CN112645960B - Electron transport material, preparation method thereof and organic electroluminescent device - Google Patents

Electron transport material, preparation method thereof and organic electroluminescent device Download PDF

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CN112645960B
CN112645960B CN202011531769.8A CN202011531769A CN112645960B CN 112645960 B CN112645960 B CN 112645960B CN 202011531769 A CN202011531769 A CN 202011531769A CN 112645960 B CN112645960 B CN 112645960B
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transport material
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CN112645960A (en
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马晓宇
王进政
张鹤
贾宇
陈振生
徐佳楠
汪康
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses an electron transport material, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of chemistry and organic luminescent materials, wherein the general structural formula of the electron transport material is as follows:

Description

Electron transport material, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of chemical and organic luminescent materials, in particular to an electron transport material, a preparation method thereof and an organic electroluminescent device.
Background
With the rapid development of the electronic information industry, a hardware device for information display, namely a display, is used as an indispensable carrier for human-computer interaction, and plays a crucial role in the development process of the information display technology. Since 2000, OLED displays, which have been known as third generation display technologies, have received great attention in the industry because they have superior performance that is not comparable to other display technologies.
The key to realizing the industrialization of the OLED display is to prolong the service life of the OLED and improve the luminous efficiency. The efficiency and stability of the organic light emitting device are improved by forming a multi-layered structure formed of different materials on the organic material layer. The organic layer includes a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). A voltage is applied between the two electrodes, electrons are injected from the cathode and holes are injected from the anode, the injected electrons and holes are recombined in the light-emitting layer, and the electronic state is changed from the ground state to the excited state. Since the excited state is extremely unstable, the excited state returns to a stable ground state. At this point, energy is released, in the form of light.
With the increasing demand of the market for organic EL devices, devices having high efficiency and long life have become a trend. Therefore, the research on novel electron transport materials is very important.
Disclosure of Invention
An object of an embodiment of the present invention is to provide an electron transport material, so as to solve the problems mentioned in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an electron transport material, which has a structural general formula as formula I:
Figure BDA0002852296130000021
wherein m and n are independently 0 or 1, and are not 0 at the same time;
w, Q, Z is independently C or N, and at least one of the three is N;
x, Y independently O or S;
L1、L2independently at least one of a linkage, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3-to 10-membered) heteroaryl;
ring a is any one of substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 10-membered) heteroaryl, substituted or unsubstituted C3-C12 cycloalkyl;
Ar1、Ar2independently represent at least one of substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-to 20-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 10-membered) heteroaryl, substituted or unsubstituted (3-to 15-membered) heteroarylamino, substituted or unsubstituted (C6-C60) arylamino, substituted or unsubstituted C10-C24 fused ring, substituted or unsubstituted C10-C30 spiro ring.
Preferably, X, Y are both O.
Preferably, the heteroatom in the substituted or unsubstituted (3-to 20-membered) heterocycloalkyl group is at least one of O, N, S.
Preferably, the heteroatom of the substituted or unsubstituted (3-to 10-membered) heteroaryl is at least one of O, N, S.
Preferably, the heteroatom of the substituted or unsubstituted (3-to 15-membered) heteroarylamine group is at least one of O, N, S.
Preferably, the chemical structural formula of the electron transport material is any one of formula a 01-formula a 40:
Figure BDA0002852296130000031
Figure BDA0002852296130000041
Figure BDA0002852296130000051
。
in the present specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are connected, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
Heterocyclyl is meant to include both aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl and the like, and cyclic ethers/thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene and the like. In addition, the heterocyclic group may be optionally substituted.
Another objective of the embodiments of the present invention is to provide a method for preparing the above electron transport material, which includes the following steps:
under the protective atmosphere, dissolving a raw material A and a raw material B in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate 1;
under the protective atmosphere, dissolving the raw material C and the raw material D in a solvent, and adding palladium tetratriphenylphosphine and potassium carbonate for reaction to obtain an intermediate 2;
under the protection atmosphere, dissolving the intermediate 1 and the intermediate 2 in a dimethylformamide solution, then adding potassium phosphate, and then adding N, N' -bis (2-phenylphenyl) oxalic acid and cuprous iodide for reaction to obtain an intermediate 3;
under the protection atmosphere, dissolving the intermediate 3 in a tetrahydrofuran solution, then cooling, dropwise adding n-BuLi, dissolving the raw material E in the tetrahydrofuran solution, and dropwise adding the raw material E into the system to perform stirring reaction to obtain an intermediate 4;
under the protective atmosphere, mixing the intermediate 4 with glacial acetic acid, then dropwise adding concentrated sulfuric acid for stirring, then cooling, and adding a sodium bicarbonate solution to terminate the reaction, thereby obtaining the electron transport material;
the structural formula of the raw material A is shown as a formula A, the structural formula of the raw material B is shown as a formula B, the structural formula of the raw material C is shown as a formula C, the structural formula of the raw material D is shown as a formula D, and the structural formula of the raw material E is shown as a formula E:
Figure BDA0002852296130000071
preferably, the solvent is a mixed solution of toluene, ethanol and water.
Specifically, the synthetic route of the preparation method is as follows:
Figure BDA0002852296130000072
。
wherein Ar is1～Ar2、L1～L2X, W, Z, Y, Q, n, m, ring A are as defined above for formula I.
In addition, the preparation method can specifically comprise the following steps:
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, raw material A (1.0eq) and raw material B (1.0eq) were dissolved in toluol and water (V)tol:VToluene:VWater (W)Adding palladium tetratriphenylphosphine (0.01eq) and potassium carbonate (2.0eq) into the mixed solution of (3: 1:1), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 1;
step two: preparation of intermediate 2
Under the protection of nitrogen, raw material C (1.0eq) and raw material D (1.0eq) were dissolved in toluol and water (V)tol:VToluene:VWater (W)Adding palladium tetratriphenylphosphine (0.01eq) and potassium carbonate (2.0eq) into the mixed solution of (3: 1:1), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 2;
step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(1.0eq) and the intermediate 2(1.5eq) in an anhydrous DMF (0.4eq) solution, adding dry potassium phosphate (2.0eq), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.02eq) and cuprous iodide (CuI) (0.02eq), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, slowly dropping the solution into water after the solution is cooled to room temperature, stirring for 1 hour, standing the solution, precipitating out, filtering to obtain a solid, leaching with absolute ethyl alcohol and petroleum ether in sequence, and drying. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 3;
step four: preparation of intermediate 4
Adding the intermediate 3(1.0eq) into a three-neck flask under the protection of nitrogen, adding anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (1.2eq), and stirring for 2 hours at-78 ℃. Dissolving a raw material E (1.0eq) in a tetrahydrofuran solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying to prepare an intermediate 4;
step five: preparation of chemical formula 1
Adding the intermediate 4(1.0eq) into a three-neck flask, adding glacial acetic acid (10eq), heating to 120 ℃, adding concentrated sulfuric acid (0.1eq) dropwise, and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate solution until the solution becomes neutral, stopping the reaction, separating the solution, extracting the water phase with dichloromethane for three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the electron transport material shown in the chemical formula 1.
Another object of the embodiments of the present invention is to provide a use of the above electron transport material in the preparation of organic electroluminescent devices.
It is another object of the embodiments of the present invention to provide an organic electroluminescent device, which includes an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes the above-mentioned electron transport material.
Preferably, the organic layer includes an electron transport layer; the electron transport layer partially or completely contains the electron transport material.
Specifically, the organic material layer of the organic light emitting device of the present disclosure may be formed in a single layer structure, but may also be formed in a multilayer structure in which a layer and two or more organic material layers are present. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.
Among them, the anode preferably contains a material having a high work function. Such as Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO). Since the lifetime of the device of the invention is shortened in the presence of water and/or air, the device is suitably (depending on the application) structured, provided with contacts and finally sealed.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and has high hole mobility. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer. As the electron blocking layer, a material known in the art, for example, an arylamine-based organic material, may be used.
The material of the light emitting layer is a material capable of emitting visible light by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the received holes and electrons.
Preferably, the light emitting layer includes a host material and a dopant material; the host material partially or completely contains the electron transport material. The mass ratio of the host material to the doping material is (90-99.5) to (0.5-10).
The host material can adopt EMH-1; the doping material may include fluorescent doping and phosphorescent doping.
The phosphorescent dopant material is a phosphorescent material including a metal complex of iridium, platinum, or the like. For example, Ir (ppy)3Isogreen phosphorescent materials, FIrpic, FIr6Iso-blue phosphorescent material and Btp2Red phosphorescent materials such as ir (acac).
As the hole-blocking layer material, a compound having a hole-blocking effect known in the art, for example, a phenanthroline derivative such as Bathocuproine (BCP), an oxazole derivative, a triazole derivative, a triazine derivative, or the like can be used, but the invention is not limited thereto.
The electron injection layer may function to promote electron injection. Has the ability of transporting electrons and prevents excitons generated in the light emitting layer from migrating to the hole injection layer. The electron injecting material used in the present invention includes fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but is not limited thereto.
The cathode, generally preferably a material having a small work function, allows electrons to be smoothly injected into the organic material layer. Such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof.
In the embodiment of the present invention, the various functional layers described above may be formed by a solution coating method and a vacuum deposition method. The solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, etc., but is not limited thereto.
The organic electroluminescent device can be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), or the like, according to the same principle, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the electronic transmission material provided by the embodiment of the invention, the benzo-heterocycle rigid structure is introduced, so that the electronic transmission material has good film-forming property and thermal stability. The electron transport material provided by the invention has high electron injection and moving speed. Therefore, with the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the electron transport-type material of the present invention, the electron transport efficiency from the electron transport layer to the light emitting layer can be improved, so that the light emitting efficiency of the device can be improved, and the driving voltage of the device can be reduced, so that the durability of the resulting organic electroluminescent device can be enhanced.
Detailed Description
The following examples are provided to aid the understanding of the present invention and are not intended to limit the scope of the present invention. In addition, the preparation methods of the compounds which are not specifically listed in the embodiments of the present invention are methods generally applied in the related industries, and the methods described in the embodiments can be referred to when preparing other compounds.
Example 1
The embodiment provides an electron transport material, and the preparation method comprises the following steps:
Figure BDA0002852296130000121
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1(16.13g, the yield is 83.1%, and the MW: 388.28).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(11.56g, the yield is 92.1%, and the MW: 251.06).
Step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the intermediate 2(45mmol) in an anhydrous DMF (12mmol) solution, adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropwise adding the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(13.59g, the yield is 81.1%, and the MW: 558.41).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(11.33g, yield 78.9%, MW: 717.71).
Step five: preparation of formula A04
Adding intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid (150mmol), heating to 120 deg.C, adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the electron transport material shown as chemical formula A04 (7.71g, the yield is 73.5%, MW: 699.75).
Example 2
The embodiment provides an electron transport material, and the preparation method comprises the following steps:
Figure BDA0002852296130000141
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1(16.09g, the yield is 82.9%, and the MW: 388.25).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(11.63g, the yield is 93.0%, and the MW: 250.13).
Step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the intermediate 2(45mmol) in an anhydrous DMF (12mmol) solution, adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropwise adding the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(13.53g, the yield is 80.9%, and the MW: 557.43).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(11.95g, 77.9% yield, MW: 766.83).
Step five: preparation of formula A09
Adding intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid (150mmol), heating to 120 deg.C, adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the electron transport material shown as chemical formula A09 (8.07g, the yield is 71.8%, MW: 748.81).
Example 3
The embodiment provides an electron transport material, and the preparation method comprises the following steps:
Figure BDA0002852296130000171
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1(13.86g, the yield of 81.7 percent, MW: 339.23).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(11.62g, the yield is 92.9%, and the MW: 250.17).
Step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the intermediate 2(45mmol) in an anhydrous DMF (12mmol) solution, adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropwise adding the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(12.40g, the yield is 81.3%, and the MW: 508.45).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, the solution was then suction filtered hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(11.60g, 78.3% yield, MW: 740.85).
Step five: preparation of formula A16
Adding intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid (150mmol), heating to 120 deg.C, adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the electron transport material shown as chemical formula A16 (7.68g, the yield is 70.8%, MW: 722.83).
Example 4
The embodiment provides an electron transport material, and the preparation method comprises the following steps:
Figure BDA0002852296130000191
the method comprises the following steps: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50mmol) and a raw material B (55mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.55mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1(9.63g, the yield is 82.3%, and the MW: 234.13).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50mmol) and a raw material D (55mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetrakistriphenylphosphine palladium (0.5mmol) and potassium carbonate (100mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using 100mL of ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (3) completely dissolving the solid organic matter by using 30mL of dichloromethane, slowly dropwise adding the dichloromethane into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2(16.12g, the yield is 91.8%, and the MW: 351.23).
Step three: preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 1(30mmol) and the intermediate 2(45mmol) in an anhydrous DMF (12mmol) solution, adding dried potassium phosphate (60mmol), then adding N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6mmol) and cuprous iodide (CuI) (0.6mmol), stirring the mixture, heating to 90 ℃, refluxing for 24 hours, after the solution is cooled to room temperature, slowly dropwise adding the solution into water, stirring for 1 hour, standing the solution, precipitating, filtering to obtain a solid, leaching with 300mL of anhydrous ethanol and 200mL of petroleum ether in sequence, and drying. And (3) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 3(12.48g, the yield is 82.5%, and the MW: 504.38).
Step four: preparation of intermediate 4
Under nitrogen protection, intermediate 3(20mmol) was added to a three-necked flask, anhydrous tetrahydrofuran (85mL) was added, the reaction was then cooled to-78 deg.C, n-BuLi (24mmol) was added dropwise, and the mixture was stirred at-78 deg.C for 2 h. Dissolving the raw material E (20mmol) in a tetrahydrofuran (30mmol) solution, then dropwise adding the solution into the reaction system, heating to room temperature after dropwise adding, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, after which the solution was filtered with suction while hot to give a solid which was then rinsed with petroleum ether and dried to give intermediate 4(10.45g, 79.1% yield, MW: 660.74).
Step five: preparation of formula A28
Adding intermediate 4(15mmol) into a three-neck flask, adding glacial acetic acid (150mmol), heating to 120 deg.C, adding concentrated sulfuric acid (1.5mmol), and stirring for 5 min. Cooling to room temperature, adding a sodium bicarbonate (15mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, carrying out suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying to prepare the electron transport material shown as chemical formula A28 (6.92g, the yield is 71.8%, MW: 642.73).
Examples 5 to 9
Because the synthetic route and principle of the preparation method of other electron transport materials with the structural general formula of formula I in the disclosure are the same as those of the above-listed example 1, the raw materials are only required to be replaced by the raw materials corresponding to the target product, and the dosage of the raw materials is adjusted according to the corresponding stoichiometric ratio, so that the synthesis of the electron transport materials a01, a20, a30, a36 and a40 is completed in the examples of the present invention with reference to the preparation methods of examples 1 to 4, and the mass spectra, chemical formulas and yields are shown in table 1.
TABLE 1
Examples Electron transport material Molecular formula Calculated mass spectrum Mass spectrometric test values
Example 5 A01 C35H23N3O2 517.59 517.55
Example 6 A20 C47H29N3O2 667.77 667.71
Example 7 A30 C41H27N5O2 621.70 621.73
Example 8 A36 C47H31N3O2 669.78 669.71
Example 9 A40 C57H37N5O2 823.96 823.95
In addition, other compounds of the present application can be obtained by the preparation method according to the above-mentioned examples, and therefore, they are not illustrated herein.
Device example 1
The embodiment of the device provides an organic electroluminescent device, which has the following structure: the specific preparation method of the ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer comprises the following steps:
a. an ITO anode: coating with a thickness of
Figure BDA0002852296130000221
The ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, then repeatedly cleaned with distilled water for 2 times, and ultrasonically cleaned for 10 timesAnd (3) after washing is finished, sequentially washing with methanol, acetone and isopropanol by ultrasonic waves (5 min for each time), drying, transferring to a plasma cleaning machine for washing for 5min, conveying to an evaporation machine, and sequentially evaporating other functional layers on the substrate serving as an anode.
b. HIL (hole injection layer): the HAT-CN layer was deposited by evaporation to a thickness of 10nm to form a hole injection layer.
c. HTL (hole transport layer): a hole transport layer was formed by evaporation of TAPC 15 nm.
d. EmL (light-emitting layer): the host material EMH-1 and the doping material EMD-1 are mixed and evaporated by weight ratio of 97: 3 for 40nm to form a luminescent layer.
f. ETL (electron transport layer): the electron transport layer was formed by depositing 40nm of the electron transport material (i.e., compound a04) provided in example 1.
g. EIL (electron injection layer): and evaporating Yb to 1.0nm to form an electron injection layer.
h. Cathode: and (3) evaporating and plating magnesium and silver at 18nm in a weight ratio of 1:9 to obtain the organic electroluminescent device.
i. Light extraction layer: IDX001 was vacuum-deposited on the cathode to a thickness of 70nm as a light extraction layer.
Wherein, the chemical structural formula of the partial raw materials is as follows:
Figure BDA0002852296130000231
device example 2-device example 9
With reference to the production method provided in device example 1 above, the electron transport material (i.e., compound a04) used in device example 1 was replaced with compounds a01, a09, a16, a20, a28, a30, a36, and a40 provided in the above examples, respectively, as the materials of the electron transport layer, and the other methods and raw materials were the same, to produce corresponding organic electroluminescent devices.
Comparative device example 1
The device comparative example produced an organic electroluminescent device. Specifically, according to the preparation method of the device example 1, the electron transport material (i.e., compound a04) in the electron transport layer was replaced with the comparative compound Alq3 and vapor deposition was performed, and the other methods and raw materials were the same, to prepare an organic electroluminescent device. Wherein comparative compound Alq3 has the following structural formula:
Figure BDA0002852296130000232
the organic electroluminescent devices obtained in the above device examples 1 to 9 and device comparative example 1 were characterized at a luminance of 15000(nits) for driving voltage, luminous efficiency and lifetime, and the results are shown in the following table 2:
TABLE 2
Figure BDA0002852296130000241
As can be seen from the results in table 2 above, the organic electroluminescent device prepared by using the electron transport material provided by the present invention as an electron transport layer has a significantly reduced driving voltage, and significantly improved luminous efficiency and lifetime compared to the organic electroluminescent device prepared by using the existing Alq3 as an electron transport layer.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (3)

1. An electron transport material, wherein the chemical structural formula of the electron transport material is any one of formulas A01, A02, A03, A04, A05, A06, A07, A08, A09 and A10:
Figure FDA0003463294370000011
。
2. an organic electroluminescent device comprising an anode, a cathode and at least one organic layer disposed between said anode and said cathode, wherein said organic layer comprises the electron transport material of claim 1.
3. An organic electroluminescent device according to claim 2, wherein the organic layer comprises an electron injection layer and/or an electron transport layer; the electron injection layer and/or the electron transport layer partially or completely contain the electron transport material.
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