CN115894491B - Electron transport material, preparation method thereof, light-emitting device and light-emitting device - Google Patents

Electron transport material, preparation method thereof, light-emitting device and light-emitting device Download PDF

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CN115894491B
CN115894491B CN202211484361.9A CN202211484361A CN115894491B CN 115894491 B CN115894491 B CN 115894491B CN 202211484361 A CN202211484361 A CN 202211484361A CN 115894491 B CN115894491 B CN 115894491B
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electron transport
toluene
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transport material
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CN115894491A (en
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汪康
孟范贵
魏威
李飞
陈振生
李金磊
华伟东
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The application is suitable for the technical field of materials, and provides an electron transport material, a preparation method thereof, a light emitting device and a light emitting device.

Description

Electron transport material, preparation method thereof, light-emitting device and light-emitting device
Technical Field
The application belongs to the technical field of materials, and particularly relates to an electron transport material, a preparation method thereof, a light-emitting device and a light-emitting device.
Background
Along with the rapid development of information technology, new targets and requirements are also put forward on the performance of an information display system, and a display has high brightness, high resolution, wide viewing angle and low energy consumption, so that the display becomes a research hot spot. The organic electroluminescence (OLED) display technology can meet the requirements of people, and has the advantages of wide working temperature, flexible display and the like. It has the following structure: an anode, a cathode, and an organic material layer interposed therebetween. In order to improve efficiency and stability of the organic electroluminescent element, the organic material layer generally includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In such an organic light emitting element, when a voltage is applied between an anode and a cathode, holes from the anode and electrons from the cathode are injected into an organic material layer, and generated excitons generate light having a specific wavelength when they migrate to a ground state.
The electron transport layer is a key component in the OLED structure and is responsible for adjusting the injection speed and injection quantity of electrons, and in order to improve the injection and transport of electrons, high-mobility electron injection and transport materials are needed. Electron transport materials are required to have a high glass transition temperature (Tg), and Bphen, TPBi, BCP, BAlq, TAZ is a widely used electron transport material. In some light emitting devices, particularly blue light devices, however, it is desirable that the triplet energy level of the electron transporting material is higher than that of the luminescent dye, so that excitons are sufficiently confined in the light emitting layer.
The structure of the electron transport material used as the electron transport layer at present usually contains electron withdrawing groups such as pyridine, pyrimidine, oxadiazole, triazole, imidazole and other nitrogen-containing heterocycle with electron transport performance, but the electron mobility of the general organic material is low, the hole mobility is higher, and the electron-hole in the light emitting device is unbalanced, so that the problems of reduced device efficiency, poor stability, short service life and the like are caused.
Disclosure of Invention
The purpose of the application is to provide an electron transport material, and aims to solve the problems of low electron mobility, reduced device efficiency, poor stability, short service life and the like of the existing electron transport material.
The application is realized in such a way that an electron transport material has a structural formula shown in formula I:
wherein R is 1 Independently selected from hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, phenanthryl, pyridyl and one of the following groups:
* Represents a group attachment position;
l is one of a connecting bond, phenyl, biphenyl, naphthyl, terphenyl, phenanthryl, methylphenyl, phenylnaphthyl, fluorenyl, cyanophenyl, phenylpyridyl, triazinyl, dibenzofuranyl, dibenzothienyl, pyridyl, pyrimidinyl, quinolinyl and quinoxalinyl;
Z 1 -Z 4 independently selected from C, N, wherein the number of N is 1 or 2;
Z 5 -Z 8 independently selected from C, N, wherein the number of N is 1 or 2;
Ar 1 ，Ar 2 each independently selected from one of substituted or unsubstituted C6-C24 aryl and substituted or unsubstituted C6-C24 heteroaryl, and the heteroatom is N, O, S.
Another object of the present application is a process for the preparation of an electron transport material, when R 1 In the case of hydrogen, the preparation method of the electron transport material comprises the following steps:
Hal 1 selected from Br, I;
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 85-95 ℃ and reacting for 8-12h to obtain an intermediate C-I;
After the intermediate C-I and the reactant D-I were dissolved in xylene, pd (OAc) was added under nitrogen protection 2 Heating the reaction temperature of X-Phos and t-Buona to 130-140 ℃, stirring and mixing for 8-12h to obtain a compound shown in a general formula I;
or,
Hal 1 selected from Br, I;
after adding the reactants A-I and B-I in toluene, pd was added under nitrogen protection 2 (dba) 3 、P(t-Bu) 3 t-Buona, heating to 80-90 ℃, stirring and mixing for 8-12h to obtain an intermediate C-I;
N 2 under the protection, respectively adding an intermediate C-I, a reactant D-I, palladium acetate, 2-cyclohexyl-2, 4, 6-triisopropyl biphenyl and cesium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain a compound shown in a general formula I;
when R is 1 When the electron transport material is not hydrogen, the preparation method of the electron transport material comprises the following steps:
Hal 1 selected from Br, I;
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
after the intermediate C-I and the reactant D-I were dissolved in xylene, pd (OAc) was added under nitrogen protection 2 X-Phos, t-Buona; the reaction temperature is raised to 130-140 ℃, and the mixture is stirred and mixed for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction container, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
N 2 under the protection, respectively adding an intermediate F-I, reactants G-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain a compound shown in a general formula I;
or,
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under protection, intermediate C-I, reactant D-I, pd (OAc) 2 Respectively adding X-Phos and cesium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction container, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
after the intermediate F-I and the reactant G-I are added into a reaction vessel and dissolved in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 And (3) raising the temperature of t-Buona to 80-90 ℃, and stirring and mixing for 8-12h to obtain the compound shown in the general formula I.
Another object of the present application is a light emitting device comprising the electron transporting material described above.
Another object of the present application is a light emitting device comprising the light emitting device described above.
The electron transport material provided by the application contains functional groups with strong electron withdrawing capability such as triazine, pyridine and pyrimidine, can effectively improve the electron mobility of the electron transport material, contains specific functional groups of polyazacarbazole, can further improve the electron mobility of the electron transport material, improves the problem of unbalance of electron-holes in an organic electroluminescent device, ensures high triplet energy level (ET) of the material, has a wide band gap, further improves the luminous efficiency, improves the energy level matching degree of each layer of the device, reduces the driving voltage, prolongs the service life of the device, and has excellent device performance compared with the prior art.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate C-80 provided in example 2 of the present application;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 80 provided in example 2 of the present application;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of intermediate C-117 provided in example 4 of the present application;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of intermediate E-117 provided in example 4 of the present application;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of intermediate F-117 provided in example 4 of the present application;
fig. 6 is a nuclear magnetic resonance hydrogen spectrum of compound 117 provided in example 4 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The application provides an electron transport material, which has a structure as shown in formula I:
wherein R is 1 Independently selected from the group consisting of hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, phenanthryl, pyridinyl, and the following:
* Representing the position of the radical attachment.
L is a bond, phenyl, biphenyl, naphthyl, terphenyl, phenanthryl, methylphenyl, phenylnaphthyl, fluorenyl, cyanophenyl, phenylpyridyl, triazinyl, dibenzofuranyl, dibenzothienyl, pyridinyl, pyrimidinyl, quinolinyl, quinoxalinyl.
Z 1 -Z 4 Independently selected from C, N, wherein the number of N is 1 or 2.
Z 5 -Z 8 Independently selected from C, N, wherein the number of N is 1 or 2.
Ar 1 ，Ar 2 Each independently selected from substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C6-C24 heteroaryl, the heteroatom may be N, O, S.
Further, ar 1 ，Ar 2 In the case of a substituted or unsubstituted C6-C24 heteroaryl group, each is independently selected from the group consisting of substituted or unsubstituted pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazolyl, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolinyl, isoquinolinyl, acridinyl, benzofuryl, benzothienyl, benzimidazolyl, benzothiazolyl, benzotriazolyl, benzoxadiazolyl, cinnoline, quinoxalinyl, dibenzofuranyl, dibenzothienyl, phenylpyridyl, phenylcarbazolyl, carbazolyl, phenanthroline, indolizinyl, naphthyridinyl, phenylpyridyl, phenylpyrimidinyl, phthalazinyl, 9-dimethyl-9 h-xanthene, 9-phenyl-9 h-carbazole.
Further, ar 1 ，Ar 2 In the case of a substituted or unsubstituted C6-C24 aryl group, each is independently selected from the group consisting of substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, phenanthryl, anthracenyl, pyrenyl, spirobifluorenyl, 9-dimethylfluorenyl, diphenylfluorenyl, perylenyl, indenyl, azulenyl, benzophenanthryl, methylphenyl, ethylphenyl, methoxyphenyl, and cyanophenyl.
Further, formula I is selected from structures represented by formulas (1) - (17):
further, L is selected from the group consisting of a linkage, phenyl, biphenyl, naphthyl.
Further, ar 1 ，Ar 2 Selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, phenylpyridyl, carbazolyl, 9-dimethyl-9 h-xanthene, 9-phenyl-9 h-carbazole.
In the present application, phenanthrene substitution positions are defined as follows:
in the above technical scheme, 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; C1-C6 alkyl; cycloalkyl of C3-C10; an alkoxy group; C6-C18 aryl; a heterocyclic group of C3 to C24, or a substituent connected with 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.
The electron transport material has the following structure, but is not limited thereto:
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The method successfully obtains the target compound through process optimization by a synthesis method and nuclear magnetic resonance hydrogen spectrum verification, and the optimized synthesis route is as follows:
(1) When R is 1 When hydrogen:
Hal 1 selected from Br, I.
Step 1:
N 2 under protection, the reaction A-I (1.0 eq), the reaction B-I (1-1.2 eq) and Pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01-0.02 eq) and K 2 CO 3 Adding (potassium carbonate) (2.0-2.4 eq) into mixed solvent of toluene, ethanol and water (2-4:1:1), heating to 85-9The reaction is carried out for 8 to 12 hours at the temperature of 5 ℃, diatomite is used for carrying out suction filtration while the mixture is hot, salt and catalyst are removed, after the filtrate is cooled to the room temperature, a rotary evaporator is used for removing solvent, and the obtained solid is dried and then passes through a silica gel funnel, and methylene dichloride is used: the volume ratio of petroleum ether is 1 (3-6) as developing agent, filtrate is removed by a rotary evaporator, and obtained solid is dried to obtain intermediate C-I.
Step 2:
after adding intermediate C-I (1.0 eq) and reactant D-I (1.0-1.4 eq) to the reaction vessel and dissolving in xylene, pd (OAc) was added under nitrogen protection 2 (0.02-0.05 eq), X-Phos (0.04-0.15 eq), t-Buona (2.0-2.4 eq); after the addition, the reaction temperature is slowly increased to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1: and (2-7) using dichloromethane and petroleum ether as eluent, and purifying the residual substances by using column chromatography to obtain the compound shown in the general formula I.
Or,
Hal 1 selected from Br, I.
Step 1:
after adding reactants A-I (1.0 eq) and B-I (1.0-1.4 eq) to toluene in a reaction vessel, pd was added under nitrogen 2 (dba) 3 (0.01-0.02eq)、P(t-Bu) 3 (0.02-0.04 eq), t-Buona (2.0-2.4 eq); after the addition, the reaction temperature is slowly increased to 80-90 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and spun downRemoving the solvent by an evaporator; the volume ratio is 1: and (2-7) using dichloromethane and petroleum ether as eluent, and purifying the residual substances by column chromatography to obtain an intermediate C-I.
Step 2:
N 2 under protection, intermediate C-I (1.0 eq), reactant D-I (1-1.2 eq), palladium acetate (Pd (OAc) 2 ) (0.01-0.05 eq) and 2-cyclohexyl-2, 4, 6-triisopropyl biphenyl (X-Phos) (0.05-0.2 eq) cesium carbonate (2.0-2.3 eq) are respectively added into a mixed solvent of toluene, ethanol and water (2-4:1:1), the temperature is raised to 80-100 ℃, the reaction is carried out for 8-12H, the temperature is cooled to room temperature, and H is added 2 And O, filtering after the solid is precipitated, drying a filter cake, heating and dissolving the obtained solid by using toluene, passing through a silica gel funnel while the solid is hot, and using methanol: the volume ratio of dichloromethane is 1 (40-60) as developing agent, the solvent is removed from the obtained rotary evaporator, and the obtained solid is dried to obtain the compound shown in the general formula I.
(2)R 1 When not hydrogen:
Hal 1 selected from Br, I.
Step 1:
N 2 under protection, the reaction A-I (1.0 eq), the reaction B-I (1.0-1.2 eq) and Pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01-0.05 eq) and K 2 CO 3 (Potassium carbonate) (2.2 eq) is added into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, the temperature is raised to 80-90 ℃, the reaction is carried out for 8-12h, diatomite is used for carrying out suction filtration while the mixture is hot, salt and catalyst are removed, the filtrate is cooled to room temperature, a rotary evaporator is used for removing the solvent, and the obtained solid is dried and then passes through a silica gel funnel, and methylene dichloride is adopted: the volume ratio of petroleum ether is 1 (3-6) as developing agent, filtrate is removed by a rotary evaporator, and obtained solid is dried to obtain intermediate C-I.
Step 2:
after adding intermediate C-I (1.0 eq) and reactant D-I (1.1-1.3 eq) to the reaction vessel and dissolving in xylene, under nitrogen protectionPd (OAc) is added 2 (0.01-0.05 eq), X-Phos (0.02-0.15 eq), t-Buona (2.0-2.4 eq); after the addition, the reaction temperature is slowly increased to 130-140 ℃, and the mixture is stirred for 8-12h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:2-4, and purifying the remaining material by column chromatography with dichloromethane and petroleum ether as eluent to obtain intermediate E-I.
Step 3:
adding an intermediate E-I (1.0 eq) into a reaction vessel, adding DMF and acetic acid, stirring, adding NBS (1.0-1.2 eq), heating to 100-140 ℃, reacting overnight, cooling to room temperature, adding deionized water, stirring, suction filtering, sequentially eluting a filter cake with water and ethanol, drying the obtained solid, filtering by a silica gel funnel, removing the filtrate by a rotary evaporator, and drying the obtained solid to obtain the intermediate F-I.
Step 4:
N 2 under the protection, intermediate F-I (1.0 eq), reactant G-I (1.1-1.3 eq) Pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01-0.05 eq) and K 2 CO 3 (Potassium carbonate) (2.0-2.2 eq) is added into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, the temperature is raised to 80-90 ℃, the reaction is carried out for 8-12h, diatomite is used for carrying out suction filtration while the mixture is hot, salt and catalyst are removed, the filtrate is cooled to room temperature, a rotary evaporator is used for removing the solvent, and the obtained solid is dried and then passes through a silica gel funnel, and dichloromethane is used for carrying out: petroleum ether with the volume ratio of 1:3-6 is used as a developing agent, filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain the compound shown in the general formula I.
Or,
step 1:
N 2 protection ofNext, reactant A-I (1.0 eq), reactant B-I (1.0-1.2 eq), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01 eq) and K 2 CO 3 (Potassium carbonate) (2.0-2.3 eq) is added into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, the temperature is raised to 80-90 ℃, the reaction is carried out for 8-12h, diatomite is used for carrying out suction filtration while the mixture is hot, salt and catalyst are removed, the filtrate is cooled to room temperature, a rotary evaporator is used for removing the solvent, and the obtained solid is dried and then passes through a silica gel funnel, and dichloromethane is used for carrying out: the volume ratio of petroleum ether is 1 (2-4) as developing agent, filtrate is removed by a rotary evaporator, and obtained solid is dried to obtain intermediate C-I.
Step 2:
N 2 under protection, intermediate C-I (1.0 eq), reactant D-I (1.1-1.2 eq), pd (OAc) 2 (0.01-0.05 eq) and X-Phos (0.05-0.15 eq) cesium carbonate (2.0-2.2 eq) are respectively added into a mixed solvent of toluene, ethanol and water (2-4:1:1), the temperature is raised to 80-90 ℃, the reaction is carried out for 8-12H, the temperature is cooled to room temperature, and H is added 2 And O, filtering after the solid is precipitated, drying a filter cake, heating and dissolving the obtained solid by using toluene, passing through a silica gel funnel while the solid is hot, and using methanol: the volume ratio of dichloromethane is 1 (40-60) as developing agent, the solvent is removed from the obtained rotary evaporator, and the obtained solid is dried to obtain an intermediate E-I.
Step 3:
adding an intermediate E-I (1.0 eq) into a reaction vessel, adding DMF and acetic acid, stirring, adding NBS (1.1-1.3 eq), heating to 100-140 ℃, reacting overnight, cooling to room temperature, adding deionized water, stirring, suction filtering, sequentially eluting a filter cake with water and ethanol, drying the obtained solid, filtering by a silica gel funnel, removing the filtrate by a rotary evaporator, and drying the obtained solid to obtain the intermediate F-I.
Step 4:
after adding intermediate F-I (1.0 eq) and reactant G-I (1.1-1.3 eq) to toluene in a reaction vessel, pd was added under nitrogen protection 2 (dba) 3 (0.01-0.05eq)、P(t-Bu) 3 (0.02-0.1 eq), t-BuONa (2.0-2.4 eq); after the addition, the reaction temperature is slowly increased to 80-90 ℃, and the mixture is stirred for 8-12h; using diatomFiltering while soil is hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1: and (2) using dichloromethane and petroleum ether as eluent, and purifying the residual substances by column chromatography to obtain the compound shown in the general formula I.
The synthesis method provided by the application carries out a series of palladium catalytic coupling reactions, on one hand, the difference that the activity of Br is larger than that of Cl is utilized, on the other hand, the reaction sites are controlled by controlling the reaction conditions, and the byproducts are removed by column chromatography or silica gel funnel purification reaction, so that the target compound is obtained. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-crabtree (Robert H.Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
For the reaction site of Br on phenanthrene, my department refers to the existing common knowledge: sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzenes with Aromatic Bromides for the Synthesis of Polycyclic Aromatic Compounds, 10.1002/anie.201910792, page 3, scheme 4; CN113234010a, paragraph [0133] of the specification, performs process optimization on the synthesis method, and successfully obtains the target reactant through nuclear magnetic resonance hydrogen spectrum verification.
The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the electron transport materials of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments.
Example 1: synthesis of Compound 8
CAS：A-8：1345345-08-5
CAS：B-8：2170029-68-0
CAS：D-8：108349-62-8
Step 1:
N 2 under protection, reactant A-8 (100 mmol), reactant B-8 (120 mmol), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (1 mmol) and K 2 CO 3 (Potassium carbonate) (220 mmol) was added to a mixed solvent of toluene, ethanol and water (450 mL:150 mL), the temperature was raised to 90℃and the mixture was reacted for 8 hours, the salt and the catalyst were removed by suction filtration with celite, the filtrate was cooled to room temperature, the solvent was removed by a rotary evaporator, and the obtained solid was dried and passed through a silica gel funnel with methylene chloride: petroleum ether with a volume ratio of 1:4 is used as a developing agent, the filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-8 (32.04 g, yield: 72%, test value MS (ESI, M/Z): [ M+H ] ] + ＝444.95)。
Step 2:
after adding intermediate C-8 (70 mmol) and reactant D-8 (77 mmol) to the reaction vessel and dissolving in xylene (350 mL), pd (OAc) was added under nitrogen blanket 2 (3.5 mmol), X-Phos (7.7 mmol), t-BuONa (147 mmol); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 10h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:3, and petroleum ether as eluent, and purifying the remaining material by column chromatography to give Compound 8 (33.16 g, yield: 82%, test value MS (ESI, M/Z): [ M+H ]] + ＝577.68)。
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,81.23; h,4.20; n,14.57
Test value: c,81.08; h,4.31; n,14.66
Example 2: synthesis of Compound 80
Step 1:
after adding reactant A-80 (100 mmol) and reactant B-80 (110 mmol) to toluene in a reaction vessel, pd was added under nitrogen 2 (dba) 3 (1mmol)、P(t-Bu) 3 (2 mmol), t-BuONa (2.2 mmol); after the addition, the reaction temperature was slowly raised to 90 ℃ and the mixture was stirred for 8h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:4, and Petroleum ether as eluent, and purifying the remaining material by column chromatography to obtain intermediate C-80 (23.18 g, yield: 61%, test value MS (ESI, M/Z): [ M+H ]] + ＝379.96)。
The nuclear magnetic data of intermediate C-80 is shown in FIG. 1.
Step 2:
N 2 under protection, intermediate C-80 (60 mmol), reactant D-80 (66 mmol), pd (OAc) 2 (1.2 mmol) and X-Phos (6 mmol) cesium carbonate (132 mmol) were added to a mixed solvent of toluene, ethanol, and water (240 mL:80 mL), respectively, and the mixture was heated to 90℃and reacted for 10 hours, cooled to room temperature, and H was added 2 And O, filtering after the solid is precipitated, drying a filter cake, heating and dissolving the obtained solid by using toluene, passing through a silica gel funnel while the solid is hot, and using methanol: the solvent was removed by a rotary evaporator with a methylene chloride volume ratio of 1:40 as a developing solvent, and the obtained solid was dried to obtain compound 80 (37.22 g, yield: 85%, test) Value MS (ESI, M/Z) [ M+H ]] + ＝729.88)。
The nuclear magnetic data of compound 80 is shown in FIG. 2.
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c,84.04; h,4.43; n,11.53
Test value: c,83.86; h,4.51; n,11.73
Example 3: synthesis of Compound 113
CAS：A-113：1518823-39-6
CAS：B-113：892550-44-6
Step 1:
N 2 under protection, reactant A-113 (100 mmol), reactant B-113 (120 mmol), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (1 mmol) and K 2 CO 3 (Potassium carbonate) (220 mmol) was added to a mixed solvent of toluene, ethanol and water (450 mL:150 mL), the temperature was raised to 90℃and the mixture was reacted for 8 hours, the salt and the catalyst were removed by suction filtration with celite, the filtrate was cooled to room temperature, the solvent was removed by a rotary evaporator, and the obtained solid was dried and passed through a silica gel funnel with methylene chloride: petroleum ether with a volume ratio of 1:4 is used as a developing agent, the filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-113 (39.60 g, yield: 76%, test value MS (ESI, M/Z): [ M+H ]] + ＝521.06)。
Step 2:
after adding intermediate C-113 (70 mmol) and reactant D-113 (77 mmol) to the reaction vessel and dissolving in xylene (350 mL), pd (OAc) was added under nitrogen blanket 2 (3.5 mmol), X-Phos (7.7 mmol), t-BuONa (147 mmol); after the addition, the reaction temperature was slowly raised to 135 ℃ and the mixture was stirred for 10h; filtering with diatomite while the diatomite is hot,removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:3, and petroleum ether as eluent, and purifying the remaining material by column chromatography to give compound 113 (40.27 g, yield: 88%, test value MS (ESI, M/Z): [ M+H ]] + ＝653.78)。
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,82.80; h,4.32; n,12.87
Test value: c,82.70; h,4.38; n,12.98
Example 4: synthesis of Compound 117
Step 1:
intermediate C-117 is the same as intermediate C-8 of example 1, and has the same reaction and is not described in detail. Intermediate C-117 (144 mmol) was obtained.
The nuclear magnetic data of intermediate C-117 is shown in FIG. 3.
Step 2:
intermediate E-117 is the same as compound 8 of example 1, and has the same reaction, and is not described in detail. Intermediate E-117 (114.8 mmol) was obtained.
The nuclear magnetic data of intermediate E-117 is shown in FIG. 4.
Step 3:
adding an intermediate E-117 (112 mmol) into a reaction vessel, adding 560mL of DMF and 56mL of acetic acid, stirring, adding NBS (123.2 mmol) and heating to 100 ℃, reacting overnight, cooling to room temperature after finishing, adding deionized water, stirring, filtering, eluting a filter cake with water and ethanol in sequence, drying the obtained solid, and thenThe silica gel funnel was removed from the filtrate using a rotary evaporator, and the resulting solid was dried to give intermediate F-117 (40.44 g, yield: 55%, test value MS (ESI, M/Z): [ M+H ]] + ＝656.57)。
The nuclear magnetic data of intermediate F-117 is shown in FIG. 5.
Step 4:
N 2 under protection, intermediate F-117 (60 mmol), reactant G-117 (72 mmol), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.6 mmol) and K 2 CO 3 (Potassium carbonate) (126 mmol) was added to a mixed solvent of toluene, ethanol and water (300 mL:100 mL), the temperature was raised to 90℃and the mixture was reacted for 8 hours, the salt and the catalyst were removed by suction filtration with celite, the filtrate was cooled to room temperature, the solvent was removed by a rotary evaporator, and the obtained solid was dried and passed through a silica gel funnel with methylene chloride: petroleum ether with a volume ratio of 1:4 is used as developing agent, the filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain compound 117 (34.13 g, yield: 87%, test value MS (ESI, M/Z): [ M+H ] ]+＝653.78)。
The nuclear magnetic data of compound 117 is shown in FIG. 6.
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.7%.
Elemental analysis:
theoretical value: c,82.80; h,4.32; n,12.87
Test value: c,82.68; h,4.38; n,13.02
Example 5: synthesis of Compound 127
CAS: reactant D-127:693774-10-6
Step 1:
intermediate C-117 is the same as intermediate C-8 of example 1, and has the same reaction and is not described in detail. Intermediate C-117 (144 mmol) was obtained.
Step 2:
N 2 under protection, intermediate C-127 (140 mmol), reactant D-127 (154 mmol), pd (OAc) 2 (2.8 mmol) and X-Phos (14 mmol) cesium carbonate (294 mmol) were added to a mixed solvent of toluene, ethanol, and water (450 mL:150 mL), respectively, and the mixture was heated to 90℃and reacted for 10 hours, cooled to room temperature, and H was added 2 And O, filtering after the solid is precipitated, drying a filter cake, heating and dissolving the obtained solid by using toluene, passing through a silica gel funnel while the solid is hot, and using methanol: the solvent was removed from the resulting rotary evaporator and the resulting solid was dried to give intermediate E-127 (64.62 g, yield: 78%, test value MS (ESI, M/Z): [ M+H ]]+＝591.77)。
Step 3:
To the reaction vessel was added intermediate E-127 (112 mmol), followed by 560mL DMF and 56mL acetic acid with stirring, NBS (123.2 mmol) was added and heated to 100deg.C, after the completion of the reaction, cooled to room temperature, deionized water was added with stirring, suction filtration, the cake was washed with water, ethanol in this order, the obtained solid was dried, and then passed through a silica gel funnel, the filtrate was removed by a rotary evaporator, and the obtained solid was dried to obtain intermediate F-127 (45.07, yield: 60%, test value MS (ESI, M/Z): [ M+H ] + = 670.65).
Step 4:
after adding intermediate F-127 (60 mmol) and reactant G-127 (66 mmol) to toluene in a reaction vessel, pd was added under nitrogen 2 (dba) 3 (0.6mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (132 mmol); after the addition, the reaction temperature was slowly raised to 90 ℃ and the mixture was stirred for 8h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:4, and petroleum ether as eluent, and purifying the remaining material by column chromatography to give compound 127 (36.88 g, yield: 81%, test value MS (ESI, M/Z): [ M+H ] ]+＝758.93)。
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,82.41; h,4.65; n,12.94
Test value: c,82.25; h,4.71; n,13.13
Example 6: synthesis of Compound 135
CAS: reactant a-135:329214-79-1
CAS: reactant B-135:2649616-14-6
Step 1:
N 2 under protection, reactant A-135 (200 mmol), reactant B-135 (240 mmol), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (2 mmol) and K 2 CO 3 (Potassium carbonate) (440 mmol) was added to a mixed solvent of toluene, ethanol and water (900 mL:300 mL), the temperature was raised to 90℃and the mixture was reacted for 8 hours, the salt and the catalyst were removed by suction filtration with celite, the filtrate was cooled to room temperature, the solvent was removed by a rotary evaporator, and the obtained solid was dried and passed through a silica gel funnel with methylene chloride: petroleum ether with a volume ratio of 1:4 is used as a developing agent, the filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-135 (42.34 g, yield: 73%, test value MS (ESI, M/Z): [ M+H ]]+＝289.99)。
Step 2:
N 2 under protection, intermediate C-135 (140 mmol), reactant D-135 (154 mmol), pd (OAc) 2 (2.8 mmol) and X-Phos (14 mmol) cesium carbonate (294 mmol) were added to a mixed solvent of toluene, ethanol, and water (450 mL:150 mL), respectively, and the mixture was heated to 90℃and reacted for 10 hours, cooled to room temperature, and H was added 2 And O, filtering after the solid is precipitated, drying a filter cake, heating and dissolving the obtained solid by using toluene, passing through a silica gel funnel while the solid is hot, and using methanol: dichloromethane bodyThe solvent was removed by a rotary evaporator at a product ratio of 1:40 as a developing agent, and the resulting solid was dried to give intermediate E-135 (67.87 g, yield: 86%, test value MS (ESI, M/Z): [ M+H ]]+＝563.70)。
Step 3:
to the reaction vessel was added intermediate E-135 (112 mmol), followed by 560mL DMF and 56mL acetic acid with stirring, NBS (123.2 mmol) was added and heated to 100deg.C, after the completion of the reaction, cooled to room temperature, deionized water was added with stirring, suction filtration, the cake was washed with water, ethanol in this order, the obtained solid was dried, and then passed through a silica gel funnel, the filtrate was removed by a rotary evaporator, and the obtained solid was dried to obtain intermediate F-135 (38.80 g, yield: 54%, test value MS (ESI, M/Z): [ M+H ] + = 641.59).
Step 4:
after adding intermediate F-135 (60 mmol) and reactant G-135 (66 mmol) to toluene in a reaction vessel, pd was added under nitrogen 2 (dba) 3 (0.6mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (132 mmol); after the addition, the reaction temperature was slowly raised to 90 ℃ and the mixture was stirred for 8h; filtering with diatomaceous earth while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator; the volume ratio is 1:4 as eluent, and purifying the remaining material by column chromatography to give compound 135 (35.03 g, yield: 80%, test value MS (ESI, M/Z): [ M+H ] ]+＝729.88)。
The yields in the above steps are the fractional yields of the corresponding steps.
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c,82.28; h,4.28; n,13.43
Test value: c,82.09; h,4.36; n,13.62
Examples 7 to 46
The synthesis of the following compounds was completed with reference to the synthesis methods of examples 1 to 6, and their molecular formulas and mass spectrum data are shown in table 1 below.
Table 1 molecular formula and mass spectrum
Further, since other compounds of the present application can be obtained by referring to the synthetic methods of the examples listed above, they are not exemplified herein.
The present application provides an organic electroluminescent device that may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, and the like as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller or larger number of organic layers.
According to one embodiment of the present disclosure, the organic layer has an electron transport layer, and the compound of formula I prepared herein is used as a material for the electron transport layer.
In the case of producing an organic light-emitting device, the compound represented by the formula I may be formed by vacuum vapor deposition or solution coating. The solution coating method is, but not limited to, spin coating, dip coating, blade coating, ink jet printing, screen printing, spray coating, roll coating, and the like.
The light emitting device of the present application may be of a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.
The device described herein may be used in organic light emitting devices, organic solar cells, electronic paper, organic photoreceptors, or organic thin film transistors.
As an anode material, it is usual to enable holesThe organic layer is smoothly implanted, preferably with a large work function. Specific examples of the anode material that can be used in the present application include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO A1 or SnO 2 A combination of metals such as Sb and the like and oxides; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer is preferably a p-doped hole injection layer, by which is meant a hole injection layer doped with a p-dopant. A p-dopant is a material capable of imparting p-type semiconductor characteristics. The p-type semiconductor property means a property of injecting holes or transporting holes at the HOMO level, that is, a property of a material having high hole conductivity.
The hole transporting material is a material capable of receiving holes from the anode or the hole injecting layer and transporting the holes to the light emitting layer, and has high hole mobility. The hole transport material may be selected from arylamine derivatives, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.
A light-emitting auxiliary layer (multilayer hole-transporting layer) is interposed between the hole-transporting layer and the light-emitting layer. The light-emitting auxiliary layer mainly functions as an auxiliary hole transport layer, and is therefore sometimes also referred to as a second hole transport layer. The light emitting auxiliary layer enables holes transferred from the anode to smoothly move to the light emitting layer, and can block electrons transferred from the cathode to confine electrons in the light emitting layer, reduce potential barrier between the hole transporting layer and the light emitting layer, reduce driving voltage of the organic electroluminescent device, further increase utilization ratio of holes, thereby improving luminous efficiency and lifetime of the device.
The light-emitting substance of the light-emitting layer is a substance capable of receiving and binding holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence.
The light emitting layer may include a host material and a dopant material.
The mass ratio of the host material to the doping material is (90-99.5) (0.5-10).
The host material includes aromatic condensed ring derivatives, heterocyclic compounds, and the like. Specifically, examples of the aromatic condensed ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like; examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, pyrimidine derivatives, and the like.
The dopant materials herein include fluorescent and phosphorescent dopants and may be selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
The electron transport layer may function to facilitate electron transport. The electron transporting material is a material that facilitates receiving electrons from the cathode and transporting the electrons to the light emitting layer, and preferably has high electron mobility. The electron transport layer may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of an electron transport layer and an electron injection layer. The electron transport layer material is a compound shown in a formula I.
The electron injection layer may function to promote electron injection, have an ability to transport electrons, and prevent excitons generated in the light emitting layer from migrating to the hole injection layer. The material of the electron injection layer includes, but is not limited to, metal such as oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylmethane, anthrone, their derivatives, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, or their alloys, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like.
The cathode is generally preferably of a material having a small work function so that electrons are smoothly injected into the organic material layer, which layer preferably has a layer thickness of between 0.5 and 5 nm. The cathode material is generally preferably a material having a small work function in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof: liF/A1 or LiO 2 And (3) multilayer structural materials such as (A1) and Mg/Ag.
There are no particular restrictions on the other layer materials in an OLED device, except that the electron transport layer disclosed herein comprises formula I. Existing hole injection materials, hole transport auxiliary materials, dopant materials, hole blocking layer materials, electron transport layer materials, and electron injection materials may be used.
A light emitting device provided in the present application is specifically described below with reference to specific embodiments.
Application example 1 preparation of organic electroluminescent device:
a. ITO anode: washing an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing by ultrasonic waves for 30min, repeatedly washing by distilled water for 2 times, washing by ultrasonic waves for 10min, transferring into a spin dryer for spin drying after washing, baking for 2 hours at 220 ℃ by a vacuum oven, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): to be used forThe vacuum evaporation of the hole injection layer materials HT and P-dopant is performed, and the chemical formulas are shown below. The evaporation rate ratio of HT to P-dock is 98:2, the thickness is 10nm;
c. HTL (hole transport layer): to be used forVacuum evaporating 120nm HT as a hole transport layer on the hole injection layer;
d. prime (light-emitting auxiliary layer): to be used forVacuum evaporating prime of 5nm on the hole transmission layer as the light-emitting auxiliary layer;
e. EML (light emitting layer): then on the light-emitting auxiliary layer toThe Host material (Host) and the Dopant material (Dopant) having a thickness of 25nm were vacuum-deposited as light-emitting layers, and the chemical formulas of Host and Dopant are shown below. Wherein the evaporation rate ratio of Host to Dopant is 95:5.
f. HB (hole blocking layer): to be used forIs used for vacuum evaporation of a hole blocking layer with a thickness of 5.0 nm.
g. ETL (electron transport layer): to be used forIs used as an electron transport layer, and compound 1 and Liq having a thickness of 35nm are vacuum-deposited. Wherein the evaporation rate ratio of the compound 1 to the Liq is 50:50.
h. EIL (electron injection layer): to be used forThe vapor deposition rate of Yb film layer was 1.0nm to form an electron injection layer.
i. And (3) cathode: to be used forThe vapor deposition rate ratio of magnesium and silver is 18nm, and the vapor deposition rate ratio is 1:9, so that the OLED device is obtained.
j. Light extraction layer: to be used forCPL with a thickness of 70nm was vacuum deposited on the cathode as a light extraction layer.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The device structure is as follows:
ITO/Ag/ITO/HT:P-dopant(10nm,2％)/HT(120nm)/prime(5nm)/Host:Dopant(25nm，5％)/HB(5nm)/ET:Liq(35nm,50％)/Yb(1nm)/Mg:Ag(18nm,1:9)/CPL(70nm)。
application examples 2 to 46
The organic electroluminescent devices of application examples 2 to 46 were prepared according to the above-described preparation method of the organic electroluminescent device, except that compound 1 of application example 1 was replaced with the corresponding compound, respectively, to form an electron transport layer.
Comparative example 1
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 1, wherein the structural formula of comparative compound 1 is as follows:
comparative example 2
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 2, wherein the structural formula of comparative compound 2 is as follows:
Comparative example 3
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 3, wherein the structural formula of comparative compound 3 is as follows:
comparative example 4
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 1 of application example 1 was replaced with comparative compound 4, wherein the structural formula of comparative compound 4 is as follows:
the light emitting devices obtained in the above application examples 1 to 46 and comparative examples 1 to 4 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 1000 nits)
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As known to those skilled in the art, the blue-light organic electroluminescent device is affected by the microcavity effect, and the luminous efficiency is greatly affected by chromaticity, so that a BI value is introduced as the basis of the efficiency of the blue-light luminescent material, bi=luminous efficiency/CIEy. Moreover, the problems of short lifetime and low efficiency of blue devices have been one of the problems that those skilled in the art are urgent to solve in the art.
As can be seen from table 2, the light emitting device application examples 1 to 46 prepared using the electron transport materials provided herein have improved light emitting efficiency, BI and lifetime at the driving voltage as compared with the conventional organic electroluminescent devices provided in comparative examples 1 to 4.
From the device effect, when the number of substituents on phenanthrene is 3, the service life is obviously prolonged, and the luminous efficiency is improved. When the number of substituents on phenanthrene is 2, the luminous efficiency is obviously improved, and compared with the compound 1 and the compound 29, the existence of polyazacarbazole improves the luminous efficiency of the device by 7%, and the luminous efficiency of the blue light device in the field is obviously improved.
Specifically, triazine, pyridine and pyrimidine are functional groups with strong electron withdrawing capability, so that the electron mobility of the electron transport material can be effectively improved; the specific functional group containing polyazacarbazole is used for further improving the electron mobility of the electron transport material, improving the problem of unbalance of electron and hole in the organic electroluminescent device, simultaneously ensuring the high triplet energy level (ET) of the material, having wide band gap, further improving the luminous efficiency, improving the energy level matching degree of each layer of the device, reducing the driving voltage, prolonging the service life of the device and having excellent device performance compared with the prior art.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.

Claims (5)

1. An electron transport material characterized in that the structural formula of the electron transport material is selected from structures represented by formulas (1) - (17):
wherein R is 1 Independently selected from hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, phenanthryl, pyridyl and one of the following groups:
* Represents a group attachment position;
l is selected from one of a connecting bond, phenyl, biphenyl and naphthyl;
Z 1 -Z 4 independently selected from C, N, wherein the number of N is 1 or 2;
Z 5 -Z 8 independently selected from C, N, wherein the number of N is 1 or 2;
Ar 1 ，Ar 2 one selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, phenylpyridyl, carbazolyl and 9-phenylcarbazole.
2. The electron transport material according to claim 1, wherein the electron transport material is any of the following structures:
3. the method for producing an electron transporting material according to claim 1, wherein,
When R is 1 In the case of hydrogen, the preparation method of the electron transport material comprises the following steps:
Hal 1 selected from Br, I;
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 85-95 ℃ and reacting for 8-12h to obtain an intermediate C-I;
after the intermediate C-I and the reactant D-I were dissolved in xylene, pd (OAc) was added under nitrogen protection 2 Heating the reaction temperature of X-Phos and t-Buona to 130-140 ℃, stirring and mixing for 8-12h to obtain a compound shown in a general formula I;
or,
Hal 1 selected from Br, I;
after adding the reactants A-I and B-I in toluene, pd was added under nitrogen protection 2 (dba) 3 、P(t-Bu) 3 t-Buona, heating to 80-90 ℃, stirring and mixing for 8-12h to obtain an intermediate C-I;
N 2 under the protection, respectively adding an intermediate C-I, a reactant D-I, palladium acetate, 2-cyclohexyl-2, 4, 6-triisopropyl biphenyl and cesium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-100 ℃, and reacting for 8-12h to obtain a compound shown in a general formula I;
when R is 1 When the electron transport material is not hydrogen, the preparation method of the electron transport material comprises the following steps:
Hal 1 selected from Br, I;
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
After the intermediate C-I and the reactant D-I were dissolved in xylene, pd (OAc) was added under nitrogen protection 2 X-Phos, t-Buona; the reaction temperature is raised to 130-140 ℃, and the mixture is stirred and mixed for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction container, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
N 2 under the protection, respectively adding an intermediate F-I, reactants G-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain a compound shown in a general formula I;
or,
N 2 under the protection, respectively adding reactants A-I, reactants B-I, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under protection, intermediate C-I, reactant D-I, pd (OAc) 2 Respectively adding X-Phos and cesium carbonate into a mixed solvent of toluene, ethanol and water, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction container, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
Adding the intermediate F-I and the intermediate F-I into a reaction vesselAfter the reaction G-I was dissolved in toluene, pd was added under nitrogen blanket 2 (dba) 3 、P(t-Bu) 3 Heating t-Buona to 80-90 ℃, stirring and mixing for 8-12h to obtain a compound shown in a general formula I;
ar as described above 1 ，Ar 2 ，L，R 1 ，Z 1 -Z 8 Having a range as claimed in claim 1.
4. A light-emitting device, characterized in that the light-emitting device comprises the electron transporting material according to any one of claims 1 to 2.
5. A light-emitting apparatus characterized in that it comprises the light-emitting device according to claim 4.
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