyl dicarbonate (3.27 g, 15 mmol, 1.5 eq), and 4-dimethylaminopyridine (245 mg, 2 mmol, 0.2 eq) were dispersed in a 30 mL tetrahydrofuran (THF) double-necked flask. The reaction was carried out at 78 °C for 12 h. After the reaction was completed, the solvent was evaporated, and the crude product was further purified by recrystallization using petroleum ether:dichloromethane (v / v 4:1). Intermediate product A197-1 was obtained, with a yield of 4.2 g (82%).
[0099] The chemical reaction equations for this preparation step are as follows:
[0100]
[0101] S2. Preparation of intermediate product A197-2
[0102] Under a nitrogen atmosphere, intermediate A197-1 (10.24 g, 20 mmol, 2 eq), 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole (4.46 g, 10 mmol, 1 eq), palladium acetate (Pd(OAc)2) (112 mg, 0.5 mmol, 0.05 eq), 1,1-binaphthyl-2,2-bisdiphenylphosphine (BINAP) (311 mg, 0.5 mmol, 0.05 eq), and sodium tert-butoxide (NaOtBu) (2.88 g, 30 mmol, 3 eq) were dispersed in a 30 mL tetrahydrofuran (THF) double-necked flask. The reaction was carried out at 100 °C for 12 h. After the reaction was completed, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (v / v 5:1). Intermediate product A197-2 was obtained, with a yield of 10.4 g (yield 80%).
[0103]
[0104] S3. Preparation of intermediate product A197-3
[0105] Under a nitrogen atmosphere, intermediate A197-2 (13 g, 10 mmol, 1 eq) and trifluoroacetic acid (5.7 g, 50 mmol, 1.5 eq) were dispersed in a 15 mL dichloromethane (DCM) double-necked flask. The reaction was carried out at 25 °C for 6 hours. After the reaction was completed, the pH was adjusted to weakly alkaline by adding saturated sodium bicarbonate solution, followed by extraction with dichloromethane. The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to give intermediate A197-3, with a yield of 10.3 g (93% yield).
[0106]
[0107] S4. Preparation of the target product A197: Under a nitrogen atmosphere, A197-3 (11 g, 10 mmol, 1 eq), 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole (4.46 g, 10 mmol, 1 eq), palladium acetate (Pd(OAc)2) (112 mg, 0.5 mmol, 0.05 eq), tri-tert-butylphosphine (202 mg, 1 mmol, 0.1 eq), and sodium tert-butoxide (NaOtBu) (2.88 g, 30 mmol, 3 eq) were dispersed in a 30 mL toluene double-necked flask. The reaction was carried out at 60 °C for 24 hours. After the reaction was completed, the solvent was evaporated, and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (v / v 7:1). Product A197 was obtained, with a yield of 11.28 g (81%).
[0108]
[0109] Characterization and performance testing
[0110] The benzothiadiazole macrocyclic derivative compounds A1 and A197 prepared in Examples 1 and 2 were characterized and their performance was tested. The results are as follows: Figures 1-4 As shown.
[0111] The testing method is as follows:
[0112] Compound structure determination: Bruker 400MHz superconducting nuclear magnetic resonance spectrometer, deuterated DMSO as solvent;
[0113] Ultraviolet absorption spectroscopy detection: A Shimadzu UV-2700 UV-Vis spectrophotometer was used, with a scanning range of [missing information].
[0114] 280–700 nm;
[0115] Emission spectroscopy detection: A steady-state / transient fluorescence spectrometer (FLS980) was used with an excitation wavelength of 365 nm.
[0116] The test temperature was 300K.
[0117] The test results are as follows:
[0118] from Figure 1It can be seen that the characteristic wavenumbers (ppm) of compound A1 prepared in Example 1 are as follows: ¹H NMR (400MHz, DMSO-D6) δ 8.74–8.70 (m, 4H), 8.19 (d, J = 8.3Hz, 2H), 7.84 (dd, J = 16.4, 8.8Hz, 2H), 7.73 (d, J = 8.8Hz, 1H), 7.69–7.66 (m, 2H), 7.56 (qd, J = 8.6, 7.6, 3.6Hz, 7H), 7.20–7.07 (m, 2H), 6.83–6.44 (m, 21H). The ¹H NMR peak energies correspond one-to-one with the target product, and the number is reasonable. This indicates that benzothiadiazole macrocyclic derivative compound A1 was prepared in Example 1, and the compound has a simple structure and high purity.
[0119] from Figure 2 It can be seen that the characteristic wavenumbers (ppm) of compound A197 prepared in Example 2 are as follows: 1H NMR (400MHz, Chloroform-d) δ 8.00 (s, 2H), 7.83–7.74 (m, 4H), 7.61–7.52 (m, 8H), 7.41 (s, 7H), 7.05 (dd, J = 7.5, 2.0Hz, 2H), 6.83–6.73 (m, 8H), 6.31 (t, J = 2.0Hz, 1H). The molecular proton magnetic resonance peak energies correspond one-to-one with the target product, and the number is reasonable. This indicates that Example 2 successfully prepared benzothiadiazole macrocyclic derivative compound A197, and the compound has a simple structure and high purity.
[0120] Figure 3 The images show the UV absorption spectra of compounds A1 and A197 prepared in Examples 1 and 2 of this application. Figure 3 It can be seen that the ultraviolet absorption peaks of compound A1 prepared in this application are at wavelengths of 300 nm and 520 nm; the ultraviolet absorption peaks of A197 are at wavelengths of 328 nm and 470 nm.
[0121] Figure 4 The PL emission patterns of compounds A1 and A197 prepared in Examples 1 and 2 of this application are shown below. Figure 4 It can be seen that the fluorescence emission peaks of compounds A1 and A197 prepared in this application are at 689 nm and 628 nm, respectively, while the full width at half maximum (FWHM) of compounds A1 and A197 are 121 nm and 115 nm, respectively, and they exhibit red light emission.
[0122] Figure 5 This is a photoluminescence quantum yield diagram of compound A1 prepared in Example 1 of this application before deoxygenation. From... Figure 5As can be seen from the above, the photoluminescence quantum yield of Al prepared in this application reached 23.6% before deoxygenation, which has a high quantum yield and can be used to make a more efficient red light emitting device.
[0123] Figure 6 Photoluminescence quantum yield diagram of compound A197 prepared in Example 2 of this application before deoxygenation. From... Figure 6 As can be seen from the above, the A197 prepared in this application has a photoluminescence quantum yield of 68.4% before deoxygenation, which is high and can be used to make more efficient red light emitting devices.
[0124] In addition to compounds A1 and A197, several other benzothiadiazole macrocyclic derivatives in this application are structurally similar to compounds A1 / A197. They are compounds with red light emission properties, consisting of benzothiadiazole derivatives as acceptors and connected with stabilizing groups and electron-donating triphenylamine derivative groups. Therefore, through similar preparation methods and the same characterization and testing methods, it can be known that these benzothiadiazole macrocyclic derivative compounds all have red light emission properties.
[0125] The benzothiadiazole macrocyclic derivatives in this application are molecules with red light emission properties. The triphenylamine structural unit acts as an electron donor, while the benzothiadiazole structural unit acts as an electron acceptor. This DADA structural design can facilitate efficient ICT processes; this enhanced luminescence efficiency is related to the strong electron-accepting ability of the benzothiadiazole acceptor and the strong electron-donating ability of the triphenylamine donor. The introduction of the triphenylamine structure and the additional benzene ring unit expands the conjugated system of the benzothiadiazole macrocyclic derivative, which helps to tune luminescence properties such as emission wavelength and luminescence efficiency. Furthermore, the derivatives of binatidine combined with triazine may form a more rigid molecular structure, which helps to reduce non-radiative transitions and improve luminescence efficiency.
[0126] This application provides a class of benzothiadiazole macrocyclic derivatives. Based on the organic compounds of benzothiadiazole macrocyclic derivatives, a series of DADA cyclic molecules are synthesized by using benzothiadiazole groups as acceptor structures and linking different triphenylamine derivative donors. These molecules can be used to prepare high-efficiency organic electroluminescent devices.
[0127] Meanwhile, this application achieves the controllable preparation of benzothiadiazole macrocyclic derivatives; the preparation cost is low, the raw material sources are wide-ranging, and large-scale production can be realized, which has broad commercial prospects.
[0128] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions 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 one or more embodiments or examples.
[0129] Although several embodiments of this application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the claims and their equivalents.
Claims
1. A benzothiadiazole cyclic derivative, which can be used as a luminescent material, characterized in that, It has the molecular structure shown in formula (1) or formula (2) as follows: Among them, R1 to R3 are benzene substituents or heteroatom benzene ring substituents.
2. The benzothiadiazole cyclic derivative according to claim 1, characterized in that, When R1 to R3 represent substituents, each is independently selected from either a benzene ring and its derivatives or a benzene ring derivative containing heteroatoms.
3. The benzothiadiazole cyclic derivative according to claim 1, characterized in that, The atoms in the ring structure contain hydrogen atoms, deuterium atoms, or substituents.
4. The benzothiadiazole cyclic derivative according to claim 1, characterized in that, The R1 to R3 substituents are selected from any one of the following from I to XXIV:
5. The benzothiadiazole cyclic derivative according to claim 1, characterized in that, It has one of the following molecular structural formulas: 。 6. The method for preparing the benzothiadiazole cyclic derivative according to claim 1, characterized in that, Includes the following steps: S1. Preparation of intermediate product A1-1 or A197-1 Under an inert gas atmosphere, N1,N3-diphenylphenyl-1,3-diamine (or N1,N3-bis([1,1′-biphenyl]-4-yl)-1,3-phenylenediamine), ditert-butyl dicarbonate, and 4-dimethylaminopyridine were reacted in a 30 mL tetrahydrofuran double-necked flask at 78 °C for 12 hours. After the reaction was completed, the solvent was evaporated. The crude product was further purified to obtain intermediate product A1-1 or A197-1. S2. Preparation of intermediate product A1-2 or A197-2 Under an inert gas atmosphere, the intermediate product A1-1 or A197-1 obtained in step S1, 4,7-dibromo-2,1,3-benzothiadiazole (or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, 1,1-binaphthyl-2,2-bisdiphenylphosphine, and sodium tert-butoxide were dispersed in a 30 mL toluene double-necked flask and reacted at 100 °C for 12 hours. After the reaction was completed, the crude product obtained after evaporating the solvent was further purified to obtain the target product A1-2 or A197-2. S3. Preparation of intermediate product A1-3 or A197-3 Under an inert gas atmosphere, the intermediate product A1-2 obtained in step S2 was reacted in a solution of trifluoroacetic acid and dichloromethane at a volume ratio of 3:1 for 6 hours. The crude product was further purified to obtain intermediate product A1-3 or A197-3. S4. Preparation of the target product A1 or A197 Under an inert gas atmosphere, A1-3,4,7-dibromo-2,1,3-benzothiadiazole (or 4,7-bis(4-bromophenyl)benzo[c][1,2,5]thiadiazole), palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide were dispersed in a 30 mL toluene double-necked flask and reacted at 60 °C for 24 hours. After the reaction was completed, the crude product obtained by evaporating the solvent was further purified to obtain the target product A1 or A197.
7. The method for preparing the benzothiadiazole derivative according to claim 6, characterized in that, The crude product in steps S1, S2 and S4 is further purified by column chromatography, while in step S3 it is purified by washing and extraction.
8. The method for preparing the benzothiadiazole derivative according to claim 7, characterized in that, The washing agent used in step S1, column chromatography purification, is petroleum ether: dichloromethane in a volume ratio of 5:
1.
9. The method for preparing the benzothiadiazole derivative according to claim 7, characterized in that, The washing agent used in step S2, column chromatography purification, is petroleum ether: dichloromethane in a volume ratio of 6:
1.
10. The use of the benzothiadiazole cyclic derivative of claim 1 as a luminescent material, luminescent device, or smart material.