CN115894491A - 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

Info

Publication number
CN115894491A
CN115894491A CN202211484361.9A CN202211484361A CN115894491A CN 115894491 A CN115894491 A CN 115894491A CN 202211484361 A CN202211484361 A CN 202211484361A CN 115894491 A CN115894491 A CN 115894491A
Authority
CN
China
Prior art keywords
electron transport
transport material
reactant
heating
toluene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211484361.9A
Other languages
Chinese (zh)
Other versions
CN115894491B (en
Inventor
汪康
孟范贵
魏威
李飞
陈振生
李金磊
华伟东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Optical and Electronic Materials Co Ltd
Original Assignee
Jilin Optical and Electronic Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Optical and Electronic Materials Co Ltd filed Critical Jilin Optical and Electronic Materials Co Ltd
Priority to CN202211484361.9A priority Critical patent/CN115894491B/en
Publication of CN115894491A publication Critical patent/CN115894491A/en
Application granted granted Critical
Publication of CN115894491B publication Critical patent/CN115894491B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The application is applicable to the technical field of materials, and provides an electron transport material and a preparation method thereof, a light-emitting device and a light-emitting device, 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 polynitrogen carbazole, can further improve the electron mobility of the electron transport material, improves the problem of unbalance of electron-hole in an organic electroluminescent device, simultaneously ensures high three linear state energy levels and wide band gap of the material, further improves the light-emitting efficiency, improves the matching degree of each layer of energy level of the device, reduces the driving voltage, prolongs the service life of the device, and has excellent device performance compared with the prior art.

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
With the rapid development of information technology, people also put new targets and requirements on the performance of information display systems, and research on displays with high brightness, high resolution, wide viewing angle and low energy consumption is hot. The organic electroluminescent (OLED) display technology can meet the above-mentioned needs of people, and has other advantages such as a wide operating temperature, and flexible display. It has the following structure: an anode, a cathode, and an organic material layer 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), an emission 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 the generated excitons generate light having a specific wavelength while shifting 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 amount of electrons, and in order to improve the injection and transport of electrons, an electron injection and transport material with high mobility needs to be used. The electron transport material needs to have a high glass transition temperature (Tg), and the electron transport materials widely used are Bphen, TPBi, BCP, BALq, TAZ and the like. In some light emitting devices, especially in blue light emitting devices, however, it is desirable that the triplet energy level of the electron transport material is higher than that of the light emitting dye so as to sufficiently confine excitons in the light emitting layer.
The electron-transporting material used as the electron-transporting layer at present generally contains electron-withdrawing groups such as pyridine, pyrimidine, oxadiazole, triazole, imidazole and other nitrogen-containing heterocycles with electron-transporting properties in the structure, but the electron mobility of general organic materials is low, and the hole mobility is high, so that the electron-hole imbalance inside the light-emitting device is caused, and the problems of low device efficiency, poor stability, short service life and the like are caused.
Disclosure of Invention
The application aims to provide an electron transport material, and aims to solve the problems that the existing electron transport material is low in electron mobility, so that the efficiency of a device is reduced, the stability is poor, the service life is short and the like.
The application is realized by the electron transport material, and the structural formula of the electron transport material is shown as the formula I:
Figure BDA0003961353450000021
wherein R is 1 Independently selected from hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, fluorenyl, phenanthryl, pyridyl and one of the following groups:
Figure BDA0003961353450000031
* Represents a group attachment position;
l is one of a connecting bond, phenyl, biphenyl, naphthyl, terphenyl, phenanthryl, methylphenyl, phenylnaphthyl, fluorenyl, cyanophenyl, phenylpyridyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, pyrimidinyl, quinolinyl and quinoxalinyl;
Z 1 -Z 4 independently selected from C and 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 is one of substituted or unsubstituted C6-C24 aryl and substituted or unsubstituted C6-C24 heteroaryl, and the heteroatom is N, O or S.
Another object of the present application is a process for the preparation of an electron transport material when R is 1 In the case of hydrogen, the preparation method of the electron transport material comprises the following steps:
Figure BDA0003961353450000041
Hal 1 selected from Br, I;
N 2 under protection, adding the reactant A-I, the reactant B-I, the tetrakis (triphenylphosphine) palladium and the potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating to 85-95 ℃, and reacting for 8-12h to obtain an intermediate C-I;
after adding the intermediate C-I and the reactant D-I into the reaction vessel and dissolving in xylene, pd (OAc) is added under the protection of nitrogen 2 Heating the reaction temperature to 130-140 ℃, stirring and mixing for 8-12h to obtain a compound shown in a general formula I;
or,
Figure BDA0003961353450000042
Hal 1 selected from Br, I;
after reactants A-I and B-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 t-BuONa, heating the reaction temperature to 80-90 ℃, and stirring and mixing for 8-12h to obtain an intermediate C-I;
N 2 under protection, respectively adding the intermediate C-I, the reactant D-I, palladium acetate, 2-cyclohexyl-2, 4, 6-triisopropylbiphenyl 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:
Figure BDA0003961353450000051
Hal 1 selected from Br, I;
N 2 under protection, adding reactants A-I, B-I, palladium tetrakis (triphenylphosphine) and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
after adding the intermediate C-I and the reactant D-I into a reaction vessel and dissolving in xylene, pd (OAc) is added under the protection of nitrogen 2 X-Phos, t-BuONa; heating the reaction temperature to 130-140 ℃, and stirring and mixing for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction vessel, 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 protection, respectively adding the intermediate F-I, the reactant 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,
Figure BDA0003961353450000061
N 2 under protection, adding reactants A-I, B-I, palladium tetrakis (triphenylphosphine) and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under protection, the intermediate C-I, the reactant D-I and 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 vessel, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
after adding intermediate F-I and reactant G-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating 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 above electron transport material.
Another object of the present application is to provide a light emitting device including the above light emitting device.
The electron transport material provided by the application contains functional groups with strong electron-withdrawing ability, such as triazine, pyridine and pyrimidine, can effectively improve the electron mobility of the electron transport material, contains specific functional groups of polynitrogen heterocyclic carbazole, can further improve the electron mobility of the electron transport material, solves the problem of unbalance of electron-hole in an organic electroluminescent device, ensures high three-linear-state energy level (ET) and wide band gap of the material, 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 NMR chart 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 herein;
FIG. 3 is a NMR spectrum of intermediate C-117 provided in example 4 of the present application;
FIG. 4 is a NMR spectrum of intermediate E-117 provided in example 4 of the present application;
FIG. 5 is a NMR spectrum of intermediate F-117 provided in example 4 of the present application;
figure 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 clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The application provides an electron transport material, the structure of which is formula I:
Figure BDA0003961353450000081
wherein R is 1 Independently selected from the group consisting of hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, fluorenyl, phenanthryl, pyridyl, and the following:
Figure BDA0003961353450000082
* Represents the position of attachment of the group.
L is a connecting bond, phenyl, biphenyl, naphthyl, terphenyl, phenanthryl, methylphenyl, phenylnaphthyl, fluorenyl, cyanophenyl, phenylpyridyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, 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 and substituted or unsubstituted C6-C24 heteroaryl, and the heteroatom can be N, O or S.
Further, ar 1 ，Ar 2 When the aryl is substituted or unsubstituted C6-C24 heteroaryl, each is independently selected from substituted or unsubstituted pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, pyridyl, thiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, triazolyl, pyridazinyl, pyrazinyl, pyridyl, triazinyl, indolyl, and the likeIsoquinolyl, acridinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzothiazolyl, benzotriazolyl, benzooxadiazolyl, benzoxazolyl, cinnoline, quinoxalinyl, dibenzofuranyl, dibenzothienyl, phenylpyridinyl, phenylcarbazolyl, carbazolyl, phenanthrolinyl, indolizinyl, naphthyridinyl, phenylpyridinyl, phenylpyrimidinyl, phthalazinyl, 9-dimethyl-9 h-xanthene, 9-phenyl-9 h-carbazole.
Further, ar 1 ，Ar 2 And when the aryl group is substituted or unsubstituted C6-C24, the aryl group is independently selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, phenanthryl, anthryl, pyrenyl, spirobifluorenyl, 9-dimethylfluorenyl, diphenylfluorenyl, perylenyl, indenyl, azulenyl, benzophenanthryl, methylphenyl, ethylphenyl, methoxyphenyl and cyanophenyl.
Further, formula I is selected from structures shown in formula (1) to formula (17):
Figure BDA0003961353450000091
Figure BDA0003961353450000101
further, L is selected from the group consisting of a linking bond, phenyl, biphenyl, naphthyl.
Further, ar 1 ，Ar 2 Selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, phenylpyridyl, carbazolyl, 9-dimethyl-9 h-xanthene, 9-phenyl-9 h-carbazole.
In the present application, the phenanthrene substitution positions are defined as follows:
Figure BDA0003961353450000102
in the above technical solutions, the term "substituted or unsubstituted" means substituted by one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; C1-C6 alkyl; a cycloalkyl group having 3 to 10 carbon atoms; an alkoxy group; C6-C18 aryl; a heterocyclic group of C3 to C24, or a substituent in which two or more substituents among the above-shown substituents are bonded, or no substituent.
For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
The electron transport material has the following structure, but is not limited thereto:
Figure BDA0003961353450000121
Figure BDA0003961353450000131
Figure BDA0003961353450000141
Figure BDA0003961353450000151
Figure BDA0003961353450000161
Figure BDA0003961353450000171
Figure BDA0003961353450000181
the target compound is successfully obtained by carrying out process optimization on the synthesis method and nuclear magnetic resonance hydrogen spectrum verification, and the optimized synthesis route is as follows:
(1) When R is 1 When hydrogen is used:
Figure BDA0003961353450000182
Hal 1 selected from Br, I.
Step 1:
N 2 under the protection, reactants A-I (1.0 eq), reactants B-I (1-1.2 eq), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01-0.02 eq) and K 2 CO 3 (potassium carbonate) (2.0 to 2.4 eq) was added to a mixed solvent of toluene, ethanol, water (2-4: petroleum ether with the volume ratio of 1 (3-6) is used as a developing solvent, filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-I.
Step 2:
after adding the intermediate C-I (1.0 eq) and the reactant D-I (1.0-1.4 eq) in xylene to a reaction vessel, pd (OAc) is 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 diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of the components is 1: and (2-7) using dichloromethane and petroleum ether as eluent, and purifying the residual substance by using column chromatography to obtain the compound shown in the general formula I.
Or,
Figure BDA0003961353450000191
Hal 1 selected from Br, I.
Step 1:
adding reactants A-I (1.0 eq) and B-I (1.0-1.4 eq) into a reaction vessel, dissolving in toluene, and adding Pd under the protection of 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 diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, 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 of the components is 1: and (2-7) eluting with dichloromethane and petroleum ether, and purifying the remaining substance by column chromatography to obtain intermediate C-I.
Step 2:
N 2 under protection, the intermediate C-I (1.0 eq), the reactant D-I (1-1.2 eq), and palladium acetate (Pd (OAc) 2 ) (0.01 to 0.05 eq) and 2-cyclohexyl-2, 4, 6-triisopropylbiphenyl (X-Phos) (0.05 to 0.2 eq) cesium carbonate (2.0 to 2.3 eq) were added to a mixed solvent of toluene, ethanol, water (2-4 2 And O, filtering after the solid is separated out, drying the filter cake, heating and dissolving the obtained solid by using methylbenzene, passing through a silica gel funnel while the solid is hot, and reacting the solid with methanol: and (3) taking dichloromethane with the volume ratio of 1 (40-60) as a developing solvent, removing the solvent by using the obtained rotary evaporator, and drying the obtained solid to obtain the compound shown in the general formula I.
(2)R 1 When hydrogen is not present:
Figure BDA0003961353450000211
Hal 1 is selected from Br and I.
Step 1:
N 2 under the protection, reactants A-I (1.0 eq), reactants B-I (1.0-1.2 eq), pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (0.01-0.05 eq) and K 2 CO 3 (potassium carbonate) (2.2 eq) was added to a mixed solvent of toluene, ethanol, water (2-4: petroleum ether with the volume ratio of 1 (3-6) is used as a developing solvent, filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-I.
Step 2:
after adding the intermediate C-I (1.0 eq) and the reactant D-I (1.1-1.3 eq) in xylene in a reaction vessel, pd (OAc) is added under nitrogen protection 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 diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of the components is 1:2-4 dichloromethane, petroleum ether as eluent, and column chromatography to purify the remaining material to obtain intermediate E-I.
And step 3:
adding the intermediate E-I (1.0 eq) into a reaction vessel, then adding DMF and acetic acid, stirring, adding NBS (1.0-1.2 eq), heating to 100-140 ℃, reacting overnight, cooling to room temperature after the reaction is finished, adding deionized water, stirring, carrying out suction filtration, sequentially eluting a filter cake with water and ethanol, drying the obtained solid, then passing through a silica gel funnel, removing the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the intermediate F-I.
And 4, step 4:
N 2 under 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 to 2.2 eq) was added to a mixed solvent of toluene, ethanol, water (2-4: and (3) taking petroleum ether with the volume ratio of 1.
Or,
Figure BDA0003961353450000231
step 1:
N 2 under the protection, reactants A-I (1.0 eq), reactants 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 to 2.3 eq) was added to a mixed solvent of toluene, ethanol, water (2-4: petroleum ether volume ratio is 1 (2-4), the petroleum ether is used as a developing solvent, filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain an intermediate C-I.
Step 2:
N 2 under protection, the intermediate C-I (1.0 eq), the 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) were added to a mixed solvent of toluene, ethanol, water (2-4 2 And O, filtering after the solid is separated out, drying the filter cake, heating and dissolving the obtained solid by using methylbenzene, passing through a silica gel funnel while the solid is hot, and reacting the solid with methanol: dichloromethane volume ratio of 1 (40-60) as developing solvent, removing solvent from the obtained rotary evaporator, and drying the obtained solid to obtain intermediate E-I.
And step 3:
adding the intermediate E-I (1.0 eq) into a reaction vessel, then adding DMF and acetic acid, stirring, adding NBS (1.1-1.3 eq), heating to 100-140 ℃, reacting overnight, cooling to room temperature after the reaction is finished, adding deionized water, stirring, carrying out suction filtration, sequentially eluting a filter cake with water and ethanol, drying the obtained solid, then passing through a silica gel funnel, removing the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the intermediate F-I.
And 4, step 4:
after adding intermediate F-I (1.0 eq) and reactant G-I (1.1-1.3 eq) into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 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; filtering with diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of the components is 1: and (2-4) using dichloromethane and petroleum ether as eluent, and purifying the residual substance by using 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 greater than that of Cl is utilized, on the other hand, reaction sites are controlled by controlling reaction conditions, and the reaction is purified by using a column chromatography or a silica gel funnel to remove byproducts, so that the target compound is obtained. Reference to common general knowledge is as follows:
transition metal organic chemistry (sixth edition of original book), robert H krabtree (Robert H crabtree), press: shanghai east China university Press, publication time: 2017-09-00, ISBN 978-7-5628-5111-0, page 388.
Experimental course of organic chemistry and photovoltaic materials, chen Runfeng, press: southeast university Press, published time: 2019-11-00, ISBN 9787564184230, page 174.
For Br reaction sites on phenanthrenes, i refer to the prior common general knowledge: "Sequential Cross-Coupling/analysis of ortho-Vinyl Bromobenzenes with Aromatic polyamides for the Synthesis of multicyclic Aromatic Compounds", 10.1002/anie.201910792, page 3, scheme 4; CN113234010A, paragraph [0133] of the specification, carries on the technological optimization to the synthetic method, through the hydrogen spectrum verification of nuclear magnetic resonance, succeed in obtaining the target reactant.
The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the electronic transmission material of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments.
Example 1: synthesis of Compound 8
Figure BDA0003961353450000251
CAS：A-8：1345345-08-5
CAS：B-8：2170029-68-0
CAS：D-8：108349-62-8
Step 1:
N 2 under protection, a reactant A-8 (100 mmol), a reactant B-8 (120 mmol) and 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, water (450ml: petroleum ether volume ratio of 1] + ＝444.95)。
Step 2:
after adding intermediate C-8 (70 mmol) and reactant D-8 (77 mmol) in xylene (350 mL) to a reaction vessel, P was added under nitrogend(OAc) 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 hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of the components is 1:3 dichloromethane, petroleum ether as eluent, column chromatography was performed to purify the remaining substance to obtain Compound 8 (33.16 g, yield: 82%, test value MS (ESI, M/Z): M + H] + ＝577.68)。
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Elemental analysis:
theoretical value: c,81.23; h,4.20; n,14.57
Test values are: c,81.08; h,4.31; n,14.66
Example 2: synthesis of Compound 80
Figure BDA0003961353450000271
Step 1:
after adding reactant A-80 (100 mmol) and reactant B-80 (110 mmol) dissolved in toluene into a reaction vessel, pd is added under the protection of 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 diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, 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 of the components is 1:4 dichloromethane and petroleum ether as eluent, purifying the remaining material by column chromatography to obtain intermediateC-80 (23.18 g, yield: 61%, test value MS (ESI, M/Z): M + H] + ＝379.96)。
The nuclear magnetic data of the intermediate C-80 is shown in the attached figure 1.
Step 2:
N 2 under protection, intermediate C-80 (60 mmol), reactant D-80 (66 mmol), pd (OAc) 2 (1.2 mmol) and cesium carbonate (132 mmol) in X-Phos (6 mmol) were added to a mixed solvent of toluene, ethanol, water (240mL 2 And O, filtering after the solid is separated out, drying the filter cake, heating and dissolving the obtained solid by using methylbenzene, passing through a silica gel funnel while the solid is hot, and purifying the solid by using methanol: the obtained rotary evaporator was used as a developing agent to remove the solvent in a volume ratio of dichloromethane of 1] + ＝729.88)。
The nuclear magnetic data for compound 80 is shown in figure 2.
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Elemental analysis:
theoretical value: c,84.04; h,4.43; n,11.53
Test values are: c,83.86; h,4.51; n,11.73
Example 3: synthesis of Compound 113
Figure BDA0003961353450000281
CAS：A-113：1518823-39-6
CAS：B-113：892550-44-6
Step 1:
N 2 under protection, a reactant A-113 (100 mmol), a reactant B-113 (120 mmol) and Pd (PPh) 3 ) 4 (tetrakis (triphenylphosphine) palladium) (1 mmol) and K 2 CO 3 (potassium carbonate) (220 mmol) was added to toluene, ethanol, water (450 mL:150ml), heating to 90 ℃, reacting for 8h, using diatomite to pump and filter while hot, removing salt and catalyst, cooling filtrate to room temperature, using rotary evaporator to remove solvent, drying obtained solid, passing through silica gel funnel, adding dichloromethane: petroleum ether volume ratio of 1] + ＝521.06)。
And 2, step:
after adding intermediate C-113 (70 mmol) and reactant D-113 (77 mmol) in xylene (350 mL) to the reaction vessel, 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 hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of the components is 1:3 dichloromethane and petroleum ether as eluent, and column chromatography to obtain compound 113 (40.27 g, yield: 88%, test value MS (ESI, M/Z): M + H] + ＝653.78)。
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Elemental analysis:
theoretical value: c,82.80; h,4.32; n,12.87
Test values: c,82.70; h,4.38; n,12.98
Example 4: synthesis of Compound 117
Figure BDA0003961353450000301
Step 1:
the intermediate C-117 is the same substance as the intermediate C-8 of example 1, and the reaction is the same and is not repeated. 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 species as compound 8 of example 1, and the reaction is the same 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.
And step 3:
adding the intermediate E-117 (112 mmol) into a reaction vessel, adding 560mL of DMF and 56mL of acetic acid, stirring, adding NBS (123.2 mmol), heating to 100 ℃, reacting overnight, cooling to room temperature after the reaction is finished, adding deionized water, stirring, performing suction filtration, sequentially leaching a filter cake with water and ethanol, drying the obtained solid, passing through a silica gel funnel, removing the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the 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.
And 4, 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, water (300100100ml), warmed to 90 ℃, reacted for 8h, filtered with celite while hot to remove salts and catalyst, the filtrate was cooled to room temperature and the solvent was removed using a rotary evaporator, the resulting solid was dried and filtered through a silica gel funnel with dichloromethane: petroleum ether volume ratio of 1]+＝653.78)。
The nuclear magnetic data of compound 117 is shown in figure 6.
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.7 percent.
Elemental analysis:
theoretical value: c,82.80; h,4.32; n,12.87
Test values are: c,82.68; h,4.38; n,13.02
Example 5: synthesis of Compound 127
Figure BDA0003961353450000321
CAS: reactant D-127:693774-10-6
Step 1:
the intermediate C-117 is the same as the intermediate C-8 of example 1, and the reaction is the same and is not repeated. 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 cesium carbonate (294 mmol) in X-Phos (14 mmol) were added to a mixed solvent of toluene, ethanol, water (450mL 2 And O, filtering after the solid is separated out, drying the filter cake, heating and dissolving the obtained solid by using methylbenzene, passing through a silica gel funnel while the solid is hot, and purifying the solid by using methanol: dichloromethane volume ratio of 1]+＝591.77)。
And step 3:
adding the intermediate E-127 (112 mmol) into a reaction vessel, adding 560mL of DMF and 56mL of acetic acid, stirring, adding NBS (123.2 mmol), heating to 100 ℃, reacting overnight, cooling to room temperature after the reaction is finished, adding deionized water, stirring, performing suction filtration, sequentially leaching a filter cake with water and ethanol, drying the obtained solid, passing through a silica gel funnel, removing the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the intermediate F-127 (45.07, yield: 60%, test value MS (ESI, M/Z): M + H ] + = 670.65).
And 4, step 4:
after adding intermediate F-127 (60 mmol) and reactant G-127 (66 mmol) in toluene in a reaction vessel, pd is added under the protection of 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 diatomite while hot, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, retaining 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 of 1:4 dichloromethane, petroleum ether as eluent, column chromatography was used to purify the remaining material to obtain compound 127 (36.88 g, yield: 81%, test value MS (ESI, M/Z): M + H]+＝758.93)。
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Elemental analysis:
theoretical value: c,82.41; h,4.65; n,12.94
Test values are: c,82.25; h,4.71; n,13.13
Example 6: synthesis of Compound 135
Figure BDA0003961353450000341
CAS: reactant A-135:329214-79-1
CAS: reactant B-135:2649616-14-6
Step 1:
N 2 under protection, a reactant A-135 (200 mmol), a reactant B-135 (240 mmol) and 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, water (900ml 300ml), heated to 90 ℃, reacted for 8 hours, filtered with celite while hot to remove salts and catalyst, and the filtrate was cooledAfter cooling to room temperature, the solvent was removed using a rotary evaporator and the resulting solid was dried and filtered through a silica gel funnel with a dichloromethane: petroleum ether volume ratio of 1]+＝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 cesium carbonate (294 mmol) in X-Phos (14 mmol) were added to a mixed solvent of toluene, ethanol, water (450mL 2 And O, filtering after the solid is separated out, drying the filter cake, heating and dissolving the obtained solid by using methylbenzene, passing through a silica gel funnel while the solid is hot, and purifying the solid by using methanol: dichloromethane volume ratio of 1]+＝563.70)。
And step 3:
intermediate E-135 (112 mmol) was added to the reaction vessel followed by 560mL of DMF and 56mL of acetic acid and stirred, NBS (123.2 mmol) was added and heated to 100 ℃ overnight, after completion cooled to room temperature, deionized water was added and stirred, suction filtration was performed, the filter cake was rinsed with water and ethanol in sequence, the resulting solid was dried and passed through a silica gel funnel, the filtrate was removed by a rotary evaporator and the resulting solid was dried to give intermediate F-135 (38.80 g, yield: 54%, test value MS (ESI, M/Z): M + H + = 641.59).
And 4, step 4:
after adding intermediate F-135 (60 mmol) and reactant G-135 (66 mmol) in toluene in a reaction vessel, pd is added under nitrogen protection 2 (dba) 3 (0.6mmol)、P(t-Bu) 3 (1.2 mmol), t-BuONa (132 mmol); after addition, the reaction temperature was slowly raised to 90 ℃ and the mixture was stirred for 8h; filtering with diatomaceous earth, removing salt and catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate, washing, separating, and keeping the organic phaseExtracting the 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 of the components is 1:4 dichloromethane and petroleum ether as eluent, and column chromatography to obtain compound 135 (35.03 g, yield: 80%, test value MS (ESI, M/Z): M + H]+＝729.88)。
The yield in each step is the fractional yield of the corresponding step.
And (3) characterization:
HPLC purity: is more than 99.8 percent.
Elemental analysis:
theoretical value: c,82.28; h,4.28; n,13.43
Test values are: c,82.09; h,4.36; n,13.62
Examples 7 to 46
The synthesis of the following compounds, whose molecular formulae and mass spectrum data are shown in table 1 below, was accomplished with reference to the synthesis methods of examples 1 to 6.
TABLE 1 molecular formulae and Mass Spectrometry
Figure BDA0003961353450000361
Figure BDA0003961353450000371
In addition, other compounds of the present application can be obtained by the synthetic methods according to the above-mentioned examples, and therefore, they are not illustrated herein.
An organic electroluminescent device may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emission auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a cap layer, and the like as organic layers. However, the structure of the organic light emitting element is not limited thereto, and a smaller or larger number of organic layers may be included.
According to one embodiment of the present specification, the organic layer has an electron transport layer, and the compound represented by formula I prepared herein is used as an electron transport layer material.
The compound represented by formula I may be formed into an organic layer by a vacuum deposition method or a solution coating method in the production of an organic light-emitting device. The solution coating method is not limited to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like.
The light emitting device of the present application may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
The device described herein may be used in an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor.
The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the anode material usable in the present application include metals such as vanadium, chromium, copper, zinc, and gold, or 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 a metal such as Sb and an oxide; and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer is preferably a p-doped hole injection layer, which means a hole injection layer doped with a p-dopant. A p-dopant is a material capable of imparting p-type semiconductor properties. The p-type semiconductor characteristics mean the characteristics of injecting holes or transporting holes at the HOMO level, that is, the characteristics of a material having high hole conductivity.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and has high hole mobility. The hole transport material may be selected from arylamine derivatives, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.
An emission auxiliary layer (a multi-layer hole transport layer) is added between the hole transport layer and the light emitting layer. The light-emission auxiliary layer mainly functions as an auxiliary hole transport layer, and is therefore sometimes 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 so as to limit the electrons in the light-emitting layer, reduce a potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, further increase the utilization rate of the holes, and improve the light-emitting efficiency and the service life of the device.
The light-emitting substance in the light-emitting layer is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light region, and is preferably a substance having high quantum efficiency with respect to 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) to (0.5-10).
The host material includes aromatic fused ring derivatives, heterocyclic compounds, and the like. Specifically, as the aromatic condensed ring derivative, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like; examples of the heterocyclic group-containing compound include carbazole derivatives, dibenzofuran derivatives, and pyrimidine derivatives.
The dopant material herein includes fluorescent doping and phosphorescent doping, and may be selected from aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
The electron transport layer may function to facilitate electron transport. The electron transport material is a material that facilitates receiving electrons from the cathode and transporting the electrons to the light emitting layer, and is preferably a material having 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 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. Examples of the material of the electron injection layer include, but are not limited to, metals such as oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and derivatives thereof, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and ytterbium, alloys thereof, metal complexes, and nitrogen-containing 5-membered ring derivatives thereof.
The cathode is generally preferably a material having a small work function so that electrons are smoothly injected into the organic material layer, the layer preferably having a layer thickness of between 0.5 and 5 nm. The cathode material is preferably a material having a small work function in order to easily inject 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, or alloys thereof: liF/A1 or LiO 2 Multilayer structure materials such as/A1, mg/Ag, and the like.
There is no particular limitation on the materials of the other layers in the 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.
The following describes a light emitting device provided in the present application with reference to specific embodiments.
Application example 1 preparation of organic electroluminescent device:
a. an 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, ultrasonically washing for 30min, repeatedly washing for 2 times by using distilled water, ultrasonically washing for 10min, transferring to a spin dryer for spin-drying after washing is finished, baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003961353450000401
Vacuum evaporation of hole injection layer materials HT and P-dopant, of formula shown below. The evaporation rate ratio of HT to P-dopant is 98:2, the thickness is 10nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003961353450000402
The evaporation rate of (3), and evaporating 120nm HT as a hole transport layer on the hole injection layer in vacuum;
d. prime (luminescence auxiliary layer): to be provided with
Figure BDA0003961353450000403
The evaporation rate of (2), 5nm of prime is evaporated on the hole transport layer in vacuum to be used as a luminescence auxiliary layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003961353450000404
The chemical formula of Host and Dopant (span) is shown below, and the Host material (Host) and Dopant (span) are vacuum-deposited to a thickness of 25nm as the light-emitting layer. Wherein the evaporation rate ratio of Host to Dopant is 95:5.
f. HB (hole blocking layer): to be provided with
Figure BDA0003961353450000405
The hole-blocking layer having a thickness of 5.0nm was vacuum-deposited at the deposition rate of (2).
g. ETL (electron transport layer): to be provided with
Figure BDA0003961353450000406
The evaporation rate of (3), and compound 1 and Liq as electron transport layers, which had a thickness of 35nm, were vacuum evaporated. Wherein the evaporation rate ratio of compound 1 to Liq is 50:50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003961353450000407
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003961353450000411
The evaporation rate ratio of (1) to (9) is 1.
j. Light extraction layer: to be provided with
Figure BDA0003961353450000412
CPL was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer.
k. And packaging the substrate subjected to evaporation. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
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)。
Figure BDA0003961353450000413
application examples 2 to 46
The organic electroluminescent devices of application examples 2 to 46 were prepared according to the above-described method for preparing an organic electroluminescent device, except that the compound 1 in 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 method for preparing an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 1, wherein comparative compound 1 has the following structural formula:
comparative example 2
An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 2, wherein comparative compound 2 has the following structural formula:
comparative example 3
The organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 3, wherein comparative compound 3 has the following structural formula:
comparative example 4
An organic electroluminescent device was prepared according to the above-described method for preparing an organic electroluminescent device, except that compound 1 in application example 1 was replaced with comparative compound 4, wherein comparative compound 4 has the following structural formula:
Figure BDA0003961353450000421
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 the following table 2:
TABLE 2 test results of luminescence characteristics (brightness 1000 nits)
Figure BDA0003961353450000431
Figure BDA0003961353450000441
As known to those skilled in the art, the blue organic electroluminescent device is affected by the microcavity effect, and the luminous efficiency is greatly affected by the chromaticity, so the BI value is introduced as the basis of the efficiency of the blue light emitting material, and BI = luminous efficiency/CIEy. Also, in the art, the problems of short lifetime and low efficiency of the blue light device have been one of the problems to be solved urgently by those skilled in the art.
As can be seen from table 2, the light emitting devices prepared using the electron transport material provided in the present application, application examples 1 to 46, were improved in driving voltage, luminous efficiency, BI and lifetime compared to the conventional organic electroluminescent devices provided in comparative examples 1 to 4.
From the device effect, when the number of the substituent groups on the phenanthrene is 3, the service life is obviously prolonged, and the luminous efficiency is improved. When the number of the substituents on the phenanthrene is 2, the luminous efficiency is obviously improved, compared with a compound 1 and a compound 29, the luminous efficiency of the device is improved by 7% due to the existence of the polyazacarbazole, and the luminous efficiency is obviously improved on a blue light device in the field.
In particular, triazine, pyridine and pyrimidine are functional groups with strong electron-withdrawing ability, so that the electron mobility of the electron transport material can be effectively improved; and the specific functional group containing the polynitrogen heterocarbazole is used for further improving the electron mobility of the electron transport material, solving the problem of unbalanced electron-hole in the organic electroluminescent device, ensuring high three linear state energy levels (ET) and wide band gap of the material, 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-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. An electron transport material having a structural formula as shown in formula I:
Figure FDA0003961353440000011
wherein R is 1 Independently selected from hydrogen, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, fluorenyl, phenanthryl, pyridyl and one of the following groups:
Figure FDA0003961353440000012
* Represents a group attachment position;
l is one of a connecting bond, phenyl, biphenyl, naphthyl, terphenyl, phenanthryl, methylphenyl, phenylnaphthyl, fluorenyl, cyanophenyl, phenylpyridyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, pyrimidinyl, quinolinyl and quinoxalinyl;
Z 1 -Z 4 independently selected from C and N, wherein the number of N is 1 or 2;
Z 5 -Z 8 independently selected from C and N, wherein the number of N is 1 or 2;
Ar 1 ，Ar 2 each independently selected from substituted or unsubstituted C6-C24 aryl and substituted or unsubstituted C6-C24 heteroaryl, and the heteroatom is N, O or S.
2. The electron transport material of claim 1, wherein Ar is 1 ，Ar 2 When substituted or unsubstituted C6-C24 heteroaryl, each is independently selected from substituted or unsubstituted pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, isoquinolyl, acridinyl, benzofuryl, benzothienyl, benzimidazolyl, benzothiazolyl, benzotriazolyl, benzooxadiazolyl, benzoxazolyl, cinnoline, quinoxalinyl, dibenzofuryl, dibenzothienyl, phenylpyridinyl, phenylcarbazolyl, carbazoleOne of a group selected from phenanthroline group, indolizinyl group, naphthyridinyl group, phenylpyridyl group, phenylpyrimidinyl group, phthalazinyl group, 9-dimethyl-9 h-xanthene and 9-phenyl-9 h-carbazole.
3. The electron transport material of claim 1 or 2, wherein the Ar is 1 ，Ar 2 And when the aryl group is a substituted or unsubstituted C6-C24 aryl group, the aryl group is one selected from substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, phenanthryl, anthryl, pyrenyl, spirobifluorenyl, 9-dimethylfluorenyl, diphenyl fluorenyl, perylene, indenyl, azulenyl, benzophenanthryl, methylphenyl, ethylphenyl, methoxyphenyl and cyanophenyl.
4. The electron transport material of claim 1, wherein the electron transport material has a structure selected from the group consisting of structures represented by formula (1) to formula (17):
Figure FDA0003961353440000031
5. the electron transport material of claim 1 or 4, wherein L is selected from one of a linkage, phenyl, biphenyl, naphthyl.
6. The electron transport material of claim 1, wherein Ar is 1 ，Ar 2 One selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, phenylpyridyl, carbazolyl, 9-dimethyl-9 h-xanthene and 9-phenyl-9 h-carbazole.
7. The electron transport material of claim 1, wherein the electron transport material is any one of the following structures:
Figure FDA0003961353440000051
Figure FDA0003961353440000061
Figure FDA0003961353440000071
Figure FDA0003961353440000081
Figure FDA0003961353440000091
Figure FDA0003961353440000101
Figure FDA0003961353440000111
8. the method for producing an electron transport material according to any of claims 1 to 7,
when R is 1 In the case of hydrogen, the preparation method of the electron transport material comprises the following steps:
Figure FDA0003961353440000112
Hal 1 selected from Br, I;
N 2 under protection, reactants A-I, reactants B-I, tetrakis (triphenylphosphine) palladium and carbonic acidRespectively adding potassium 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 adding the intermediate C-I and the reactant D-I into the reaction vessel and dissolving in xylene, pd (OAc) is added under the protection of nitrogen 2 Heating the reaction temperature to 130-140 ℃, stirring and mixing for 8-12h to obtain a compound shown in a general formula I;
or,
Figure FDA0003961353440000121
Hal 1 selected from Br, I;
after reactants A-I and B-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 Heating the reaction temperature to 80-90 ℃, and stirring and mixing for 8-12h to obtain an intermediate C-I;
N 2 under protection, respectively adding the intermediate C-I, the reactant D-I, palladium acetate, 2-cyclohexyl-2, 4, 6-triisopropylbiphenyl 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:
Figure FDA0003961353440000131
Hal 1 selected from Br, I;
N 2 under protection, adding the reactant A-I, the reactant B-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
after adding the intermediate C-I and the reactant D-I into the reaction vessel and dissolving in xylene, pd (OAc) is added under the protection of nitrogen 2 X-Phos, t-BuONa; the reaction temperature is raised to 130-140 ℃,stirring and mixing for 8-12h to obtain an intermediate E-I;
adding the intermediate E-I into a reaction vessel, 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 protection, respectively adding the intermediate F-I, the reactant G-I, the tetrakis (triphenylphosphine) palladium and the 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,
Figure FDA0003961353440000141
N 2 under protection, adding the reactant A-I, the reactant B-I, tetrakis (triphenylphosphine) palladium and potassium carbonate into a mixed solvent of toluene, ethanol and water respectively, heating to 80-90 ℃, and reacting for 8-12h to obtain an intermediate C-I;
N 2 under protection, the intermediate C-I, the reactant D-I and 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 vessel, then adding DMF and acetic acid, stirring, adding NBS, heating to 100-140 ℃, and reacting overnight to obtain an intermediate F-I;
after adding intermediate F-I and reactant G-I into a reaction vessel and dissolving in toluene, pd is added under the protection of nitrogen 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 80-90 ℃, and stirring and mixing for 8-12h to obtain the compound shown in the general formula I.
9. A light-emitting device characterized in that it comprises the electron transporting material according to any one of claims 1 to 7.
10. A light-emitting apparatus characterized by comprising the light-emitting device according to claim 9.
CN202211484361.9A 2022-11-24 2022-11-24 Electron transport material, preparation method thereof, light-emitting device and light-emitting device Active CN115894491B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211484361.9A CN115894491B (en) 2022-11-24 2022-11-24 Electron transport material, preparation method thereof, light-emitting device and light-emitting device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211484361.9A CN115894491B (en) 2022-11-24 2022-11-24 Electron transport material, preparation method thereof, light-emitting device and light-emitting device

Publications (2)

Publication Number Publication Date
CN115894491A true CN115894491A (en) 2023-04-04
CN115894491B CN115894491B (en) 2024-03-26

Family

ID=86474229

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211484361.9A Active CN115894491B (en) 2022-11-24 2022-11-24 Electron transport material, preparation method thereof, light-emitting device and light-emitting device

Country Status (1)

Country Link
CN (1) CN115894491B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486817A (en) * 2024-01-02 2024-02-02 吉林奥来德光电材料股份有限公司 Organic electroluminescent material and preparation method and application thereof
CN117777038A (en) * 2024-02-28 2024-03-29 吉林奥来德光电材料股份有限公司 Organic electroluminescent material, preparation method thereof and organic electroluminescent device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017074052A1 (en) * 2015-10-27 2017-05-04 주식회사 엘지화학 Organic light-emitting device
KR20170135669A (en) * 2016-05-30 2017-12-08 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
CN109810123A (en) * 2017-11-21 2019-05-28 北京鼎材科技有限公司 Compound and its application in organic light emission field
CN113121572A (en) * 2019-12-30 2021-07-16 陕西莱特光电材料股份有限公司 Heterocyclic compound, organic electroluminescent device, and electronic apparatus
CN116283982A (en) * 2022-09-07 2023-06-23 吉林奥来德光电材料股份有限公司 Nitrogen-containing heterocyclic organic electroluminescent material and organic electroluminescent device comprising same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017074052A1 (en) * 2015-10-27 2017-05-04 주식회사 엘지화학 Organic light-emitting device
CN108349913A (en) * 2015-10-27 2018-07-31 株式会社Lg化学 Compound and organic luminescent device comprising it
KR20170135669A (en) * 2016-05-30 2017-12-08 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
CN107445945A (en) * 2016-05-30 2017-12-08 株式会社Lg化学 Heterocyclic compound and the organic illuminating element for including it
CN109810123A (en) * 2017-11-21 2019-05-28 北京鼎材科技有限公司 Compound and its application in organic light emission field
CN113121572A (en) * 2019-12-30 2021-07-16 陕西莱特光电材料股份有限公司 Heterocyclic compound, organic electroluminescent device, and electronic apparatus
CN116283982A (en) * 2022-09-07 2023-06-23 吉林奥来德光电材料股份有限公司 Nitrogen-containing heterocyclic organic electroluminescent material and organic electroluminescent device comprising same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486817A (en) * 2024-01-02 2024-02-02 吉林奥来德光电材料股份有限公司 Organic electroluminescent material and preparation method and application thereof
CN117486817B (en) * 2024-01-02 2024-05-28 吉林奥来德光电材料股份有限公司 Organic electroluminescent material and preparation method and application thereof
CN117777038A (en) * 2024-02-28 2024-03-29 吉林奥来德光电材料股份有限公司 Organic electroluminescent material, preparation method thereof and organic electroluminescent device
CN117777038B (en) * 2024-02-28 2024-05-28 吉林奥来德光电材料股份有限公司 Organic electroluminescent material, preparation method thereof and organic electroluminescent device

Also Published As

Publication number Publication date
CN115894491B (en) 2024-03-26

Similar Documents

Publication Publication Date Title
CN111094302B (en) Polycyclic compound and organic light emitting device including the same
CN109476682B (en) Compound and organic light-emitting element comprising same
CN107428769B (en) Heterocyclic compound and organic light-emitting element comprising same
JP2021504373A (en) Heterocyclic compounds and organic light emitting devices containing them
KR20200041804A (en) Organic light emitting device
CN115745977B (en) Electron transport material, preparation method thereof and organic electroluminescent device
CN113166120B (en) Compound and organic light emitting device comprising the same
CN115894491B (en) Electron transport material, preparation method thereof, light-emitting device and light-emitting device
CN107652295B (en) Indolocarbazole-based compound and organic light-emitting element including same
KR102125619B1 (en) New compound and organic light emitting device comprising same
CN114716330A (en) Luminescent auxiliary material, preparation method and application thereof
KR101980730B1 (en) Nitrile based compound and organic light emitting device comprising the same
CN115417861B (en) Electron transport material, preparation method thereof, organic electroluminescent device comprising electron transport material and application of organic electroluminescent device
CN113875034A (en) Organic light emitting device
CN107257787B (en) Heterocyclic compound and organic light-emitting element comprising same
CN111225905A (en) Heterocyclic compound and organic light emitting device including the same
CN115872959A (en) Luminous auxiliary material, preparation method and application thereof, and luminous device
CN111556865A (en) Polycyclic compound and organic electronic device comprising same
KR20190044561A (en) Multicyclic compound and organic light emitting device comprising the same
CN115557909A (en) Electron transport organic electroluminescent compound and organic electroluminescent device comprising same
CN113336771A (en) Condensed ring carbazole derivative and organic electroluminescent device thereof
CN112105613B (en) Compound and organic light emitting device comprising the same
CN116283982B (en) Nitrogen-containing heterocyclic organic electroluminescent material and organic electroluminescent device comprising same
CN112105614A (en) Compound and organic light emitting device including the same
CN114751888A (en) Electron transport material, preparation method thereof, light-emitting device and light-emitting device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant