CN115109039B - Carbazole derivative and application thereof in OLED - Google Patents

Carbazole derivative and application thereof in OLED Download PDF

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CN115109039B
CN115109039B CN202210823591.7A CN202210823591A CN115109039B CN 115109039 B CN115109039 B CN 115109039B CN 202210823591 A CN202210823591 A CN 202210823591A CN 115109039 B CN115109039 B CN 115109039B
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organic electroluminescent
organic
carbazole derivative
substituted
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CN115109039A (en
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曹建华
谢佩
杨美跃
李留洋
王振宇
唐伟
姜坤
刘赛赛
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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Abstract

The present invention relates to carbazole derivatives and their use in Organic Light Emitting Diodes (OLEDs). The carbazole derivative has a condensed carbazole structure and a high triplet state energy level, and the conjugation of a carbazole parent nucleus is increased, so that the thermal stability of the material and the capability of transporting carriers are improved. The carbazole derivative is applied to an organic electroluminescent element, and can remarkably reduce driving voltage, improve luminous efficiency and prolong service life. The structural formula of the carbazole derivative is shown as a formula (I).

Description

Carbazole derivative and application thereof in OLED
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a carbazole derivative and application thereof in an Organic Light Emitting Diode (OLED).
Background
In general, an organic light emitting phenomenon refers to a phenomenon that emits light when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technology has tended to mature, and some products have entered the market, but in the industrialization process, many problems still remain to be solved. In particular, various organic materials for manufacturing elements, which have carrier injection and transport properties, material electroluminescent properties, service life, color purity, matching between various materials and between various electrodes, and the like, have not been solved; in particular, the luminous efficiency and the service life of the light-emitting element do not meet the practical requirements, which greatly limits the development of OLED technology. While the metal complex phosphorescent material using triplet light emission has high light emission efficiency, its green and red light materials have reached the use requirements, but the metal complex phosphorescent material requires a phosphorescent material having a high triplet energy level or a hole material to match it. Therefore, the development of phosphorescent materials or hole materials having high triplet energy levels is an urgent need for the development of current OLEDs.
Under current technological development, improvements are still needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and in terms of thermal stability during sublimation.
In view of this, the present invention has been made.
Disclosure of Invention
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as a phosphorescent material or a hole material in the organic electroluminescent element has been continuously demanded.
The invention provides a carbazole derivative, which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by the carbazole derivative can obviously reduce driving voltage, improve luminous efficiency and prolong service life.
The structural formula of the carbazole derivative is shown as a formula (I):
wherein,
L 1 selected from single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A heteroarylene group;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 the same or different radicals are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 1 -C 40 Alkoxy, C 2 -C 40 Alkenyl, C 1 -C 40 Alkylthio, C 1 -C 40 Alkoxy, C 3 -C 40 Cycloalkyl, C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron, substituted or unsubstituted amine, substituted or unsubstituted aryl phosphine, substituted or unsubstituted phosphine oxide, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
n represents an integer of 0 to 5;
Ar 1 selected from the group consisting of substituted and unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group.
Preferably, said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazole, dibenzofuran, or dibenzothiophene.
Preferably, the Ar 1 A group selected from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, benzine, terphenyl, tetrabiphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, trimeric indene, heterotrimeric indene, spiro-trimeric indene, spiro-heterotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo [5,6]Quinoline, benzo [6,7]Quinoline, benzo [7,8]Quinoline, phenothiazine, phenoxazine, and pyrazineOxazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthrooxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazaanthracene, 2, 7-diazapyrene, 2, 3-diazapyrene, 1, 6-diazapyrene, 1, 8-diazapyrene, 4, 5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorored, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 5-tetrazine, 1,2, 5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole, or a combination of groups derived from these.
Preferably, n is selected from 0, 1 or 2.
Preferably, the Ar 1 Selected from the group consisting of the groups shown in II-1 to II-17 below:
wherein,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Naphthene radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represent O, S, CR 'R "or NAr';
r ', R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl, R' and R "may optionally be joined or fused to form another one or more substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R "is methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Heteroalkyl of (C) 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; preferably Ar' is methyl, ethyl, phenyl, biphenyl or naphthyl.
Preferably, the L 1 Selected from the group consisting of the groups indicated by III-1 to III-15 below:
wherein,
Z 11 、Z 12 each independently selected from hydrogen, deuterium hydrogen, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or carboxylate thereofSulfonate, phosphate group or phosphate, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Naphthene radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 One or more of the heterocyclic aryl groups;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5;
T 3 represents O or S;
it should be emphasized that, in the present invention,ar is represented by 1 And L is equal to 1 Or a N-linked bond; "-" and "-" denote a bond.
It is emphasized that the term "substituted or unsubstituted" in the present invention means that it is selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or carboxylate thereof, sulfonic acid group or sulfonate thereof, phosphoric acid group or phosphate thereof, C 1 -C 60 Alkyl, C 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Cycloalkyl, C 3 -C 60 Cycloalkenyl, C 6 -C 60 Aryl, C 6 -C 60 Aryloxy, C 6 -C 60 Aryl sulfide group and C 2 -C 60 Heterocyclic aromaticMore than 1 substituent in the groups is substituted or unsubstituted, or a substituent in which more than 2 substituents in the above-exemplified substituents are linked is substituted or unsubstituted.
Preferably, the carbazole derivative is selected from compounds represented by the following formulas M470-M622:
wherein-g— is selected from-O-, S-, or one of the following structures:
based on the same technical concept, the invention further provides a preparation method of the carbazole derivative, as shown in scheme 1.
Scheme 1:
in scheme 1, the symbols used are as defined in formula (I), and Y 1 、Y 2 、Y 3 、Y 4 Each independently selected from Cl, br, I, or OTf;
the raw materials for synthesizing the compound shown in the formula (I) can be purchased through commercial paths, and the method principles, the operation process, the conventional post-treatment, the column purification, the recrystallization purification and other means are well known to the synthesis personnel in the field, so that the synthesis process can be completely realized to obtain the target product.
In particular, the compound of formula (I) is represented by 3-R 1 Substituted-5-halogenated carbazoles I-0 and R 2 Carrying out substitution reaction on the phenylacetylene to prepare an intermediate I-1; intermediate I-1 is subjected to ring closure reaction to prepare intermediate I-2; carrying out halogenation reaction on the carbazole intermediate I-2 to obtain I-3; the dihalogenated intermediate I-3 and the substituted 1-naphthalene boric acid are subjected to coupling reaction to prepare the condensed carbazole mother nucleus I-4; intermediates I-4 and Ar 1 -(L 1 )n-Y 4 And (3) performing a coupling reaction to prepare the compound shown as the formula (I). Intermediate Ar 1 -(L 1 )n-Y 4 Prepared by palladium-catalyzed or base-catalyzed coupling reactions.
The palladium catalyst which can be used for the palladium-catalyzed coupling reaction may be selected from: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/C、PdCl 2 、[Pd(allyl)Cl] 2 Or the like, or a mixture of two or more kinds thereof.
In addition, the base used for palladium-catalyzed or base-catalyzed coupling reactions may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amyl alcohol, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, or a mixture of two or more thereof.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from the group consisting of: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, and anisole, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and the like, and a mixture of one or more kinds of them may be used.
The invention also provides an organic electroluminescent material, which comprises the carbazole derivative as a raw material; and the organic electroluminescent material containing the carbazole derivative has the capacity of carrier transmission.
The invention also provides an application of the organic electroluminescent material in preparing the organic electroluminescent element.
The present invention also provides an organic electroluminescent element comprising: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the carbazole derivative described above.
The organic electroluminescent element comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may contain other layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and/or charge generation layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises a carbazole derivative according to the present invention.
Further, the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the electron blocking layer or hole transport layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, preference is given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process, wherein the sublimation process is carried out in a vacuum at a temperature of less than 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where at 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds the soluble compounds are obtained, for example, by suitable substitution of the compounds of formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition. These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a carbazole derivative comprising at least one of the above-indicated invention. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, the compounds may furthermore preferably comprise further compounds. Treatment of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires preparations of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, the raw materials used in the present invention are commercially available, and any range described in the present invention includes any value between the end values and any sub-range constituted by any value between the end values or any value between the end values.
The beneficial effects of the invention are as follows:
the carbazole derivative (shown in the formula (I)) has a high triplet state energy level, increases conjugation of a carbazole parent nucleus, improves material thermal stability and carrier conveying capacity, and can obviously reduce driving voltage, improve luminous efficiency and prolong service life when being applied to an organic electroluminescent element.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic view of an organic light emitting device 100. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the layers described.
Fig. 2 is a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first emissive layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second emissive layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the layers described. Because the most common OLED device has one light emitting layer, and device 200 has a first light emitting layer and a second light emitting layer, the light emitting peaks of the first and second light emitting layers may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: photoresearch PR-715 was tested using a spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: NEWPORT 1931-C test was used.
Example 1
A method for preparing compound M473 comprising the steps of:
the first step: preparation of intermediate Int-1
20.0mmol of 5-bromo-3-chlorocarbazole (reactant 1) was dissolved in 40mL of toluene and 20mL of triethylamine, and under nitrogen protection, 22.0mmol of trimethylsilylacetylene (reactant 2), 4.0mmol of cuprous iodide, 2.0mmol of PdCl were added 2 (PPh 3 ) 2 Reflux reaction is carried out for 24 hours at a temperature rise, the temperature is reduced to room temperature, the concentration is carried out under reduced pressure, and the residue is separated and purified by a silica gel column to obtain the compound Int-1 as a white solid with the yield of 42 percent.
And a second step of: preparation of intermediate Int-2
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 80mL of nitromethane and 20mL of THF, 60.0mmol of copper bromide and 10.0mmol of anhydrous potassium phosphate are added, stirring reaction is carried out at room temperature for 12 hours, 20mL of concentrated hydrochloric acid and 20mL of dichloromethane are added, stirring reaction is carried out for 1 hour, an organic phase is separated, drying, filtering and concentrating under reduced pressure, and the residue is separated and purified by a silica gel column to obtain a compound Int-2, white solid, and the yield is 84%.
Preparation of Compound B-1
Referring to the above-described similar synthetic method, the compound B-1 is prepared by replacing only trimethylsilylacetylene in the first step with aryl acetylene or alkyl acetylene or the like substituted acetylene, for example, phenylacetylene.
Preparation of Compound B-2
Referring to the similar synthetic method described above, compound B-2 was prepared by replacing only trimethylsilylacetylene in the first step with 3-pyridylacetylene.
And a third step of: preparation of intermediate Int-3
Under the protection of nitrogen, 10.0mmol of Int-2 is dissolved in 40mL of toluene, 20mL of ethanol and 20mL of water, and 12.0mmol of 1-naphthalene boric acid, 25.0mmol of anhydrous sodium carbonate and 1.0mmol of Pd (PPh) 3 ) 4 The mixture is heated, refluxed and stirred for reaction for 12 hours, 60mL of ethyl acetate and 20mL of water are added, an organic phase is separated, the water phase is extracted by ethyl acetate, the organic phase is dried and filtered, the filtrate is concentrated to dryness under reduced pressure, and the yellow solid Int-3 is obtained after separation and purification by a silica gel column, and the yield is 83%.
Fourth step: preparation of intermediate Int-4
Under the protection of nitrogen, 20.0mmol of Int-3 is dissolved in 200mL of dry THF, 0.1mol of metallic potassium is added, the temperature is raised, the reflux and stirring reaction is carried out for 20 hours, the temperature is reduced to room temperature, 20mL of tertiary butanol is added, the reaction solution is poured out to remove superfluous potassium, iodine is added to the solution in batches under stirring until the solution is purple, 50mL of saturated sodium thiosulfate aqueous solution is added, the EA is used for extraction, the organic phase is dried, filtered, concentrated to dryness under reduced pressure, and the mixture is separated and purified by a silica gel column to obtain yellow solid Int-4, and the yield is: 64%.
Fifth step: preparation of intermediate Int-5
Under the protection of nitrogen, 10.0mmol of intermediate Int-4 is dissolved in 40mL of dry DMF, the temperature is reduced to 0 ℃, 12.0mmol of 65% sodium hydride solid is added in batches, stirring reaction is carried out for 30 minutes, 11.0mmol of 2-chloro-4-biphenyl-6-phenyl-1, 3, 5-triazine (reactant 3) is added, stirring reaction is carried out for 12 hours at room temperature, the reaction solution is poured into 150mL of ice water, filtration is carried out, a filter cake is washed with water and ethanol, and separation and purification are carried out by a silica gel column to obtain yellow solid Int-5, and the yield is 79%.
Sixth step: preparation of Compound M473
10.0mmol of intermediate Int-5 was dissolved in 60mL of THF and 10mL of triethylamine, 0.5g of 10% palladium on carbon was added, hydrogen was introduced to 0.1MPa, the reaction was stirred at room temperature for 12 hours, filtration was carried out, the cake was washed with THF, the filtrate was concentrated to dryness under reduced pressure, separation and purification were carried out with a silica gel column, and recrystallization was carried out with toluene/THF to give M473 as a yellow solid in 98% yield, MS (MALDI-TOF): m/z=623.2243 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：8.56(1H,s)；8.35～8.32(2H,m)；8.21～8.13(3H,m)；7.95～7.89(3H,m)；7.75～7.72(2H,m)；7.65～7.63(2H,m)；7.51～7.42(8H,m)；7.40～7.36(3H,m)；7.27～7.24(2H,m)。
Referring to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Example 2
A process for the preparation of compound M522 comprising the steps of:
the first step: preparation of intermediate Int-6
Under the protection of nitrogen, 20.0mmol of Int-4 (reactant 1), 22.0mmol of phenylboronic acid (reactant 2), 45.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd0132, 40mL of toluene, 20mL of ethanol and 20mL of water are mixed, the mixture is heated to reflux and stirred for reaction for 12 hours, cooled to room temperature, 50mL of water is added, EA is used for extraction, an organic phase is dried, filtered, concentrated to dryness under reduced pressure, and separated and purified by a silica gel column to obtain yellow solid Int-6, and the yield: 87%.
Referring to the above-described analogous synthetic methods, the following compounds were prepared:
and a second step of: preparation of Compound M522
Under the protection of nitrogen, 10.0mmol of intermediate Int-6 is dissolved in 40mL of dry DMSO, 12.0mmol of 65% sodium hydride solid is added, stirring reaction is carried out for 30 minutes, 12.0mmol of 2-chloro-4-naphthyl-6-phenyl-1, 3, 5-triazine (reactant 3) is added, heating is carried out to 45 ℃, stirring reaction is carried out for 12 hours, cooling is carried out to room temperature, reaction solution is poured into 150mL of ice water, filtration is carried out, filter cakes are washed with water and ethanol, separation and purification are carried out by a silica gel column, toluene/THF recrystallization are carried out, yellow solid M522 is obtained, yield is 87%, MS (MALDI-TOF): m/z=673.2406 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：8.93(1H,s)；8.58～8.52(5H,m)；8.48～8.41(2H,m)；8.15～8.11(2H,m)；8.04～8.02(1H,d)；7.86～7.75(7H,m)；7.62～7.51(4H,m)；7.45～7.35(6H,m)。
Referring to the above synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
Example 3
A process for the preparation of compound M573 comprising the steps of:
the first step: preparation of intermediate Int-7
10.0mmol of intermediate Int-4 (reactant 1) is dissolved in 40mL of THF and 10mL of triethylamine, 0.2g of 10% palladium/carbon is added, hydrogen is introduced to 0.1MPa, the mixture is stirred at room temperature for reaction for 12 hours, filtration is carried out, a filter cake is washed with THF, the filtrate is concentrated to dryness under reduced pressure, separation and purification are carried out by a silica gel column, and then toluene/THF recrystallization is carried out, so that the compound Int-7 is obtained, and the yield is 100%.
And a second step of: preparation of Compound M573
Under the protection of nitrogen, 10.0mmol of intermediate Int-7 is dissolved in 50mL of dried xylene, and 12.0mmol of 2- ([ 1,1' -biphenyl) is added]-3-yl) -4- (2-bromophenyl) -6-phenyl-1, 3, 5-triazine (reactant 2), 15.0mmol sodium t-butoxide, 0.1mmol Pd 2 (dba) 3 And 0.2mmol XPhos, raise the temperature to 110 ℃ and stir for reaction for 12 hours, cool to room temperature, add 50mL water, filter, wash the filter cake with water, ethanol, separate and purify with silica gel column, re-crystallize with dichloromethane/THF to give yellow solid M573, yield 87%, MS (MALDI-TOF): m/z=699.2562 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：9.12(1H,s)；8.36～8.32(3H,m)；8.21～8.14(3H,m)；7.99～7.97(1H,m)；7.94～7.89(3H,m)；7.81～7.72(4H,m)；7.66～7.59(3H,m)；7.49～7.36(9H,m)；7.34～7.29(3H,m)。
Referring to the above synthetic method, the following compounds shown in table 4 were prepared:
TABLE 4 Table 4
In the above embodiments 1 to 3, -G-, is selected from one of-O-, S-, or the following structures:
example 4
As shown in fig. 1, the OLED element of the present embodiment is a top-emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, an electron transport layer 107 disposed on the organic light emitting layer 106, an electron injection layer 108 disposed on the electron transport layer 107, a cathode layer 109 disposed on the electron injection layer 108, and a capping layer 110 disposed on the cathode 109, wherein the method for preparing the OLED element includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, depositing metallic silver as an anode layer on the ITO film, the thickness of the deposited film beingContinuing to evaporate the compounds HI01 and HI101 as hole injection layers respectively, wherein HI101 accounts for 3% of HI01, and the evaporated film thickness is +.>
3) Continuously evaporating a compound HTM102 as a hole transport layer on the hole injection layer to obtain an evaporated film thickness of
4) Continuously evaporating compound EBL as electron blocking layer on the hole injection layer to obtain an evaporating film thickness of
5) The compound of the present invention is a host material of formula (I) and RD012 is a dopant material, RD012 is 3% of the mass of formula (I) and is deposited on the electron blocking layer, the film thickness of the organic light-emitting layer obtained by vapor deposition is
6) Continuously evaporating an electron transport layer of LiQ and ET010 as elements on the organic light-emitting layer, wherein ET010 is 50% of LiQ by mass, and the evaporating film thickness is
7) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
8) Evaporating metal magnesium and silver on the electron injection layer to form a transparent cathode layer of the element, wherein the mass ratio of magnesium to silver is 1:10, and the film thickness of the evaporated film is
9) Evaporating an NPD CPL layer as element on the transparent cathode layer to obtain an evaporation film with a thickness ofThe OLED element provided by the invention is obtained.
The structure of the compound used in example 4 above is as follows:
example 5
An organic electroluminescent device 200, the structure of which is shown in fig. 2, comprises a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first luminescent layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second luminescent layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213.
Comparative example 1
By following the same procedure as in example 4, substituting the compound of formula I in step 5) with HS01, comparative element 1 was obtained;
comparative example 2
By following the same procedure as in example 4, substituting the compound of formula I in step 5) with HS02, comparative element 2 was obtained;
the organic electroluminescent element prepared by the above process was subjected to the following performance test:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent elements prepared in example 4 and comparative examples 1 and 2 were measured using a digital source meter and a luminance meter. Specifically, the luminance of the organic electroluminescent element was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; LT90% life test is as follows: at 1000cd/m using a luminance meter 2 Brightness of lightUnder the condition of keeping constant current, the brightness decay of the organic electroluminescent element is measured to be 900cd/m 2 Time in hours. The data listed in table 5 are relative data compared to comparative element 1.
TABLE 5
Wherein Ph represents a phenyl group; phPh represents biphenyl; nap represents naphthyl; FR represents a 9, 9-fluorenyl group.
As can be seen from Table 5, the device prepared from the compound of the present invention has a lower driving voltage than HS01, a significantly improved current efficiency up to as much as 1.2 times that of the comparative device, and a significantly improved LT90% lifetime of the device at the same luminance.
The compound HS01 of comparative example 1 is different from the compound of the present invention in that the benzocarbazole has weak planar conjugation ability, is unbalanced in the transport of holes and electrons, and has a stronger ability to accept holes than electrons, and such a transport imbalance affects the formation of excitons in the light emitting layer, resulting in high voltage, lower efficiency, and reduced lifetime. The compound of the invention is condensed with naphthalene ring on the basis of benzocarbazole, which increases plane conjugation of the mother nucleus, so that the compound has excellent performance in molecular film formation and charge transmission, more balanced charge transmission in the element and improved element performance.
The compound HS02 in comparative example 2 is different from the compound of the present invention in that HS02 is naphthocarbazole, and although the planar conjugation ability is enhanced, the planar conjugation ability is weak and the incorporation of naphthalene ring forms a large conjugated fused ring planar structure as compared with the fused carbazole compound of the present invention, so that it is excellent in both molecular film formation and charge transport, and the transport of charges in the element is more balanced, and in element performance, particularly, LT90% lifetime is much higher than that of the comparative element, and therefore the carbazole derivative of the present invention is an organic electroluminescent material excellent in performance.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (6)

1. A carbazole derivative, characterized in that the carbazole derivative is selected from compounds represented by the following formulae M470-M622:
wherein-g— is selected from-O-, S-, or one of the following structures:
。
2. an organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises the carbazole derivative as described in claim 1.
3. Use of the organic electroluminescent material as claimed in claim 2 for the preparation of an organic electroluminescent element.
4. An organic electroluminescent element, characterized in that the organic electroluminescent element comprises: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layers includes the carbazole derivative as claimed in claim 1.
5. The organic electroluminescent element according to claim 4, wherein the organic layer is a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
6. A consumer product comprising the organic electroluminescent element of claim 4 or 5.
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CN115109039B (en) * 2022-07-14 2024-02-02 上海八亿时空先进材料有限公司 Carbazole derivative and application thereof in OLED
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