CN112812123B - Hole compound, preparation method thereof and organic electroluminescent device - Google Patents

Hole compound, preparation method thereof and organic electroluminescent device Download PDF

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CN112812123B
CN112812123B CN202011614819.9A CN202011614819A CN112812123B CN 112812123 B CN112812123 B CN 112812123B CN 202011614819 A CN202011614819 A CN 202011614819A CN 112812123 B CN112812123 B CN 112812123B
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CN112812123A (en
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王进政
张鹤
黄悦
张雪
汪康
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

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Abstract

The invention discloses a hole compound, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of chemistry and organic luminescent materials, wherein the hole compound has the following structural general formula:wherein X, Y is independently O, S, N-R 3 Any one of them; ring a is any one of a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (3-to 10-membered) heteroaryl group; l1, L2 are each independently at least one of a bond, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl. The hole injection layer and/or the hole transport layer of the organic electroluminescent device prepared by using the hole compound can improve the luminous efficiency of the device and reduce the driving voltage of the device, thereby enhancing the durability of the obtained organic electroluminescent device.

Description

Hole compound, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of chemistry and organic luminescent materials, in particular to a hole compound, a preparation method thereof and an organic electroluminescent device.
Background
An OLED is a hole and electron dual injection light emitting device that converts electrical energy directly into light energy of molecules of an organic semiconductor material. Compared with the traditional CRT, LCD, PDP display devices, the OLED has all the advantages of the existing display, has unique advantages, has high brightness, high contrast, high definition, wide viewing angle, wide color gamut and the like to realize high-quality images, and has the characteristics of ultra-thin, ultra-light, low driving voltage, low power consumption, wide temperature and the like to meet the requirements of portability, power saving and outdoor operation of portable equipment; the OLED display has the unique characteristics of self-luminescence, high luminous efficiency, short response time, transparency, flexibility and the like.
The study of hole-type materials is mainly focused on arylamine compounds. The arylamine compound has high hole mobility and is an ideal hole transport material. The focus of the research at present is mainly to improve the thermal stability of the compounds and the stability of the film form of the compounds. The commonly used small molecule hole materials mainly include 1, 1-bis [4- [ N, N-di (p-toluene) amino ] phenyl ] cyclohexane (TAPC), tris (4-carbazol-9-ylphenyl) amine (TcTa), N, N, N ', N ' -Tetraphenylbenzidine (TPB), N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (alpha-NPD), N, N ' -diphenyl-N, N ' - (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), and the like.
However, in organic electroluminescent devices using these materials, whether for fluorescent OLEDs or phosphorescent OLEDs, there is still a need for further improvements in terms of luminous efficiency, lifetime and operating voltage.
Disclosure of Invention
An objective of the embodiments of the present invention is to provide a hole compound, so as to solve the problems set forth in the background art.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
a cavity compound has a structural general formula as shown in formula I:
wherein m and n are natural numbers and are not zero at the same time; x, Y is independently O, S, N-R 3 Any one of them;
R 1 、R 2 、R 3 each independently is at least one of hydrogen, deuterium, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
ring a is any one of a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (3-to 10-membered) heteroaryl group;
l1, L2 are each independently at least one of a bond, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-to 30-membered heteroaryl;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each independently is a substituted or unsubstituted C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted 3-to 30-membered heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group, a substituted or unsubstituted 3-to 30-membered heteroarylamino group, a substituted or unsubstituted C6-C60 arylamino group, a C1-C30 alkoxy group, a C6-C60 aryloxy group, andadjacent substituents are joined to form at least one of a monocyclic or polycyclic C3-C30 aliphatic ring or a 3 to 30 membered aromatic ring.
Preferably, the carbon atom in the C3-C30 aliphatic or 3-to 30-membered aromatic ring, which is linked to an adjacent substituent to form a single ring or multiple rings, is replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur.
Preferably, X, Y is O.
Preferably, the heteroatoms in the heterocycloalkyl, heteroaryl, and heteroarylamine groups are independently at least one of oxygen, nitrogen, and sulfur.
Preferably, the chemical structural formula of the hole compound is any one of the formulas H01 to H48:
in the present specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron base; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkylamino group; a substituted or unsubstituted heterocyclylamino group; a substituted or unsubstituted arylamine group; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent connected by two or more substituents among the substituents shown above, or has no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl may be aryl, or may be interpreted as a substituent to which two phenyl groups are attached.
Heterocyclic groups are meant to include 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/sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.
Another object of the embodiment of the present invention is to provide a method for preparing the hole compound, which includes the following steps:
under the protective atmosphere, placing the raw material A and the raw material B in a solvent, and adding tetraphenylphosphine palladium and potassium carbonate for reaction to obtain an intermediate 1;
under the protective atmosphere, placing the raw materials C and D in a solvent, and adding tetraphenylphosphine palladium and potassium carbonate for reaction to obtain an intermediate 2;
under the protective atmosphere, placing the intermediate 1 and the intermediate 2 in Dimethylformamide (DMF), and adding potassium phosphate, N' -bis (2-phenyl) oxalic acid and cuprous iodide for reaction to obtain an intermediate 3;
under the protective atmosphere, dissolving the intermediate 3 in tetrahydrofuran solution, and then dropwise adding n-BuLi and the tetrahydrofuran solution of the raw material E for reaction to obtain an intermediate 4;
adding glacial acetic acid into the intermediate 4 in a protective atmosphere, dropwise adding concentrated sulfuric acid for reaction, and then adding sodium bicarbonate solution for terminating the reaction to obtain the cavity compound;
wherein, formula A of raw materials, formula B of raw materials, formula C of raw materials, formula D of raw materials, formula E of raw materials:
preferably, the solvent is a mixture of toluene, ethanol and water.
Specifically, the synthetic route of the preparation method is as follows:
the method specifically comprises the following steps:
step one: preparation of intermediate 1
Under the protection of nitrogen, the raw material A (1.0 eq) and the raw material B (1.0 eq) are dissolved in toluene ethanol and water (V tol :V Toluene (toluene) :V Water and its preparation method To the mixed solution of =3:1:1), tetrakis triphenylphosphine palladium (0.01 eq) and potassium carbonate (2.0 eq) were added, stirred well, warmed to 90 ℃ and refluxed for 5 hours, after the solution cooled to room temperature, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving solid organic matters by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matters into petroleum ether solution, uniformly stirring, precipitating, filtering to obtain solid, eluting the solid by using absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain an intermediate 1;
step two: preparation of intermediate 2
Under the protection of nitrogen, the raw material C (1.0 eq) and the raw material D (1.0 eq) are dissolved in toluene ethanol and water (V tol :V Toluene (toluene) :V Water and its preparation method To the mixed solution of =3:1:1), tetrakis triphenylphosphine palladium (0.01 eq) and potassium carbonate (2.0 eq) were added, stirred well, warmed to 90 ℃ and refluxed for 5 hours, after the solution cooled to room temperature, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving solid organic matters by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matters into petroleum ether solution, uniformly stirring, precipitating, filtering to obtain solid, eluting the solid by using absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain an intermediate 2;
step three: preparation of intermediate 3
Intermediate 1 (1.0 eq) and intermediate 2 (1.0 eq) were dissolved in anhydrous DMF (0.4 eq) solution under nitrogen protection, dried potassium phosphate (2.0 eq) was added followed by N, N' -bis (2-phenyl) oxalic acid (BPPO) (0.02 eq) and copper iodide (CuI) (0.02 eq) and the mixture was stirred, heated to 90 ℃, reacted for 24 hours under reflux, after the solution cooled to room temperature, the solution was slowly added dropwise to water and stirred for 1 hour, the solution was allowed to stand with precipitation, the solid was obtained by suction filtration, washed with 300mL of absolute ethanol, 200mL of petroleum ether in sequence, and dried. Completely dissolving solid organic matters by using a small amount of dichloromethane, slowly dripping the solution into petroleum ether solution, uniformly stirring, precipitating, filtering to obtain solid, eluting with 300mL of absolute ethyl alcohol and 200mL of petroleum ether in sequence, and drying to obtain an intermediate 3;
step four: preparation of intermediate 4
Under the protection of nitrogen, the intermediate 3 (1.0 eq) was added to a three-necked flask, anhydrous tetrahydrofuran was added, the reaction system was cooled to-78 ℃, n-BuLi (1.2 eq) was added dropwise, and the mixture was stirred at-78 ℃ for 2 hours. Raw material E (1.0 eq) was dissolved in tetrahydrofuran solution, then added dropwise to the above reaction system, and after the addition was completed, the temperature was raised to room temperature and stirred for 10 hours. Then, the reaction was quenched by adding a saturated ammonium chloride solution, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, and successively washed with water, saturated brine, and then dried over anhydrous magnesium sulfate. Then adding the dried solid into ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain solid, eluting with petroleum ether, and drying to obtain an intermediate 4;
step five: preparation of chemical formula 1
Intermediate 4 (1.0 eq) was added to a three-necked flask, glacial acetic acid (10 eq) was added, heated to 120 ℃, concentrated sulfuric acid (0.1 eq) was added dropwise, and stirred for 5min. Cooling to room temperature, adding sodium bicarbonate solution to terminate the reaction, separating, extracting the water phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing solvent by a rotary evaporator, adding solid organic matters into ethanol solution, heating to 80 ℃, stirring for 5 hours, filtering the solution to obtain solid after the solution is cooled to room temperature, eluting with petroleum ether, and drying to obtain the hole compound shown in the chemical formula 1.
Another object of the embodiment of the present invention is to provide an application of the hole compound in preparing an organic electroluminescent device.
Another object of the embodiments of the present invention is 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 hole compound.
Preferably, the organic layer includes a hole injection layer and/or a hole transport layer; the hole injection layer and/or the hole transport layer partially or completely contains the hole compound.
Specifically, the above-described organic material layer may be formed as a single-layer structure, but may also be formed as a multi-layer structure in which two or more organic material layers are laminated. For example, the organic layer 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 an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers or a greater number of organic material layers.
The type of the anode is not particularly limited, and is a conventional anode well known to those skilled in the art, and more preferably one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide. The thickness of the anode is preferablyThe kind of the cathode is not particularly limited, and may be a conventional cathode well known to those skilled in the art, and more preferably one of Al, li, na, K, mg, ca, au, ag, pb.
The thickness of the cathode is preferably
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprisesA host material and a dopant material; the host material may be 4,4'-N, N' -dicarbazole-biphenyl ("CBP"), or the like; the doping material may be Ir (ppy) 3 Iridium complexes.
The types of the respective functional layers are not particularly limited, and may be conventional functional layers well known to those skilled in the art. Preferably: the electron transport layer is one of Alq3, coumarin 6, triazole derivative, azole derivative, oxadiazole derivative, imidazole derivative, fluorenone derivative and anthrone derivative; the thickness of the electron transport layer is preferablyThe electron injection layer is LiF, csF, li 2 O、Al 2 O 3 One of MgO; the thickness of the electron injection layer is preferably 0.1 to 10nm.
In the embodiments of the present invention, the various functional layers described above may be formed by means of a solution coating method and a vacuum deposition method. The solution coating method means spin coating, dip coating, ink jet printing, screen printing, spray method, etc., but is not limited thereto.
The organic electroluminescent device described above may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoconductor (OPC), an Organic Thin Film Transistor (OTFT), or the like, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the hole compound provided by the embodiment of the invention, the benzo heterocycle rigid structure is introduced, so that the hole compound has good film forming property and thermal stability. In addition, the hole compound has high hole injection and movement rate; therefore, the hole injection layer and/or the hole transport layer of the organic electroluminescent device prepared by using the hole compound can improve the luminous efficiency of the device and reduce the driving voltage of the device, thereby enhancing the durability of the obtained organic electroluminescent device.
Detailed Description
The following examples of the invention are provided to aid understanding of the invention and are not intended to limit the scope of the invention. The methods for preparing the compounds not specifically shown in the examples of the present invention are methods commonly used in the related industries, and the methods described in the examples may be referred to in preparing other compounds.
Example 1
This example provides a hole compound, which is prepared as follows:
step one: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50 mmol) and a raw material B (55 mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetraphenylphosphine palladium (0.55 mmol) and potassium carbonate (100 mmol), stirring uniformly, heating to 90 ℃ and refluxing for 5 hours, keeping an organic phase after the solution is cooled to room temperature, and then extracting an aqueous phase with 100mL of ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organics were completely dissolved using 30mL of methylene chloride, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to give a solid, which was rinsed with 300mL of absolute ethanol, 200mL of petroleum ether, and dried to give intermediate 1 (16.65 g, yield 83.2%, MW: 400.31).
Step two: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50 mmol) and a raw material D (55 mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetraphenylphosphine palladium (0.5 mmol) and potassium carbonate (100 mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, keeping an organic phase after the solution is cooled to room temperature, and extracting an aqueous phase with 100mL of ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organics were completely dissolved using 30mL of methylene chloride, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to obtain a solid, which was rinsed with 300mL of absolute ethanol, 200mL of petroleum ether, and dried to obtain intermediate 2 (11.52 g, 92.5% yield, MW: 249.15).
Step three: preparation of intermediate 3
Intermediate 1 (30 mmol) and intermediate 2 (30 mmol) were dissolved in anhydrous DMF (12 mmol) under nitrogen protection, dried potassium phosphate (60 mmol) was added followed by N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6 mmol) and copper iodide (CuI) (0.6 mmol), the mixture was stirred, warmed to 90℃and reacted at reflux for 24 hours, after the solution cooled to room temperature, the solution was slowly added dropwise to water and stirred for 1 hour, the solution was allowed to stand with precipitation, the solid was obtained by suction filtration, and then rinsed with 300mL absolute ethanol, 200mL petroleum ether and dried. The solid organics were completely dissolved using a small amount of dichloromethane, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to give a solid, which was rinsed sequentially with 300mL absolute ethanol, 200mL petroleum ether, and dried to give intermediate 3 (13.90 g, 81.5% yield, MW: 568.53).
Step four: preparation of intermediate 4
Intermediate 3 (20 mmol) was added to a three-necked flask under nitrogen protection, anhydrous tetrahydrofuran (85 mL) was added, the reaction system was then cooled to-78deg.C, n-BuLi (24 mmol) was added dropwise, and stirring was carried out at-78deg.C for 2h. Raw material E (20 mmol) was dissolved in tetrahydrofuran (30 mmol) solution, then added dropwise to the reaction system, and after the addition was completed, the temperature was raised to room temperature and stirred for 10 hours. Then, the reaction was quenched by adding a saturated ammonium chloride solution, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, and successively washed with water, saturated brine, and then dried over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and heated to 80℃for 5 hours with stirring, after which the solution was filtered off with suction while hot to give a solid, which was rinsed with petroleum ether and dried to give intermediate 4 (10.48 g, 78.9% yield, MW: 663.85).
Step five: preparation of formula H01
Intermediate 4 (15 mmol) was added to a three-necked flask, glacial acetic acid was added, heated to 120 ℃, concentrated sulfuric acid (1.5 mmol) was added dropwise, and stirred for 5min. Cooling to room temperature, adding sodium bicarbonate (15 mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the solvent by a rotary evaporator, adding the solid organic matter into ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, filtering the solution to obtain solid, eluting with petroleum ether, and drying to obtain the hole compound (7.19 g, yield 74.2%, MW: 645.83) shown in the chemical formula H01.
Example 2
This example provides a hole compound, which is prepared as follows:
step one: preparation of intermediate 2
Under the protection of nitrogen, dissolving a raw material C (50 mmol) and a raw material D (55 mmol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetraphenylphosphine palladium (0.5 mmol) and potassium carbonate (100 mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, keeping an organic phase after the solution is cooled to room temperature, and extracting an aqueous phase with 100mL of ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organics were completely dissolved using 30mL of methylene chloride, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to obtain a solid, which was rinsed with 300mL of absolute ethanol, 200mL of petroleum ether, and dried to obtain intermediate 2 (23.58 g, yield 91.3%, MW: 516.45).
Step two: preparation of intermediate 3
Raw material 1 (35 mmol) and intermediate 2 (30 mmol) were dissolved in anhydrous DMF (12 mmol) under nitrogen protection, dried potassium phosphate (60 mmol) was added, then N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6 mmol) and copper iodide (CuI) (0.6 mmol) were added, the mixture was stirred, heated to 90℃and reacted at reflux for 24 hours, after the solution cooled to room temperature, the solution was slowly added dropwise to water and stirred for 1 hour, the solution was left to precipitate, a solid was obtained by suction filtration, and 300mL absolute ethanol, 200mL petroleum ether were sequentially rinsed and dried. The solid organics were completely dissolved using a small amount of dichloromethane, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to give a solid, which was rinsed sequentially with 300mL absolute ethanol, 200mL petroleum ether, and dried to give intermediate 3 (15.03 g, 82.3% yield, MW: 608.50).
Step three: preparation of intermediate 4
Intermediate 3 (20 mmol) was added to a three-necked flask under nitrogen protection, anhydrous tetrahydrofuran (85 mL) was added, the reaction system was then cooled to-78deg.C, n-BuLi (24 mmol) was added dropwise, and stirring was carried out at-78deg.C for 2h. Raw material E (20 mmol) was dissolved in tetrahydrofuran (30 mmol) solution, then added dropwise to the reaction system, and after the addition was completed, the temperature was raised to room temperature and stirred for 10 hours. Then, the reaction was quenched by adding a saturated ammonium chloride solution, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, and successively washed with water, saturated brine, and then dried over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and heated to 80℃for 5 hours with stirring, after which the solution was filtered off with suction while hot to give a solid, which was rinsed with petroleum ether and dried to give intermediate 4 (12.35 g, 79.4% yield, MW: 777.93).
Step four: preparation of formula H04
Intermediate 4 (15 mmol) was added to a three-necked flask, glacial acetic acid was added, heated to 120 ℃, concentrated sulfuric acid (1.5 mmol) was added dropwise, and stirred for 5min. Cooling to room temperature, adding sodium bicarbonate (15 mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the solvent by a rotary evaporator, adding the solid organic matter into ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, filtering the solution to obtain solid, eluting with petroleum ether, and drying to obtain the hole compound (8.41 g, yield 73.8%, MW: 759.96) shown in the chemical formula H04.
Example 3
This example provides a hole compound, which is prepared as follows:
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step one: preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (50 mmol) and a raw material B (55 mol) in a mixed solution of 150mL of toluene, 50mL of ethanol and 50mL of water, adding tetraphenylphosphine palladium (0.55 mmol) and potassium carbonate (100 mmol), stirring uniformly, heating to 90 ℃ and refluxing for 5 hours, keeping an organic phase after the solution is cooled to room temperature, and then extracting an aqueous phase with 100mL of ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organics were completely dissolved using 30mL of methylene chloride, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to give a solid, which was rinsed with 300mL of absolute ethanol, 200mL of petroleum ether, and dried to give intermediate 1 (16.53 g, 82.4% yield, MW: 401.33).
Step two: preparation of intermediate 3
Intermediate 1 (30 mmol) and raw material 2 (35 mmol) were dissolved in anhydrous DMF (12 mmol) under nitrogen protection, dried potassium phosphate (60 mmol) was added followed by N, N' -bis (2-phenylphenyl) oxalic acid (BPPO) (0.6 mmol) and copper iodide (CuI) (0.6 mmol), the mixture was stirred, warmed to 90℃and reacted at reflux for 24 hours, after the solution cooled to room temperature, the solution was slowly added dropwise to water and stirred for 1 hour, the solution was allowed to stand with precipitation, a solid was obtained by suction filtration, and then rinsed with 300mL absolute ethanol, 200mL petroleum ether and dried. The solid organics were completely dissolved using a small amount of dichloromethane, then slowly added dropwise to the petroleum ether solution, stirred well with precipitation, suction filtered to give a solid, which was rinsed with 300mL of absolute ethanol, 200mL of petroleum ether, and dried to give intermediate 3 (12.09 g, yield 81.7%, MW: 493.45).
Step four: preparation of intermediate 4
Intermediate 3 (20 mmol) was added to a three-necked flask under nitrogen protection, anhydrous tetrahydrofuran (85 mL) was added, the reaction system was then cooled to-78deg.C, n-BuLi (24 mmol) was added dropwise, and stirring was carried out at-78deg.C for 2h. Raw material E (20 mmol) was dissolved in tetrahydrofuran (30 mmol) solution, then added dropwise to the reaction system, and after the addition was completed, the temperature was raised to room temperature and stirred for 10 hours. Then, the reaction was quenched by adding a saturated ammonium chloride solution, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, and successively washed with water, saturated brine, and then dried over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and heated to 80℃for 5 hours with stirring, after which the solution was filtered off with suction while hot to give a solid, which was rinsed with petroleum ether and dried to give intermediate 4 (11.92 g, 77.9% yield, MW: 764.83).
Step five: preparation of formula H22
Intermediate 4 (15 mmol) was added to a three-necked flask, glacial acetic acid was added, heated to 120 ℃, concentrated sulfuric acid (1.5 mmol) was added dropwise, and stirred for 5min. Cooling to room temperature, adding sodium bicarbonate (15 mL) solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the solvent by a rotary evaporator, adding the solid organic matter into ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, filtering the solution to obtain solid, eluting with petroleum ether, and drying to obtain the hole compound (8.27 g, yield 73.8%, MW: 746.88) shown in the chemical formula H22.
Examples 4 to 8
The synthetic route and principle of the preparation method of other hole compounds with the structural general formula of the chemical formula I in the summary are the same as those of the above-listed examples 1-3, and the corresponding hole compounds can be obtained only by replacing raw materials with raw materials corresponding to the corresponding ligand structures in target products respectively and adjusting the material dosage according to the corresponding stoichiometric ratio, so that the synthesis of the hole compounds H18, H28, H35, H42 and H45 is completed by referring to the preparation methods of examples 1-3, and mass spectra and molecular formulas of the hole compounds are shown in table 1.
TABLE 1
Examples Compounds of formula (I) Molecular formula Theoretical mass spectrum value Mass spectrometry test values
Example 4 H18 C 41 H 33 NO 2 571.72 571.75
Example 5 H28 C 58 H 42 N 2 O 2 798.99 798.98
Example 6 H35 C 46 H 32 N 2 O 2 644.77 644.75
Example 7 H42 C 49 H 34 N 2 O 2 682.82 682.84
Example 8 H44 C 50 H 34 N 4 O 2 722.85 722.87
Device example 1
The embodiment of the device provides an organic electroluminescent device, and a specific preparation method thereof comprises the following steps:
first, ITO (anode) is deposited with N1- (naphthalene-2-yl) -N4, N4-bis (4- (naphthalene-2-yl (phenyl) amino) phenyl) -N1-phenyl-1, 4-diamine ("2-TNATA") 50nm thick, then the above hole compound H01 is deposited with a thickness of 40nm as a hole transport layer, a host material 4,4'-N, N' -dicarbazole-biphenyl ("CBP") and a dopant material tris (2-phenylpyridine) iridium ("Ir (ppy) 3 ") according to 95: the thickness of the mixed evaporation coating is 5 weight percent, the thickness of the mixed evaporation coating is 30nm, the thickness of the evaporation coating hole blocking layer ("BAlq") is 10nm, the thickness of the evaporation coating Alq3 is 35nm, the thickness of the evaporation coating electron injection layer LiF is 0.2nm, and the thickness of the evaporation coating cathode Al is 120nm, so that the organic electroluminescent device is formed.
Device example 2 to device example 8
Referring to the preparation method provided in the device example 1, the hole compound H01 used in the device example 1 is replaced by the hole compounds H04, H18, H22, H35, H42 and H44 provided in the above examples, respectively, as hole transport layer materials, so as to prepare the corresponding organic electroluminescent devices.
Device comparative example 1
The device comparative example an organic electroluminescent device was manufactured. Specifically, the hole compound H01 used in the device example 1 was replaced with the comparative compound NPB as a hole transport layer material, and a corresponding organic electroluminescent device was prepared. Wherein, the structural formula of NPB is as follows:
the organic electroluminescent devices obtained in the above device examples 1 to 8 and device comparative example 1 were characterized in terms of driving voltage, luminous efficiency and lifetime at 6000 (nits) luminance, and the characterization results are shown in table 2 below.
TABLE 2
The results in table 2 show that the hole compound provided by the invention can be applied to an organic electroluminescent device, and compared with the hole transport layer material NPB, the organic electroluminescent device containing the hole compound provided by the invention has lower starting voltage, and the luminous efficiency and the service life are obviously improved.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (3)

1. A hole compound, wherein the chemical structural formula of the hole compound is any one of the following structural formulas:
2. an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the hole compound of claim 1.
3. An organic electroluminescent device according to claim 2, wherein the organic layer comprises a hole injection layer and/or a hole transport layer; the hole injection layer and/or the hole transport layer partially or completely contains the hole compound.
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