CN115160316A - Orange red photo-thermal activation delayed fluorescent material and synthetic method thereof - Google Patents
Orange red photo-thermal activation delayed fluorescent material and synthetic method thereof Download PDFInfo
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- CN115160316A CN115160316A CN202210922085.3A CN202210922085A CN115160316A CN 115160316 A CN115160316 A CN 115160316A CN 202210922085 A CN202210922085 A CN 202210922085A CN 115160316 A CN115160316 A CN 115160316A
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention relates to an orange-red thermally-activated delayed fluorescence material and a preparation method thereof, wherein the material names are 4, 4'' - (dibenzo [ f, h ] pyrido [2,3-b ] quinoxaline-3, 6, 11-triyl) tri (N, N-diphenyl aniline) (3, 6, 11-tritA-BPQ) and 4, 4'' - (dibenzo [ f, h ] pyrido [2,3-b ] quinoxaline-3, 6, 12-triyl) tri (N, N-diphenyl aniline) (3, 6, 12-tritA-BPQ). The compound provided by the invention has ultrahigh horizontal dipole orientation and good thermal stability, is a typical Thermally Activated Delayed Fluorescence (TADF) material, has few synthesis and preparation steps, easily obtained raw materials, simple synthesis and purification process and high yield, and can be synthesized and prepared on a large scale.
Description
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to an orange red photo-thermal activation delayed fluorescent material which can be industrialized and has high efficiency and an electroluminescent device thereof.
Background
Although second generation phosphorescent materials can utilize both singlet and triplet radiative transitions, the highest IQE can be as high as 100%; however, the phosphorescent material requires the use of expensive heavy metals such as Ir, pt or Os to form a complex, thereby greatly increasing the manufacturing cost of the OLED device. The third generation of OLED luminescent material, thermal Activation Delayed Fluorescence (TADF), has three-linear excitons that can reach the singlet state through the triplet-singlet state reverse system cross-over (RISC) process, thereby reaching 100% of IQE, and simultaneously taking into account the advantages of high efficiency and low cost, and becoming the mainstream direction of the current organic luminescent material research.
At present, the development of blue and green TADF materials is rapid and the device efficiency is high, but the development of red TADF materials is far behind. The efficiency of red TADF materials is limited by the law of energy gap. Longer wavelengths mean from T 1 State to ground state (S) 0 ) Is narrow, the non-radiative decay process is significantly enhanced. Therefore, the high-efficiency red light material becomes a key problem to be solved urgently in the field of the OLED.
Disclosure of Invention
The invention discloses two efficient orange red thermal activation delayed fluorescent materials and a preparation method thereof, wherein the chemical names of the thermal activation delayed fluorescent materials are 4, 4'' - (dibenzo [ f, h ] pyrido [2,3-b ] quinoxaline-3, 6, 11-triyl) tri (N, N-diphenyl aniline) (3, 6, 11-tritA-BPQ) and 4, 4'' - (dibenzo [ f, h ] pyrido [2,3-b ] quinoxaline-3, 6, 12-triyl) tri (N, N-diphenyl aniline) (3, 6, 12-tritA-BPQ), and the problems that the conventional TADF material has multiple synthesis and preparation steps, expensive raw materials, complex synthesis and purification processes, low yield and difficult large-scale mass production are solved.
The invention adopts the following technical scheme:
an orange red thermal activation delayed fluorescence material is 3,6, 11-tritA-BPQ or 3,6, 12-tritA-BPQ; the chemical structural formula is as follows:
the preparation method of the thermal activation delayed fluorescence material comprises the following steps: 3, 6-dibromophenanthrenequinone and 6-bromopyridine-2, 3-diamine (or 5-bromopyridine-2, 3-diamine) are used as raw materials to react to prepare an intermediate 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline (or 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline) of a target material; the mol ratio of the 3, 6-dibromo phenanthrenequinone to the 6-bromopyridine-2, 3-diamine is 1: 1.1-1.2; the mol ratio of the 3, 6-dibromo phenanthrenequinone to the 5-bromopyridine-2, 3-diamine is 1: 1.1-1.2; the reaction is carried out in ethanol under the protection of nitrogen, the reaction temperature is 80-100 ℃, and the reaction time is 6-8 h. The reaction can be referred to as follows:
further, the mol ratio of 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline (or 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline) to 4- (diphenylamino) phenylboronic acid is 1: 3.3-3.6; the reaction is carried out under the protection of nitrogen, the reaction temperature is 90-100 ℃, and the reaction time is 36-48 h. After the reaction is finished, extracting reaction liquid, then combining organic phases, performing suction filtration, and performing column chromatography separation and purification to obtain the thermally activated delayed fluorescence materials 3,6, 11-trita-BPQ and 3,6, 12-trita-BPQ; preferably, the extraction solvent may be dichloromethane or trichloromethane. The reaction can be referred to as follows:
the invention discloses application of the thermal activation delayed fluorescence material in preparation of an organic electroluminescent device or in preparation of a light-emitting layer of the organic electroluminescent device. The thermal activation delayed fluorescence material is used as a guest material and doped with a host material to be used as a light emitting layer. Preferably, the orange-red thermally-activated delayed fluorescence materials 3,6, 11-trita-BPQ and 3,6, 12-trita-BPQ have doping concentrations of 7 to 13wt% and 5 to 10wt%, respectively.
The invention has the following beneficial effects:
1. the 3,6, 11-tritA-BPQ and 3,6, 12-tritA-BPQ thermal activation delayed fluorescence materials provided by the invention have high-level dipole factors of not less than 90%, thermal Activation Delayed Fluorescence (TADF) property, high fluorescence quantum yield (PLQY) of 100% and good stability.
2. The thermal activation delayed fluorescence material provided by the invention has the advantages of few synthesis and preparation steps, cheap and easily-obtained raw materials, simple synthesis and purification process, high yield and large-scale synthesis and preparation. The organic electroluminescent device based on the organic electroluminescent material has great application prospect and economic value in the fields of illumination, flat panel display and the like.
Drawings
FIG. 1 is a schematic reaction diagram of 3,6,11-tritA-BPQ and 3,6,12-tritA-BPQ.
FIG. 2 is a nuclear magnetic hydrogen spectrum (400 MHz, CDCl) of the compound 3,6, 11-tritA-BPQ prepared in example 1 3 )。
FIG. 3 is a nuclear magnetic carbon spectrum (101 MHz, CDCl) of the compound 3,6, 11-tritAP-BPQ prepared in example 1 3 )。
FIG. 4 is a mass spectrum of compound 3,6, 11-tritA-BPQ prepared in example 1.
FIG. 5 is a nuclear magnetic hydrogen spectrum (400 MHz, CDCl) of the compound 3,6, 12-tritA-BPQ prepared in example 1 3 )。
FIG. 6 is the nuclear magnetic carbon spectrum (101 MHz, CDCl) of compound 3,6, 12-tritAP-BPQ prepared in example 1 3 )。
FIG. 7 is a mass spectrum of compound 3,6, 12-tritA-BPQ prepared in example 1.
FIG. 8 is a graph showing the results of the efficiencies of the 3,6,11-tritA-BPQ device and the 3,6,12-tritA-BPQ device.
Detailed Description
The raw materials involved in the invention are conventional commercial products, and the specific operation method and the test method are conventional in the field. For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the descriptions are intended to further illustrate the features and advantages of the invention and are not intended to limit the scope of the claims which follow
The invention provides two high-efficiency orange-red thermally-activated delayed fluorescence materials, namely 3,6, 11-tritA-BPQ and 3,6, 12-tritA-BPQ. The preparation method can comprise the following steps:
(1) 3, 6-dibromophenanthrenequinone and 6-bromopyridine-2, 3-diamine (or 5-bromopyridine-2, 3-diamine) are used as raw materials to react to prepare an intermediate of a target material;
(2) Reacting the 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline (or 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline) obtained in the step (1) with 4- (diphenylamino) phenylboronic acid to obtain the target products 3,6, 11-tritA-BPQ and 3,6, 12-tritA-BPQ.
FIG. 1 is a schematic diagram of the above reaction.
The organic electroluminescent device based on the thermal activation delayed fluorescence material disclosed by the invention is characterized in that Indium Tin Oxide (ITO) is used as an anode, and the thickness of the double-pyrazino [2,3-f:2',3' -h ] quinoxaline-2, 3,6,7,10, 11-Hexanenitrile (HATCN) as Hole Injection Layer (HIL), 4'- (cyclohexane-1, 1-diyl) bis (N, N-di-p-Tolylaniline) (TAPC) as Hole Transport Layer (HTL), triphenylamine compound 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA) as Exciton Blocking Layer (EBL), said thermally activated delayed fluorescent material as guest material doped with 4, 4'-N, N' -dicarbazolylbiphenyl (CBP) host material jointly as light emitting layer (EML), 4, 6-bis (3, 5-bis (3-pyridin) ylphenyl) -2-methylpyrimidine (B3 PYMPM) as Electron Transport Layer (ETL), lithium fluoride (LiF) as Electron Injection Layer (EIL), aluminium (Al) as cathode; further, the specifications of each layer of the organic electroluminescent device are as follows: ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (10 nm)/CBP TADF material (X wt%) (20 nm)/B3 PYMPM (45 nm)/LiF (1 nm)/Al (100 nm).
Example 1
3,6,11-trita-BPQ: a mixture of 3, 6-dibromophenanthrenequinone (0.80 g, 2.18 mmol) and 6-bromopyridine-2, 3-diamine (0.45 g, 2.40 mmol) was dissolved in 50 mL of ethanol. The mixed solution is at 90 ℃ and N 2 Reflux under atmosphere for 6 hours. The precipitate was collected by filtration and washed with ethanol to give purified 3,6,11-triBr-BPQ (1.03 g, 1.99 mmol) without further purification. The yield was 91%. 3,6,11-triBr-BPQ (1.00 g, 1.93 mmol), (4 (diphenylamine) phenyl) boronic acid (1.84 g, 6.26 mmol), K 2 CO 3 (0.79 g, 5.75 mmol) was added to 60 mL1, 4-dioxane and water (10/1, v/v). Then, pd (PPh) was added in a nitrogen atmosphere 3 ) 4 (67 mg, 0.058 mmol), after heating at 90 ℃ for 48 h, the reaction mixture was cooled to room temperature. This was poured into 100 mL of water and extracted with Dichloromethane (DCM). The resulting layer was evaporated under reduced pressure and purified by column chromatography using DCM as eluent to give 3,6, 11-tritA-BPQ as an orange solid (1.46 g, 1.39 mmol). The yield was 70%.
3,6,12-triTPA-BPQ: the same procedure as for the preparation of 3,6,11-tritA-BPQ was followed except that 5-bromopyridine-2, 3-diamine (0.45 g, 2.40 mmol) was used instead of 6-bromopyridine-2, 3-diamine to give 3,6,12-tritA-BPQ, which was then reacted to give 3,6,12-tritA-BPQ as an orange solid (1.53 g, 1.51 mmol). The yield was 77%.
FIG. 2 is a nuclear magnetic hydrogen spectrum of Compound 3,6, 11-tritA-BPQ obtained as described above; FIG. 3 is a nuclear magnetic carbon spectrum of Compound 3,6, 11-tritA-BPQ obtained as described above; FIG. 4 is a mass spectrum of compound 3,6, 11-tritA-BPQ obtained above. FIG. 5 is a nuclear magnetic hydrogen spectrum of Compound 3,6, 12-tritA-BPQ obtained as described above; FIG. 6 is a nuclear magnetic carbon spectrum of Compound 3,6, 12-tritA-BPQ obtained as described above; FIG. 7 is a mass spectrum of compound 3,6, 12-tritA-BPQ obtained above.
From the above results, it was found that the structures of the compounds 3,6, 11-tritA-BPQ and 3,6, 12-tritA-BPQ were correct. The physical properties of the two compounds are shown in table 1.
The effect of the compound synthesized by the present invention as a material for a light emitting layer in a device is illustrated by the following application examples.
Application examples
The invention relates to a specific preparation process of an organic electroluminescent device based on a thermal activation delayed fluorescent material and the prior art of materials of each layer, such as vacuum evaporation, wherein the vacuum degree is less than or equal to 2 multiplied by 10 -4 Pa, a deposition rate of the functional layer of 2A/s, a deposition rate of the host material of 1A/s, a deposition rate of the LiF layer of 0.1A/s, a deposition rate of Al of 8A/s. Creation of the inventionThe method is characterized in that a novel thermal activation delayed fluorescence material with a non-doping property is provided, and a doped host material or a non-doped material is independently used as a light emitting layer of the organic electroluminescent device.
Taking 3,6, 11-trita-BPQ with a doping concentration of 10wt% as an example of the fabrication of an organic electroluminescent device having a light-emitting layer, the following steps were performed:
(1) Pretreatment of the glass anode: selecting a glass substrate (3 multiplied by 3 mm) with an Indium Tin Oxide (ITO) film as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) Vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10 -4 Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (60 nm)/TCTA (10 nm)/CBP: 10wt% by weight 3,6, 11-tritA-BPQ (20 nm)/B3 PYMPM (45 nm)/LiF (1 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) Packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
And changing the doping concentration or the doping compound to obtain the organic electroluminescent device.
The current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed.
The device performance is shown in figure 8.
There is no particular limitation on the preparation method of the organic electroluminescent device formed based on the thermally activated delayed fluorescence material according to the present invention and other raw materials. The organic film formed by the invention has high surface smoothness, stable chemical and physical properties, high luminous efficiency and low concentration quenching property, and the formed organic electroluminescent device has excellent performance. The OLED device based on the thermal activation delayed fluorescence material has the advantages of low driving voltage, high luminous brightness and high luminous stability, and the external quantum efficiency EQE of the doped device respectively reaches 32.0 percent and 19.9 percent.
Claims (10)
1. An orange-red thermally-activated delayed fluorescent material, which is characterized in that: the chemical structural formula of the orange-red thermal activation delayed fluorescence material is one of the following formulas:
2. the method for preparing a thermally activated delayed fluorescence material of claim 1, comprising the steps of: 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline or 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline and 4- (diphenylamino) phenylboronic acid are used as raw materials to react to prepare the orange-red thermally-activated delayed fluorescence material.
3. The method for preparing a thermally activated delayed fluorescence material according to claim 2, wherein 3, 6-dibromophenanthrenequinone and 6-bromopyridine-2, 3-diamine are used as raw materials to react to prepare 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline; 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline is prepared by reacting 3, 6-dibromophenanthrenequinone and 5-bromopyridine-2, 3-diamine as raw materials.
4. The method for preparing a thermally activated delayed fluorescence material according to claim 3, wherein the molar ratio of 3, 6-dibromophenanthrenequinone to 6-bromopyridine-2, 3-diamine is 1: 1.1 to 1.2; the mol ratio of the 3, 6-dibromo phenanthrenequinone to the 5-bromopyridine-2, 3-diamine is 1: 1.1-1.2.
5. The method for preparing a thermally activated delayed fluorescence material according to claim 3, wherein the reaction is carried out in ethanol under the protection of nitrogen, the reaction temperature is 80-100 ℃, and the reaction time is 6-8 h.
6. The method for preparing a thermally activated delayed fluorescence material according to claim 2, wherein the molar ratio of 3,6, 11-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline to 4- (diphenylamino) phenylboronic acid is 1: 3.3 to 3.6; the mol ratio of 3,6, 12-tribromodibenzo [ f, h ] pyrido [2,3-b ] quinoxaline to 4- (diphenylamino) phenylboronic acid is 1: 3.3-3.6.
7. The method for preparing a thermally activated delayed fluorescence material according to claim 2, wherein the reaction is performed under the protection of nitrogen, the reaction temperature is 90-100 ℃, and the reaction time is 36-48 h.
8. Use of a thermally activated delayed fluorescence material as claimed in claim 1 for the preparation of an organic electroluminescent device.
9. Use of the thermally activated delayed fluorescence material of claim 1 in the preparation of a light emitting layer of an organic electroluminescent device.
10. The use according to claim 9, wherein the thermally activated delayed fluorescence material is doped as a guest material with a host material as a light emitting layer.
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| CN113173927A (en) * | 2021-05-13 | 2021-07-27 | 南昌万季科技有限公司 | Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof |
| CN114649489A (en) * | 2022-03-01 | 2022-06-21 | 苏州大学 | Red light electroluminescent device based on double-pyridine phenazine thermal activation delayed fluorescent material |
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| CN113173927A (en) * | 2021-05-13 | 2021-07-27 | 南昌万季科技有限公司 | Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof |
| CN114649489A (en) * | 2022-03-01 | 2022-06-21 | 苏州大学 | Red light electroluminescent device based on double-pyridine phenazine thermal activation delayed fluorescent material |
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