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CN112279816B - Electron transport material and organic electroluminescent device using same - Google Patents

Electron transport material and organic electroluminescent device using same Download PDF

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CN112279816B
CN112279816B CN201910659857.7A CN201910659857A CN112279816B CN 112279816 B CN112279816 B CN 112279816B CN 201910659857 A CN201910659857 A CN 201910659857A CN 112279816 B CN112279816 B CN 112279816B
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room temperature
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钱超
许军
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Jiangsu Gaoguang New Materials Technology Co., Ltd.
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Nanjing Topto Materials Co Ltd
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Abstract

本发明公开了一种电子传输材料及使用该种材料的有机电致发光器件，其结构式如下所示：

Figure DDA0002138136220000011
本发明提供的电子传输材料的电子迁移率较高，电子很容易传输；而且电子亲和势很高，电子比较容易从阴极注入；化学稳定性高，与发光层的材料不会反应形成激基复合物；且具有较好的溶解性、成膜性和薄膜形态稳定性，含氮的芳香杂环与萘的共同存在可有效地保持该类材料较高电子传输材料的三线态能级以阻挡三线态激子迁移到电子传输层中，器件实验表明，使用本发明电子传输材料的有机电致发光器件电子传输速率高，电子传输性能好，发光效率和发光寿命均有所提高，而且驱动电压降低。

Figure 201910659857

The invention discloses an electron transport material and an organic electroluminescence device using the material, and its structural formula is as follows:

Figure DDA0002138136220000011
The electron transport material provided by the invention has high electron mobility, and electrons are easily transported; and the electron affinity is high, and electrons are relatively easy to inject from the cathode; and the chemical stability is high, and it will not react with the material of the light-emitting layer to form an excimer and has good solubility, film formation and film morphological stability, and the coexistence of nitrogen-containing aromatic heterocycles and naphthalene can effectively maintain the triplet energy level of such materials as high electron transport materials to block The triplet excitons migrate into the electron transport layer, and device experiments show that the organic electroluminescence device using the electron transport material of the present invention has high electron transport rate, good electron transport performance, improved luminous efficiency and luminous life, and the driving voltage reduce.

Figure 201910659857

Description

Electron transport material and organic electroluminescent device using same
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an electron transport material and an organic electroluminescent device using the same.
Background
With the development of science and technology, electronic display devices are indispensable tools in human daily life, and play a pivotal role in the interaction process between human beings and machines; meanwhile, with the emergence of new display technologies, the market of electronic display devices is developing at a speed which is far from masking. Conventional CRT displays are not only heavy but also bulky, which causes great inconvenience to users, and therefore, they have been gradually replaced by thin and light plasma Display panels (pdp) and liquid Crystal Display (lcd). Among the newly emerging flat panel display technologies, OLED (Organic Light Emitting Diode) is the new technology with the most market prospect. The electronic display device with the advantages of lightness, thinness, easy distortion, low power consumption and the like can be manufactured by utilizing the element and the technology, compared with the traditional electronic display device, the display has wide visual angle and short response time, overcomes the defect that the traditional electronic display device has image ghosting, and is a trend of the future development of the flat panel display.
The first article on OLEDs was published by Pope in 1963: when the Anthracene crystal is passed by a voltage of several hundred volts, the phenomenon of the Anthracene crystal emitting light can be clearly seen. However, the voltage used was high and the luminous efficiency was low, so that the research researchers did not pay attention at that time. With the continuous progress of the technology, c.w.tang et al of Kodak company in 1987 made a double-layer sandwich structure OLED device by using 8-hydroxyquinoline aluminum (AIq3) as a luminescent material and adopting a vacuum evaporation method, the lighting voltage was only a few volts, the brightness was as high as 1000cd/m2, marking that the OLED has a great step toward practical application, so that the OLED has strong commercial application potential, thereby attracting global attention, and the OLED has also become a research hotspot.
The balanced injection of carriers is a key factor for improving the luminous efficiency of the OLED element, and therefore, the problem of how to achieve the balanced injection of carriers in the device needs to be solved. However, many light-emitting materials have a relatively weak electron affinity, and thus, holes are used as main carriers in most cases. The method can be divided into the following steps according to different carriers: an electron-transporting material and a hole-transporting material,
the electron transport layer is an essential component of an organic electroluminescent device, and generally, electron transport materials all have a planar aromatic compound with a large conjugated structure, have good electron accepting capability, and can effectively transfer electrons under a certain forward bias. The currently available electron transport materials mainly include 8-hydroxyquinoline aluminum compounds, oxadiazole compounds, imidazole compounds, oxazole compounds, triazole compounds, nitrogen-containing six-membered heterocycles, perfluorinated electron transport materials, organosilicon electron transport materials and the like.
At present, in an organic electroluminescent device, a hole transmission speed is far greater than an electron transmission speed, the difference value of the hole transmission speed and the electron transmission speed is often up to an order of magnitude, and in order to ensure the balance of electrons and holes in the device, people often need to introduce a special hole blocking layer or require an electron transmission layer to have certain hole blocking capacity, so that the development of an electron transmission material with excellent performance has strong practical significance.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above technical problems, the present invention provides
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
an electron transport material having the structural formula:
Figure BDA0002138136200000021
wherein L is a single bond or phenylene;
x, Y, Z are each independently selected from C or N, and at least two of X, Y, Z are N;
r1 and R2 are respectively and independently selected from substituted or unsubstituted C6-C18 aromatic group and substituted or unsubstituted C6-C30 heteroaromatic group;
m is 0 or 1.
Further, R1 and R2 are independently selected from unsubstituted C6-C18 aryl, C1-C4 alkyl substituted C6-C18 aryl, trideuteromethyl substituted C6-C18 aryl, phenyl substituted C6-C18 aryl, unsubstituted C6-C30 heteroaryl, and phenyl substituted C6-C30 heteroaryl.
Further, R1, R2 are each independently selected from the group of the following structural formula:
Figure BDA0002138136200000022
Figure BDA0002138136200000031
further, the electron transport material is one of the compounds of the following structural formula:
Figure BDA0002138136200000032
Figure BDA0002138136200000041
Figure BDA0002138136200000051
Figure BDA0002138136200000061
Figure BDA0002138136200000071
Figure BDA0002138136200000081
Figure BDA0002138136200000091
Figure BDA0002138136200000101
the preparation method of the electron transport material comprises the following steps:
(1)
Figure BDA0002138136200000102
under the protection of inert gas, the general formula of the structure is
Figure BDA0002138136200000103
Dissolving the compound a in anhydrous tetrahydrofuran, cooling to below-78 deg.C, slowly dripping n-butyllithium in hexane solution, stirring for 20-50min, and adding
Figure BDA0002138136200000104
Adding the compound b into anhydrous tetrahydrofuran, dissolving, dripping into a reaction system, stirring for 20-50min after dripping is finished, slowly returning to room temperature for reaction for 8-15h, quenching the reaction after the reaction is finished, adding ethyl acetate, stirring for 20-50, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain a compound c;
(2)
Figure BDA0002138136200000105
adding magnesium and iodine into anhydrous tetrahydrofuran under the protection of inert gas, stirring at room temperature for 10-30min, heating to 50-60 deg.C, and stirring for 10-30min to obtain solution A with general structural formula R1-BrAdding the compound e into anhydrous tetrahydrofuran, stirring for dissolving, then dripping into the solution A, stirring for 1-3h after dripping, heating to reflux reaction, stirring for 2-4h, cooling to room temperature, then carrying out ice bath to obtain a solution B, and reacting the compound e with the structural formula
Figure BDA0002138136200000111
Compound d of (1) is added toStirring and dissolving in tetrahydrofuran water, then dripping into the solution B, stirring and reacting at room temperature for 5-10h after dripping is finished, dripping hydrochloric acid after the reaction is finished, stirring for 10-30min, adding toluene, continuing stirring for 10-30min, separating liquid, drying an organic phase, then concentrating under reduced pressure, and purifying by column chromatography to obtain a compound f;
(3)
Figure BDA0002138136200000112
adding magnesium and iodine into anhydrous tetrahydrofuran under the protection of inert gas, stirring at room temperature for 10-30min, heating to 50-60 deg.C, and stirring for 10-30min to obtain solution A with general structural formula R2Adding a compound g of-Br into anhydrous tetrahydrofuran, stirring and dissolving, then dripping into the solution A, stirring for 1-3h after dripping, heating to reflux reaction, stirring for 2-4h, cooling to room temperature, then carrying out ice bath to obtain a solution B, and adding a compound g of-Br into anhydrous tetrahydrofuran, wherein the structural formula is shown in the specification
Figure BDA0002138136200000113
Adding the compound f into anhydrous tetrahydrofuran, stirring for dissolving, then dripping into the solution B, stirring for reacting for 5-10h at room temperature after dripping, dripping hydrochloric acid after the reaction is finished, stirring for 10-30min, then adding toluene, continuing stirring for 10-30min, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain a compound h;
(4)
Figure BDA0002138136200000114
has a structural general formula of
Figure BDA0002138136200000115
Compound h of the general structural formula
Figure BDA0002138136200000116
Adding the compound c and sodium tetraborate into anhydrous tetrahydrofuran and water, stirring to dissolve, adding bis (triphenylphosphine) palladium (II) dichloride and hydrazine hydrate, and adding inert gasHeating to reflux under the protection of a body, stirring for reacting for 45-60h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain the electron transport material.
The use of the above electron transport material in the preparation of an organic electroluminescent device.
An organic electroluminescent device comprises a cathode, an electron injection layer, an electron transport layer, a luminescent layer, a hole transport layer, a hole injection layer and an anode which are sequentially arranged, wherein the electron transport layer contains at least one electron transport material.
Further, the electron transport layer contains one or two of the above electron transport materials.
An electronic display device comprising the above organic electroluminescent device.
An illumination apparatus comprising the above organic electroluminescent device.
The room temperature of the invention is 25 +/-5 ℃.
The invention has the beneficial effects that:
the electron transport material provided by the invention has the following two structural characteristics:
1. the structure II has the structural characteristics that the structure II has rich electron cloud density and good thermal stability due to the structural characteristics of six methyl groups and five-membered rings formed by the six methyl groups and naphthalene rings, the rich electron cloud density improves the carrier migration rate of material molecules, the LOMO energy level of the material molecules is greatly reduced, and the two characteristics determine that the material can be used as an electron transport material with excellent performance.
Figure BDA0002138136200000121
2. When X, Y, Z in the structure is one or more of nitrogen, the electron cloud density of the structure is greatly improved due to the redundant pair of lone pair electrons on the nitrogen atom, so that the material molecule taking the structure as a group has good carrier transmission performance, the introduction of the group increases the molecular weight of the material molecule, the Tg of the material molecule can be effectively improved, the crystallinity of the material molecule is reduced, and the structure II are combined for use, so that a good multiplication effect can be achieved.
Figure BDA0002138136200000122
The device proves that the electron transport material provided by the invention has very high electron mobility and electron affinity and good thermal stability, and device experiments show that the luminous efficiency and the luminous service life of the organic electroluminescent device using the electron transport material are remarkably improved, and the driving voltage is greatly reduced.
Drawings
FIG. 1 is a graph showing the relationship between luminance and voltage according to application example 1, comparative example 1 and comparative example 2 of the present invention;
fig. 2 is a graph of the luminous lifetime of application example 1 of the present invention.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
Figure BDA0002138136200000131
the specific synthesis method of the electron transport material (1) is as follows:
(1)
Figure BDA0002138136200000132
under the protection of nitrogen, compound 1(10g, 330g/mol, 30.3mmol) is added into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 1) and stirred to dissolveCooling liquid nitrogen to-78 deg.C after decomposition, slowly dropping n-butyllithium (33.33mmol) in hexane (1.6M), stirring for 30min after dropping, adding compound 2(1.1eq, 6.2g, 186.14g/mol, 33.33mmol) into anhydrous tetrahydrofuran (62g, 10 times of compound 2 mass), stirring for dissolving, dropping into the reaction system, stirring for 30min after dropping, slowly returning to room temperature for reaction for 10h, quenching the reaction with saturated ammonium chloride solution (500g, 50 times of compound 1 mass), adding ethyl acetate (500g, 50 times of compound 1 mass), stirring for 20min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain compound 3(10.6g, yield 92.6%, MS (M), (EI) 378 (M)+))。
(2)
Figure BDA0002138136200000141
Adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 5(2.1eq, 205.97g/mol, 23.65g, 114.8mmol) into anhydrous tetrahydrofuran (236.5g, 10 times of the mass of compound 5), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, and purifying by column chromatography to obtain compound 6(10.07g, yield 50.2%, MS (EI): 367(M +)).
(3)
Figure BDA0002138136200000142
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 6(1eq, 9.71g, 367g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of the mass of compound 3) and water (30g, 3 times of the mass of compound 3), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (1) (11.18 g), yield 72.5%, ms (ei): 583(M +)).
Example 2:
Figure BDA0002138136200000151
the specific synthesis method of the electron transport material (2) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000152
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 5(2.1eq, 205.97g/mol, 23.65g, 114.8mmol) into anhydrous tetrahydrofuran (236.5g, 10 times of the mass of compound 5), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, cooling to ice bath to obtain solution B, adding compound 7(10g, 181.92g/mol, 57.97mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 8(10.88g, yield 51.3%, MS (EI): 366(M +)).
(3)
Figure BDA0002138136200000153
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 8(1eq, 9.68g, 366g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of compound 3 in mass) and water (30g, 3 times of compound 3 in mass), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (2) (11.07 g), yield 71.9%, ms (ei): 582(M +)).
Example 3:
Figure BDA0002138136200000161
the specific synthesis method of the electron transport material (3) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000162
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 9(2.1eq, 231.99g/mol, 26.63g, 114.8mmol) into anhydrous tetrahydrofuran (266.3g, 10 times of the mass of compound 9), stirring to dissolve, adding dropwise into solution A, stirring for 1h after dropwise addition, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, adding dropwise into solution B, stirring at room temperature for 5h after dropwise addition, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 10(11.57g, yield 50.5%, MS (EI): 419(M +)).
(3)
Figure BDA0002138136200000171
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 10(1eq, 11.09g, 419.12g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of the mass of compound 3) and water (30g, 3 times of the mass of compound 3), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing silica gel with sample, purifying by column chromatography to obtain electron transport material (3) (11.07 g), yield 71.9%, ms (ei): 582(M +)).
Example 4:
Figure BDA0002138136200000172
the specific synthesis method of the electron transport material (4) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000173
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 9(2.1eq, 231.99g/mol, 26.63g, 114.8mmol) into anhydrous tetrahydrofuran (266.3g, 10 times of the mass of compound 9), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, ice-cooling to obtain solution B, adding compound 7(10g, 181.92g/mol, 54.96mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h, stirring at room temperature for 10% hydrochloric acid, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 11(11.62g, yield 50.6%, MS (EI): 418(M +)).
(3)
Figure BDA0002138136200000181
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 11(1eq, 11.06g, 418g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of compound 3 in mass) and water (30g, 3 times of compound 3 in mass), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (4) (11.84 g), yield 70.6%, ms (ei): 634(M +)).
Example 5:
Figure BDA0002138136200000182
the specific synthesis method of the electron transport material (5) is as follows:
(1)
Figure BDA0002138136200000183
under the protection of nitrogen, adding compound 12(10g, 406g/mol, 24.6mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 12), stirring and dissolving, cooling liquid nitrogen to-78 ℃, slowly dropping n-butyllithium (33.33mmol) in hexane solution (1.6M), stirring for 30min after dropping, adding compound 2(1.1eq, 5.2g, 186.14g/mol, 28.0mmol) into anhydrous tetrahydrofuran (52g, 10 times of the mass of compound 2), stirring and dissolving, dropping into a reaction system, stirring for 30min after dropping, slowly returning to room temperature for reaction for 10h, quenching the reaction by saturated ammonium chloride solution (500g, 50 times of the mass of compound 12), adding ethyl acetate (500g, 50 times of the mass of compound 12), stirring for 20min, separating, drying an organic phase by anhydrous sodium sulfate, concentrating under reduced pressure, silica gel column chromatography purification to obtain compound 13(10.3g, yield 92.3%, MS (EI): 454 (M)+))。
(2)
Figure BDA0002138136200000191
Adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 5(2.1eq, 205.97g/mol, 23.65g, 114.8mmol) into anhydrous tetrahydrofuran (236.5g, 10 times of the mass of compound 5), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 6(10.29g, yield 51.3%, MS (EI): 367(M +)).
(3)
Figure BDA0002138136200000192
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 6(1eq, 8.09g, 367.09g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (5) (10.34 g), yield 71.2%, ms (ei): 659(M +)).
Example 6:
Figure BDA0002138136200000201
the specific synthesis method of the electron transport material (6) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000202
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 5(2.1eq, 205.97g/mol, 23.65g, 114.8mmol) into anhydrous tetrahydrofuran (236.5g, 10 times of the mass of compound 5), stirring to dissolve, adding dropwise into solution A, stirring for 1h after dropwise addition, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 7(10g, 181.92g/mol, 57.97mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, adding dropwise into solution B, stirring at room temperature for 5h after dropwise addition, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 8(10.78g, yield 50.8%, MS (EI): 366(M +)).
(3)
Figure BDA0002138136200000211
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 8(1eq, 8.06g, 366.09g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, separating, extracting, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain an electronic transmission material (6) (10.24 g), yield 70.5%, ms (ei): 658(M +)).
Example 7:
Figure BDA0002138136200000212
the specific synthesis method of the electron transport material (7) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000213
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 9(2.1eq, 231.99g/mol, 26.63g, 114.8mmol) into anhydrous tetrahydrofuran (266.3g, 10 times of the mass of compound 9), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, cooling to ice bath to obtain solution B, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 10(11.77g, yield 51.4%, MS (EI): 419(M +)).
(3)
Figure BDA0002138136200000221
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 10(1eq, 9.23g, 419.12g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (7) (11.15 g), yield 71.2%, ms (ei): 711(M +)).
Example 8:
Figure BDA0002138136200000222
the specific synthesis method of the electron transport material (8) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000223
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 9(2.1eq, 231.99g/mol, 26.63g, 114.8mmol) into anhydrous tetrahydrofuran (266.3g, 10 times of the mass of compound 9), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, ice-cooling to obtain solution B, adding compound 7(10g, 181.92g/mol, 54.96mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h, stirring at room temperature for 10% hydrochloric acid, stirring for 30min, adding toluene, stirring for 10min, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 11(11.53g, yield 50.2%, MS (EI): 418(M +)).
(3)
Figure BDA0002138136200000231
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 11(1eq, 9.21g, 418.12g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (7) (11.18 g), yield 71.5%, ms (ei): 710(M +)).
Example 9:
Figure BDA0002138136200000232
the specific synthesis method of the electron transport material (9) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000241
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 14(2.1eq, 245.97g/mol, 28.24g, 114.8mmol) into anhydrous tetrahydrofuran (282.4g, 10 times of the mass of compound 14), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, cooling to ice bath to obtain solution B, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 15(12.56g, yield 51.4%, MS (EI): 447(M +)).
(3)
Figure BDA0002138136200000242
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 15(1eq, 9.85g, 447g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times of the mass of compound 13) and water (30g, 3 times of the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (9) (11.85 g), yield 72.8%, ms (ei): 739(M +)).
Example 10:
Figure BDA0002138136200000251
the specific synthesis method of the electron transport material (10) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000252
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 16(2.1eq, 261.95g/mol, 30.23g, 115.4mmol) into anhydrous tetrahydrofuran (302.3g, 10 times of the mass of compound 16), stirring to dissolve, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 7(10g, 181.92g/mol, 54.96mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, dropping into solution B, stirring at room temperature for 5h after dropping, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 17(12.9g, yield 49.2%, MS (EI): 478(M +)).
(3)
Figure BDA0002138136200000253
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 17(1eq, 10.49g, 478g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (10) (12.77g, yield 75.4%, ms (ei): 770(M +)).
Example 11:
Figure BDA0002138136200000261
the specific synthesis method of the electron transport material (11) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000262
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 16(2.1eq, 261.95g/mol, 30.07g, 114.8mmol) into anhydrous tetrahydrofuran (300g, 10 times of the mass of compound 16), stirring to dissolve, adding dropwise into solution A, stirring for 1h after dropwise addition, heating to reflux reaction, stirring for 2h, cooling to room temperature, ice-cooling to obtain solution B, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), stirring to dissolve, adding dropwise into solution B, stirring at room temperature for 5h after dropwise addition, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, and purifying by column chromatography to obtain compound 18(12.9g, yield 49.6%, MS (EI): 479(M +)).
(3)
Figure BDA0002138136200000271
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 18(1eq, 12.67g, 479g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of compound 3 in mass) and water (30g, 3 times of compound 3 in mass), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (1) (14.12g, yield 76.8%, ms (ei): 695(M +)).
Example 12:
Figure BDA0002138136200000272
the specific synthesis method of the electron transport material (12) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000273
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 19(2.1eq, 245.97g/mol, 28.24g, 114.8mmol) into anhydrous tetrahydrofuran (282.4g, 10 times of the mass of compound 19), stirring to dissolve, adding dropwise into solution A, stirring for 1h after dropwise addition, heating to reflux reaction, stirring for 2h, cooling to room temperature, adding compound 7(10g, 181.92g/mol, 54.96mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, adding dropwise into solution B, stirring at room temperature after dropwise addition, stirring for 5h, hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, and purifying by column chromatography to obtain compound 20(12.9g, yield 52.9%, MS (EI): 446(M +)).
(3)
Figure BDA0002138136200000281
Adding compound 3(10g, 378g/mol, 26.46mmol), compound 20(1eq, 11.83g, 446g/mol, 26.46mmol), sodium tetraborate (1.5eq, 15.14g, 381.37g/mol, 39.69mmol) into THF (100g, 10 times of the mass of compound 3) and water (30g, 3 times of the mass of compound 3), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.37g, 701.9g/mol, 0.53mmol) and hydrazine hydrate (3% eq, 0.039g, 50.06g/mol, 0.79mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (12.99 g), yield 74.2%, ms (ei): 662(M +)).
Example 13:
Figure BDA0002138136200000282
the specific synthesis method of the electron transport material (26) is as follows:
step (1) is essentially the same as example 1, with the following remaining steps:
(2)
Figure BDA0002138136200000291
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 21(1eq, 302g/mol, 16.5g, 54.67mmol) into anhydrous tetrahydrofuran (165g, 10 times of the mass of compound 21), stirring for dissolving, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, cooling to obtain solution B in an ice bath, adding compound 4(10g, 182.92g/mol, 54.67mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 4), dropping into solution B after stirring for dissolving, stirring for 5h at room temperature after dropping, dropping hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, and purifying by column chromatography to obtain compound 22(8.55g, yield 46.4%, MS (EI): 371(M +)).
(3)
Figure BDA0002138136200000292
Adding magnesium (3.0eq, 1.57g, 24.3g/mol, 64.68mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (78.5g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 23(1eq, 155.96g/mol, 3.36g, 21.56mmol) into anhydrous tetrahydrofuran (33.6g, 10 times of the mass of compound 23), stirring for dissolving, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, cooling to obtain solution B, adding compound 22(8g, 371g/mol, 21.56mmol) into anhydrous tetrahydrofuran (80g, 10 times of the mass of compound 22), stirring for dissolving, dropping into solution B, stirring at room temperature for 5h, dropping hydrochloric acid with concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, and purifying by column chromatography to obtain compound 24(5.93g, yield 60.5%, MS (EI): 413(M +)).
(4)
Figure BDA0002138136200000301
Adding compound 3(5g, 378g/mol, 13.23mmol), compound 24(1eq, 5.46g, 413g/mol, 13.23mmol), sodium tetraborate (1.5eq, 7.57g, 381.37g/mol, 19.85mmol) into THF (50g, 10 times of compound 3 in mass) and water (15g, 3 times of compound 3 in mass), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.16g, 701.9g/mol, 0.27mmol) and hydrazine hydrate (3% eq, 0.0195g, 50.06g/mol, 0.395mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (26) (6.38g, yield 76.7%, ms (ei): 629(M +)).
Example 14:
Figure BDA0002138136200000302
the specific synthesis method of the electron transport material (28) is as follows:
the steps (1) and (2) are basically the same as the embodiment 13, and the rest steps are as follows:
(3)
Figure BDA0002138136200000303
adding magnesium (3.0eq, 1.57g, 24.3g/mol, 64.68mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (78.5g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 25(1eq, 173g/mol, 3.73g, 21.56mmol) into anhydrous tetrahydrofuran (37.3g, 10 times of the mass of compound 25), stirring for dissolving, dropping into solution A, stirring for 1h after dropping, heating to reflux reaction, stirring for 2h, cooling to room temperature, obtaining solution B, adding compound 22(8g, 371g/mol, 21.56mmol) into anhydrous tetrahydrofuran (80g, 10 times of the mass of compound 22), stirring for dissolving, dropping into solution B, stirring for 5h at room temperature after dropping, dropping hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 26(6.4g, yield 62.8%, MS (EI): 430(M +)).
(4)
Figure BDA0002138136200000311
Adding compound 3(5g, 378g/mol, 13.23mmol), compound 26(1eq, 5.69g, 430g/mol, 13.23mmol), sodium tetraborate (1.5eq, 7.57g, 381.37g/mol, 19.85mmol) into THF (50g, 10 times of compound 3 in mass) and water (15g, 3 times of compound 3 in mass), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.16g, 701.9g/mol, 0.27mmol) and hydrazine hydrate (3% eq, 0.0195g, 50.06g/mol, 0.395mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (28) (6.73g, yield 78.8%, ms (ei): 646(M +)).
Example 15:
Figure BDA0002138136200000312
the specific synthesis method of the electron transport material (97) is as follows:
step (1) is essentially the same as example 5, with the following remaining steps:
(2)
Figure BDA0002138136200000321
adding magnesium (3.0eq, 3.98g, 24.3g/mol, 164mmol) and iodine (catalytic amount) into anhydrous tetrahydrofuran (199g, 50 times of the mass of magnesium) under the protection of nitrogen, stirring at room temperature for 20min, heating to 55 ℃, stirring for 10min to obtain solution A, adding compound 23(2.1eq, 155.96g/mol, 17.9g, 114.8mmol) into anhydrous tetrahydrofuran (179g, 10 times of the mass of compound 23), stirring to dissolve, adding dropwise into solution A, stirring for 1h after dropwise addition, heating to reflux reaction, stirring for 2h, cooling to room temperature, ice-cooling to obtain solution B, adding compound 7(10g, 181.92g/mol, 54.96mmol) into anhydrous tetrahydrofuran (100g, 10 times of the mass of compound 7), stirring to dissolve, adding dropwise into solution B, stirring at room temperature for 5h after dropwise addition, adding hydrochloric acid with the concentration of 10%, stirring for 30min, adding toluene, stirring for 10min, separating, drying organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, stirring with silica gel, and purifying by column chromatography to obtain compound 20(8.5g, yield 58.5%, MS (EI): 266(M +)).
(3)
Figure BDA0002138136200000322
Adding compound 13(10g, 454g/mol, 22.03mmol), compound 27(1eq, 5.86g, 266g/mol, 22.03mmol), sodium tetraborate (1.5eq, 12.6g, 381.37g/mol, 33.05mmol) into THF (100g, 10 times the mass of compound 13) and water (30g, 3 times the mass of compound 13), stirring, mixing and dissolving, adding bis (triphenylphosphine) palladium (II) dichloride (2% eq, 0.31g, 701.9g/mol, 0.44mmol) and hydrazine hydrate (3% eq, 0.033g, 50.06g/mol, 0.66mmol), heating to reflux under nitrogen protection, stirring for reaction for 48h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting, separating, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, mixing with silica gel, purifying by column chromatography to obtain electron transport material (97) (9.12 g), yield 74.2%, ms (ei): 558(M +)).
The present invention will be described in detail below by way of examples and comparative examples. The following examples are given in the comparative examples only for illustrating the present invention, and the scope of the present invention is not limited to the following examples and comparative examples.
Application example 1:
the method comprises the steps of adopting ITO as a reflecting layer anode substrate material, performing surface treatment on the reflecting layer anode substrate material by N2 plasma or UV-Ozone, depositing HAT-CN with the thickness of 10 nanometers on a Hole Injection Layer (HIL), selectively using NPD to form a Hole Transport Layer (HTL) with the thickness of 120 nanometers on the Hole Injection Layer (HIL), forming 9,10-Bis (2-naphthyl) Antifhraces (ADN) of blue EML as a luminescent layer by vacuum evaporation on the Hole Transport Layer (HTL), forming 2,5,8,11-Tetra-Butyl-Perilene (t-Bu-Perylene) as a dopant material, doping the luminescent layer with the thickness of 25 nanometers of about 5 percent, selecting the organic electroluminescent material 1 of the invention on the luminescent layer, doping according to the proportion of 1: LiQ 1:1, and forming an Electron Transport Layer (ETL) with the thickness of 35 nanometers by evaporation, then, evaporation is carried out on the electron transport layer by LiQ with the thickness of 2 nanometers to form an Electron Injection Layer (EIL), magnesium (Mg) and silver (Ag) are mixed in a ratio of 9:1 at a cathode and evaporation is carried out on the mixture with the thickness of 15 nanometers, and N4, N4 '-BIS [4-BIS (3-methylphenyl) Amino phenyl) ] -N4, N4' -Diphenyl- [1,1 '-Biphenyl ] -4, 4' -diamin (DNTPD) with the thickness of 65 nanometers is deposited on the cathode sealing layer.
Further, the surface of the cathode is sealed with a UV hardening adhesive and a sealing film (seal cap) containing a moisture remover to protect the organic electroluminescent device from atmospheric oxygen or moisture, so that the organic electroluminescent device is prepared.
Figure BDA0002138136200000331
Figure BDA0002138136200000341
Application examples 2 to 15
The electron transport materials (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (26), (28) and (97) in examples 2 to 15 of the present invention were used as Electron Transport Layers (ETLs), and the other parts were identical to those in application example 1, thereby producing organic electroluminescent devices of application examples 2 to 15.
Comparative examples 1 and 2
The organic electroluminescent devices of comparative examples 1 and 2 were fabricated in the same manner as in application example 1 except that PBD and p-EtAZ were used as the Electron Transport Layer (ETL), respectively, in application example 1.
The characteristics of the organic electroluminescent element manufactured in the above application example and the organic electroluminescent element manufactured in the comparative example were that the current density was 10mA/cm2The results of measurements under the conditions of (1) are shown in Table 1.
Table 1 device performance test results for different experimental groups:
Figure BDA0002138136200000342
as can be seen from the experimental comparison data in table 1 above, in the application examples 1 to 15 of the organic electroluminescent device prepared by using the electron transport material of the present invention as the electron transport layer, compared with the comparative examples 1 and 2, the voltage is reduced to a certain extent, the light emitting efficiency is improved by more than 90%, and the blue color saturation of the OLED device is improved to a certain extent.

Claims (9)

1. An electron transport material having a structural formula as shown below:
Figure FDA0003585734810000011
wherein L is a single bond or phenylene;
x, Y, Z are each independently selected from CH or N, and at least two of X, Y, Z are N;
r1 and R2 are respectively and independently selected from unsubstituted C6-C18 aryl, C1-C4 alkyl substituted C6-C18 aryl, trideuteromethyl substituted C6-C18 aryl, phenyl substituted C6-C18 aryl, unsubstituted C6-C30 heteroaryl, and phenyl substituted C6-C30 heteroaryl;
m is 0 or 1.
2. An electron transport material having a structural formula as shown below:
Figure FDA0003585734810000012
wherein L is a single bond or phenylene;
x, Y, Z are each independently selected from CH or N, and at least two of X, Y, Z are N;
m is 0 or 1;
r1, R2 are each independently selected from the group of the following structural formula:
Figure FDA0003585734810000013
Figure FDA0003585734810000021
3. an electron transport material, wherein the electron transport material is one of the compounds of the following structural formula:
Figure FDA0003585734810000022
Figure FDA0003585734810000031
Figure FDA0003585734810000041
Figure FDA0003585734810000051
Figure FDA0003585734810000061
Figure FDA0003585734810000071
Figure FDA0003585734810000081
4. a method for preparing an electron transport material according to any of claims 1 to 3, comprising the steps of:
(1)
Figure FDA0003585734810000091
under the protection of inert gas, the general formula of the structure is
Figure FDA0003585734810000092
Dissolving the compound a in anhydrous tetrahydrofuran, cooling to below-78 deg.C, slowly dripping n-butyllithium in hexane solution, stirring for 20-50min, and adding
Figure FDA0003585734810000093
Adding the compound b into anhydrous tetrahydrofuran, dissolving, dripping into a reaction system, stirring for 20-50min after dripping is finished, slowly returning to room temperature for reaction for 8-15h, quenching the reaction after the reaction is finished, adding ethyl acetate, stirring for 20-50, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain a compound c;
(2)
Figure FDA0003585734810000094
adding magnesium and iodine into anhydrous tetrahydrofuran under the protection of inert gas, stirring at room temperature for 10-30min, heating to 50-60 deg.C, and stirring for 10-30min to obtain solution A with general structural formula R1Compound e of-Br is added to anhydrous tetrahydrofuran,stirring for dissolving, dripping into the solution A, stirring for 1-3h, heating to reflux reaction, stirring for 2-4h, cooling to room temperature, and ice-bath to obtain solution B
Figure FDA0003585734810000095
Adding the compound d into anhydrous tetrahydrofuran, stirring for dissolving, then dripping into the solution B, stirring for reacting for 5-10h at room temperature after dripping, dripping hydrochloric acid after the reaction is finished, stirring for 10-30min, then adding toluene, continuing stirring for 10-30min, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain a compound f;
(3)
Figure FDA0003585734810000101
adding magnesium and iodine into anhydrous tetrahydrofuran under the protection of inert gas, stirring at room temperature for 10-30min, heating to 50-60 deg.C, and stirring for 10-30min to obtain solution A with general structural formula R2Adding a compound g of-Br into anhydrous tetrahydrofuran, stirring and dissolving, then dripping into the solution A, stirring for 1-3h after dripping, heating to reflux reaction, stirring for 2-4h, cooling to room temperature, then carrying out ice bath to obtain a solution B, and adding a compound g of-Br into anhydrous tetrahydrofuran, wherein the structural formula is shown in the specification
Figure FDA0003585734810000102
Adding the compound f into anhydrous tetrahydrofuran, stirring for dissolving, then dripping into the solution B, stirring for reacting for 5-10h at room temperature after dripping, dripping hydrochloric acid after the reaction is finished, stirring for 10-30min, then adding toluene, continuing stirring for 10-30min, separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain a compound h;
(4)
Figure FDA0003585734810000103
general formula of structure is
Figure FDA0003585734810000104
Compound h of the general structural formula
Figure FDA0003585734810000105
Adding the compound c and sodium tetraborate into anhydrous tetrahydrofuran and water, stirring and dissolving, then adding bis (triphenylphosphine) palladium (II) dichloride and hydrazine hydrate, heating to reflux under the protection of inert gas, stirring and reacting for 45-60h, cooling to room temperature, filtering, concentrating under reduced pressure to remove a certain amount of THF, adding ethyl acetate, extracting and separating liquid, drying an organic phase, concentrating under reduced pressure, and purifying by column chromatography to obtain the electronic transmission material.
5. Use of an electron transport material according to any of claims 1 to 3 for the preparation of an organic electroluminescent device.
6. An organic electroluminescent device comprising a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode, which are sequentially provided, wherein the electron transport layer contains at least one electron transport material according to any one of claims 1 to 3.
7. The organic electroluminescent device as claimed in claim 6, wherein the electron transport layer contains one or two electron transport materials as claimed in any one of claims 1 to 3.
8. An electronic display device comprising the organic electroluminescent device according to claim 6.
9. An illumination device characterized by comprising the organic electroluminescent device according to claim 6.
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