CN115850247A - Asymmetric thermal activation delayed fluorescent material based on triazine and fluorene unit derivatives, and preparation and application thereof - Google Patents
Asymmetric thermal activation delayed fluorescent material based on triazine and fluorene unit derivatives, and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 230000003111 delayed effect Effects 0.000 title claims abstract description 34
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 27
- 238000007725 thermal activation Methods 0.000 title claims abstract description 24
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims description 9
- DDGPPAMADXTGTN-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 DDGPPAMADXTGTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010898 silica gel chromatography Methods 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- HDVVFJKYLNSKOG-UHFFFAOYSA-N [4-(4-methoxy-n-(4-methoxyphenyl)anilino)phenyl]boronic acid Chemical compound C1=CC(OC)=CC=C1N(C=1C=CC(=CC=1)B(O)O)C1=CC=C(OC)C=C1 HDVVFJKYLNSKOG-UHFFFAOYSA-N 0.000 claims description 2
- TWWQCBRELPOMER-UHFFFAOYSA-N [4-(n-phenylanilino)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 TWWQCBRELPOMER-UHFFFAOYSA-N 0.000 claims description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims 2
- -1 D15 boronic acid derivatives Chemical class 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 abstract 1
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- 238000000746 purification Methods 0.000 abstract 1
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- 239000000843 powder Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
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- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 description 3
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
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- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VTNULXUEOJMRKZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(2H-tetrazol-5-ylmethyl)benzamide Chemical compound N=1NN=NC=1CNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O VTNULXUEOJMRKZ-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to derivatives based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene units and their use in organic electroluminescent devices. This is based on 2-chloro-4, 6-diphenyl-1,derivatives of 3, 5-triazine and fluorene units, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives by sp coupling reaction catalyzed by base 3 The hybridized carbon atoms are fixed in a single molecule to prepare the D-2A asymmetric thermal activation delayed fluorescent material. The material of the invention has simple synthesis method, cheap and easily obtained raw materials and easy purification. The luminescent property and the thermal stability of the final product can be adjusted by connecting different groups, and an OLED device prepared by taking the luminescent material as a luminescent layer has high luminescent brightness, good stability and higher external quantum efficiency.
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to an asymmetric thermal activation delayed fluorescence material containing 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives, a preparation method of the material, and application of the material in organic electroluminescence.
Background
In recent years, organic electroluminescent diodes (OLEDs) have been widely used in flat panel displays due to their advantages of light weight, thin profile, fast response speed, high stability, and the like. The traditional organic fluorescent material has low device efficiency because only 25 percent of singlet excitons can emit light due to orbital spin forbidden resistance; although organic phosphorescent materials doped with heavy metals such as iridium, platinum, and osmium can achieve 100% internal quantum efficiency through orbital spin coupling, heavy metals are stored in small amounts, are expensive, and are non-renewable resources, and these conditions greatly limit the large-scale application of OLEDs. Meanwhile, the phosphorescent material has obvious disadvantages in the aspects of blue light emission, device stability and service life. Therefore, efficient and stable organic light emitting materials are still a necessary trend for the commercialization of OLEDs.
The thermal activation delayed fluorescent material has small energy difference between singlet excitons and triplet excitons, so that the triplet excitons can return to the singlet state through a reverse intersystem crossing process and then return to the ground state in a radiative transition mode to release instantaneous or delayed fluorescence, and the internal quantum efficiency of 100 percent is realized.
The design idea of the D-A type thermal activation delayed fluorescent material is that proper electron-donating groups and electron-withdrawing groups are introduced into the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO), and the two parts are separated properly in space, so that the singlet excitons and the triplet excitons have smaller energy difference, the reverse intersystem crossing process of the triplet excitons is facilitated, and the luminous efficiency of the device is improved.
However, the external quantum efficiency of the D-a type thermal activation delayed fluorescent material is low due to the intramolecular charge transfer characteristic, and the roll-off value of the operating efficiency of the electroluminescent device prepared by using the D-a type thermal activation delayed fluorescent material is also large, so that a more stable thermal activation delayed fluorescent material is yet to be further developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a space-conjugated thermal activation delayed fluorescent material, in particular to an asymmetric thermal activation delayed fluorescent material containing 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives, and also relates to a preparation method of the material and application of the material in an electroluminescent device.
The invention is solved by the following technical scheme.
The invention relates to an asymmetric thermal activation delayed fluorescence material based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives, which has the following structural general formula:
in the structural general formula, D is an electron donating group, A 1 Are electron withdrawing groups.
In a preferred embodiment, A in the general structural formula 1 Comprises the following steps: one of cyano, 4-toluene thiophenol and p-methyl benzene sulfonyl chloride.
In a preferred embodiment, D in the general structural formula is a group formed by one of the following boronic acid derivatives D1 to D15:
in this application, when A 1 When the cyano group is present, the structure of the thermally activated delayed fluorescence materialThe formula is one of the following:
in this application, when A 1 In the case of 4-toluene thiophenol, the structural formula of the thermal activation delayed fluorescence material is one of the following:
in this application, when A 1 When the fluorescent material is p-toluenesulfonyl chloride, the structural formula of the thermal activation delayed fluorescent material is one of the following formulas:
the application relates to a preparation method of an asymmetric thermal activation delayed fluorescence material based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives, which comprises the following steps:
step 1: putting boric acid derivatives, fluorenyl derivatives and potassium carbonate into a dry two-mouth bottle, sealing, vacuumizing, introducing nitrogen to an anhydrous and oxygen-free state, and keeping a nitrogen atmosphere; adding toluene for dissolving, heating and refluxing, and cooling to room temperature after the reaction is finished; adding dichloromethane and water for extraction, collecting an organic layer, drying by using anhydrous sodium sulfate, concentrating, preparing a sample, and purifying by using a silica gel column chromatography method to obtain an intermediate product 1;
and step 3: the intermediate product 2 obtained in the step 2 is mixed with A 1 Putting sodium carbonate into a dry two-mouth bottle, sealing, vacuumizing, introducing nitrogen to a water-free and oxygen-free state, and keeping a nitrogen atmosphere; adding N, N-dimethylformamide for dissolving, heating and refluxing, and cooling to room temperature after the reaction is finished; adding dichloromethane and water for extraction, collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, concentrating the organic layer, preparing a sample, and purifying the sample by using a silica gel column chromatography method to obtain the asymmetric heat-activated delayed fluorescent material based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives.
In a preferred embodiment, the molar ratio of the boronic acid derivative, the fluorenyl derivative and the potassium carbonate in step 1 is 1.2:1:2, refluxing at 90-120 ℃ for 12-24h; step 2 the molar ratio of intermediate 1, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and sodium hydride is 1:1.2:5, refluxing at 90-100 ℃ for 24h; intermediate products 2 and A in step 3 1 The mol ratio of sodium carbonate is 1:2:5, the reflux temperature is 120-140 ℃, and the reflux time is 24h.
In the application, the boric acid derivative is one of 4-diphenylaminobenzeneboronic acid, (4- (di (4-methoxyphenyl) amino) phenyl) boronic acid and N-phenyl-3-carbazole boronic acid;
A 1 is one of cyano, 4-toluene thiophenol and p-methyl benzene sulfonyl chloride.
The following is an example of a specific preparation method.
Step 1: and D is introduced. The 2, 7-dibromo-9-fluorenone and boric acid derivatives are introduced into D under the catalysis of alkali, and the 2, 7-dibromo-9-fluorenone is preferentially adopted as the raw material, so that the preparation process is simple and the yield is high.
And 2, step: introduction of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine. Taking the product obtained in the step 1 as a raw material, and introducing 2-chloro-4, 6-diphenyl-1, 3, 5-triazine by electrophilic substitution reaction under the catalysis of alkali.
And step 3: a. The 1 The introduction of (1). And (3) taking the product obtained in the step (2) as a raw material, and preparing the target product in a protic polar solvent by a one-pot method.
In the preparation processes of the steps 1,2 and 3, the reaction is carried out under the conditions of no water, no oxygen and heating reflux. In the steps 1 and 2, the alkali is preferably potassium carbonate and sodium hydride. In step 3, the protic polar solvent is preferably N, N-dimethylformamide.
In addition, the application also relates to the application of the asymmetric thermal activation delayed fluorescence material based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives in an organic electroluminescent device.
Compared with the prior art, the invention has the following beneficial effects: the present invention is based on the utilization of sp within a single molecule 3 The hybridized carbon atoms are introduced into electron donating and withdrawing groups to form bipolar molecules, so that the material is endowed with balanced carrier transmission capability, the composition of holes and electrons in an emission layer is promoted, and the reduction of starting voltage and roll-off efficiency are facilitated. In addition, a large steric hindrance group is introduced to the structure of the fluorene unit derivative, so that a large steric hindrance is formed in molecules, and the triplet state energy level of the material is favorably improved, so that the obtained luminescent material is favorable for improving the device efficiency of OLEDs.
Drawings
FIG. 1 shows a scheme for preparing Compound 1 of the present invention 1 HNMR spectrogram.
FIG. 2 shows a scheme for preparing Compound 1 13 CNMR spectrogram.
FIG. 3 is a high resolution mass spectrum of Compound 1.
FIG. 4 is a chart of UV-VIS absorption spectrum of Compound 1 in dichloromethane solution.
FIG. 5 is a graph of luminance and current density as a function of voltage for organic electroluminescent devices prepared from Compound 1.
FIG. 6 is a graph showing the power efficiency and external quantum efficiency of an organic electroluminescent device prepared from Compound 1 as a function of luminance.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The embodiments described below are exemplary only for the purpose of illustrating the present invention and should not be construed as limiting the present invention.
Example 1: compound 1 was prepared as follows.
(1) And D is introduced.
2, 7-dibromo-9-fluorenone (1.69g, 5 mmol), N-phenyl-3-carbazolboronic acid (2.15g, 7.5 mmol), p-toluenesulfonylhydrazide (1.4g, 7.5 mmol), and K were reacted with toluene sulfonic acid 2 CO 3 (1.38g, 10mmol) was placed in a dry 100ml two-necked flask, and nitrogen gas was introduced into the flask under vacuum to be in an anhydrous oxygen-free state while maintaining a nitrogen atmosphere, and after adding an appropriate amount of a toluene solution to dissolve the mixture, the temperature was raised to 110 ℃ to react for 5 hours. After the reaction was completed, the reaction solution was cooled to room temperature and extracted three times with methylene chloride and water. Collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, preparing a sample by spin drying, and purifying by using a column chromatography mode, wherein an eluent is a compound of 1:10 dichloromethane: petroleum ether mixed solution. 2.46g of white powder are obtained, with a yield of 87%.
(2) The introduction of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine.
Intermediate 1 (1.13g, 2mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (642mg, 2.4mmol), naH (120mg, 10mmol) were placed in a dry 100ml two-necked flask, and vacuum was applied by introducing nitrogen gas to an anhydrous oxygen-free state while maintaining a nitrogen atmosphere. Adding a proper amount of 1, 4-dioxane solution to dissolve, heating to 120 ℃, and heating and refluxing for reaction for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted three times with dichloromethane and water. Collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, preparing a sample by spin drying, and purifying by using a column chromatography mode, wherein an eluent is a mixture of 1: dichloromethane of 8: petroleum ether mixed solution. 993.4mg of pale yellow powder was obtained, representing a yield of 67%.
(3)A 1 Introduction of (2)
Putting the intermediate 2 (797mg, 1mmol), sodium carbonate (530mg, 5mmol) and CuCN (231mg, 2mmol) into a dry 50ml two-neck flask, vacuumizing, introducing nitrogen to a water-free and oxygen-free state, keeping a nitrogen atmosphere, adding a proper amount of N, N-dimethylformamide solution, dissolving, and heating to 130 ℃ for reaction for 10 hours. After the reaction is finished and the reaction solution is cooled, extracting the reaction solution for three times by using dichloromethane and water, collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, then carrying out spin drying to prepare a sample, and purifying the sample by using a silica gel column chromatography mode, wherein an eluent is a compound of 1:2 dichloromethane and petroleum ether solution. 537.3mg of a yellow solid was obtained, yield 78%.
Example 2: compound 2 was prepared as follows.
(1) And D is introduced.
Synthesis method of Compound 2 with introduction of D group referring to example 1, the pure product was white powder with a yield of 77%.
(2) Introduction of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine.
Synthesis method of Compound 2 for introducing 2-chloro-4, 6-diphenyl-1, 3, 5-triazine group referring to example 1, the pure product was pale yellow powder with a yield of 64%.
(3)A 1 The introduction of (2).
Example 3: compound 3 was prepared as follows.
(1) And D is introduced.
Synthesis method for introducing D group into Compound 3 referring to example 1, pure product is white powder with yield of 48%.
(2) The introduction of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine.
Synthesis method of Compound 3 for introducing 2-chloro-4, 6-diphenyl-1, 3, 5-triazine group referring to example 1, the pure product was pale yellow powder with a yield of 64%.
(3)A 1 The introduction of (1).
Compound 3 introduction of A 1 Synthesis of the radicals with reference to example 1, the pure product is a yellow powder with a yield of 71%.
Example 4: compound 4 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in Compound 4 was the same as in example 1.
(1)A 1 The introduction of (1). Putting the intermediate 2 (797mg, 1mmol), 4-toluene thiophenol (248mg, 2mmol) and potassium carbonate (5308mg, 5mmol) into a dry 50ml two-neck flask, vacuumizing, introducing nitrogen to a water-free and oxygen-free state, keeping nitrogen atmosphere, adding a proper amount of N, N-dimethylformamide solution, dissolving, and heating to 130 ℃ for reaction for 10 hours. After the reaction is finished and the reaction solution is cooled, extracting the reaction solution for three times by using dichloromethane and water, collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, then carrying out spin drying to prepare a sample, and purifying the sample by using a silica gel column chromatography mode, wherein an eluent is a compound of 1:1 of dichloromethane and petroleum ether. 724mg of a yellow solid are obtained, yield 82%.
Example 5: compound 5 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in Compound 5 was the same as in example 2.
(1)A 1 The introduction of (1). Compound 5 introduction A 1 Synthesis of the radicals with reference to example 4, the pure product is a yellow powder with a yield of 87%.
Example 6: compound 6 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in Compound 6 was the same as in example 3.
(1)A 1 The introduction of (2). Compound 6 introduction of A 1 Synthesis of the radical referring to example 4, the pure product is a yellow powder with a yield of 74%.
Example 7: compound 7 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in compound 7 was the same as in example 1. Introduction of 4-Methylthiophenol reference example 4.
(1) Sulfur is oxidized to sulfones.
Intermediate 3 (883mg, 1mmol) was placed in a dry 50ml two-necked flask, glacial acetic acid (10 ml) and aqueous hydrogen peroxide (30%, 18 ml) were added and the mixture was stirred at 120 ℃ for 12h. After the reaction was completed, the reaction mixture was cooled to room temperature, and then distilled water was added thereto, followed by filtration, washing and drying to obtain 900mg of a yellow solid with a yield of 95%.
Example 8: compound 8 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in Compound 8 was the same as in example 2. Introduction of 4-Methylthiophenol reference example 5.
(1) Oxidation of sulfur to sulfones
The sulfur oxidation to sulfone in compound 8 was performed in 95% yield as a yellow solid, as described in example 7.
Example 9: compound 9 was prepared as follows.
The introduction of D and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine groups in Compound 9 was the same as in example 3. Introduction of 4-Methylthiophenol reference example 6.
(1) Sulfur is oxidized to sulfones. The sulfur was oxidized to sulfone in compound 9 in the same manner as in example 7, and the pure product was a yellow solid with a yield of 95%.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.
Claims (10)
1. The asymmetric thermal activation delayed fluorescence material based on triazine and fluorene unit derivatives is characterized in that the thermal activation delayed fluorescence material has the following structural general formula:
in the structural general formula, D is an electron donating group, A 1 Are electron withdrawing groups.
2. The asymmetric thermally activated delayed fluorescence material based on triazine and fluorene unit derivatives as claimed in claim 1, wherein A in the structural general formula 1 Comprises the following steps: one of cyano, 4-toluene thiophenol and p-methyl benzene sulfonyl chloride.
3. The asymmetric thermally activated delayed fluorescence material based on triazine and fluorene unit derivatives as claimed in claim 1, wherein D in the structural general formula is a group formed by one of the following D1 to D15 boronic acid derivatives:
4. triazine-based and of claim 1The asymmetric heat-activated delayed fluorescent material of the fluorene unit derivative is characterized in that when A is 1 When the fluorescent material is cyano, the structural formula of the thermal activation delayed fluorescent material is one of the following formulas:
5. the asymmetric type thermal activation delayed fluorescence material based on triazine and fluorene unit derivatives as claimed in claim 1, wherein when A is 1 In the case of 4-toluene thiophenol, the structural formula of the thermal activation delayed fluorescence material is one of the following:
6. the asymmetric type thermal activation delayed fluorescence material based on triazine and fluorene unit derivatives as claimed in claim 1, wherein when A is 1 When the fluorescent material is p-toluenesulfonyl chloride, the structural formula of the thermal activation delayed fluorescent material is one of the following formulas:
7. method for the preparation of an asymmetric thermally activated delayed fluorescence material based on derivatives of triazine and fluorene units as claimed in any of the claims 1 to 6, characterized in that it comprises the following steps:
step 1: placing boric acid derivatives, fluorenyl derivatives and potassium carbonate into a dry two-mouth bottle, sealing, vacuumizing, introducing nitrogen to a water-free and oxygen-free state, and keeping a nitrogen atmosphere; adding toluene for dissolving, heating and refluxing, and cooling to room temperature after the reaction is finished; adding dichloromethane and water for extraction, collecting an organic layer, drying by using anhydrous sodium sulfate, concentrating, preparing a sample, and purifying by using a silica gel column chromatography method to obtain an intermediate product 1;
step 2, putting the intermediate product 1 obtained in the step 1, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and sodium hydride into a dry two-mouth bottle, sealing the mouth, vacuumizing, introducing nitrogen to a water-free and oxygen-free state, and keeping a nitrogen atmosphere; adding 1, 4-dioxane for dissolving, heating and refluxing, and cooling to room temperature after the reaction is finished; adding dichloromethane and water for extraction, collecting an organic layer, drying by using anhydrous sodium sulfate, concentrating, preparing a sample, and purifying by using a silica gel column chromatography method to obtain an intermediate product 2;
and step 3: the intermediate product 2 obtained in the step 2 is mixed with A 1 Putting sodium carbonate into a dry two-mouth bottle, sealing, vacuumizing, introducing nitrogen to an anhydrous and oxygen-free state, and keeping a nitrogen atmosphere; adding N, N-dimethylformamide for dissolving, heating and refluxing, and cooling to room temperature after the reaction is finished; adding dichloromethane and water for extraction, collecting an organic layer, drying the organic layer by using anhydrous sodium sulfate, concentrating the organic layer, preparing a sample, and purifying the sample by using a silica gel column chromatography method to obtain the asymmetric heat-activated delayed fluorescent material based on 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and fluorene unit derivatives.
8. The method for preparing the asymmetric type thermal activation delayed fluorescence material based on the triazine and fluorene unit derivatives according to claim 7, wherein:
in the step 1, the molar ratio of the boric acid derivative to the fluorenyl derivative to the potassium carbonate is 1.2:1:2, refluxing at 90-120 ℃ for 12-24h;
step 2 the molar ratio of the intermediate 1, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to sodium hydride is 1:1.2:5, refluxing at 90-100 ℃ for 24h;
intermediate products 2 and A in step 3 1 The mol ratio of sodium carbonate is 1:2:5, the reflux temperature is 120-140 ℃, and the reflux time is 24h.
9. The method for preparing an asymmetric thermally activated delayed fluorescence material based on triazine and fluorene unit derivatives as claimed in claim 7, wherein the boric acid derivatives are one of 4-diphenylaminobenzeneboronic acid, (4- (di (4-methoxyphenyl) amino) phenyl) boronic acid, N-phenyl-3-carbazole boronic acid;
A 1 is one of cyano, 4-toluene thiophenol and p-methyl benzene sulfonyl chloride.
10. Use of an asymmetric thermally activated delayed fluorescence material based on derivatives of triazine and fluorene units as claimed in any of claims 1 to 6 in organic electroluminescent devices.
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