CN114957226B - Phenanthridine derivative and application thereof - Google Patents

Phenanthridine derivative and application thereof Download PDF

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CN114957226B
CN114957226B CN202210651914.9A CN202210651914A CN114957226B CN 114957226 B CN114957226 B CN 114957226B CN 202210651914 A CN202210651914 A CN 202210651914A CN 114957226 B CN114957226 B CN 114957226B
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organic electroluminescent
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CN114957226A (en
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曹建华
冯静
张九敏
李程辉
刘殿君
唐伟
唐怡杰
王志杰
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a phenanthridine derivative and application thereof. The phenanthridine derivative with the structural formula shown in the formula (I) has a large plane structure of the phenanthridine bonded by the hetero atoms, increases the conjugated area of phenanthrene or aza-phenanthrene molecules, improves the thermal stability, film forming performance and carrier conveying capacity of the molecules, and can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life when being applied to an organic electroluminescent element.

Description

Phenanthridine derivative and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a phenanthridine derivative and application thereof.
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, the 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, green and red light materials thereof have reached the use requirements, the metal complex phosphorescent material requires a phosphorescent material or a hole material having a high triplet energy level to match with, and thus, development of a phosphorescent material or a hole material having a high triplet energy level is an urgent need for the current development of 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 order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, there is a need for the 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.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a phenanthridine derivative, which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by using the phenanthridine derivative can obviously reduce driving voltage, improve luminous efficiency and prolong service life; it is a further object of the present invention to provide the use of the compounds.
Specifically, the invention provides the following technical scheme:
the invention provides a phenanthridine derivative, which has a structural formula shown in 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 group consisting of heteroarylenes;
X 1 、X 2 、X 3 、X 4 、X 5 、X 6 each independently is N or CR 1 ；
Y is selected from O, S, CR 2 R 3 、SiR 4 R 5 Or NAr 2 ；
R 1 、R 2 、R 3 、R 4 、R 5 At each occurrence, the same or different radicals are selected from the group consisting of hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl, carboxylate, sulfonate, phosphate, 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 groupSubstituted or unsubstituted amino, substituted or unsubstituted aryl phosphino, substituted or unsubstituted phosphine oxide, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
Ar 1 、Ar 2 each independently selected from the group consisting of substituted or 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, the R 1 、R 2 、R 3 、R 4 、R 5 Each occurrence is independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
According to an embodiment of the invention, the R 1 Selected from hydrogen or deuterium.
According to an embodiment of the invention, the R 2 、R 3 、R 4 、R 5 Each independently selected from the group consisting of hydrogen, methyl, phenyl, fluorenyl.
Preferably, the Ar 1 、Ar 2 Each independently selected from the group consisting of: 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 and phenoxazinePyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, 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, 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, carboxylate, sulfonate, 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;
x1 is an integer from 1 to 4; x2 is an integer from 1 to 3; x3 is 1 or 2; x4 is an integer from 1 to 6; x5 is an integer from 1 to 5;
T 1 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 A heterocyclic aryl group, R' and R "optionally two or more groups adjacent to each other are 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;
is Ar (Ar) 1 And L is equal to 1 Is a connecting key of (a).
Preferably, in the above compound, 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 the group consisting of hydrogen, deuterium hydrogen, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl, carboxylate, sulfonate, 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 is 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 is an integer from 1 to 4; y2 is an integer from 1 to 6; y3 is an integer from 1 to 3; y4 is an integer from 1 to 5;
T 2 is a single bond, an oxygen atom or a sulfur atom;
is Ar with 1 Or a linkage of a phenanthridine main structure.
In the present invention, the term "substituted or unsubstituted" means that the compound is selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group, carboxylate group, sulfonate group, phosphate group, 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 More than 1 substituent in the heterocyclic aryl group is substituted or unsubstituted, or a substituent formed by connecting more than 2 substituents in the above-mentioned substituents is substituted or unsubstituted.
Preferably, the phenanthridine derivative is selected from the group consisting of compounds represented by the following formulas J383-J474:
wherein-y—isselected from-O-, S-, or one of the following structures:
*—T 3 -O-, S-, or one of the following structures:
* And- (ii) is a bond.
The invention also provides a preparation method of the phenanthridine derivative, which is shown in scheme 1:
in the case of scheme 1, the method comprises,
in scheme 1, the symbols used are as defined in formula (I), and X is Cl, br or I;
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.
Specifically, the compound of the formula (I) is prepared by carrying out addition reaction on a compound S0 containing nitrile groups and having a dibenzofuran, dibenzothiophene, carbazole or fluorene structure and an organolithium reagent or a Grignard reagent to prepare an imine intermediate S1; the imine intermediate is subjected to a free radical cyclization reaction to prepare the compound shown as the formula (I). Intermediate Ar 1 -L 1 X is 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 Etc., or a mixture of two or more 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, and the like, and mixtures of one or 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 phenanthridine derivative; the organic electroluminescent material comprising the phenanthridine derivative has the capability of carrier transmission.
The invention also provides application of the phenanthridine derivative in preparation of an 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 comprises the phenanthridine 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 also comprise further layers, for example in each case 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-generating 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 the phenanthridine derivative according to the 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 Under a pressure of between Pa and 1PaThe material is applied. 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, for example, are obtained by appropriate substitution. 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 phenanthridine derivatives 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, it may be preferable to include other compounds in addition to the phenanthridine derivative. Treatment of the phenanthridine derivatives according to the invention from the liquid phase, for example by spin coating or by printing methods, requires treatment of the formulations 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, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
the phenanthridine derivative shown in the formula (I) provided by the invention has a large plane structure of the phenanthridine bonded by the heteroatom, the conjugated area of phenanthrene or azaphenanthrene molecules is increased, the thermal stability, film forming performance and carrier conveying capacity of the molecules are improved, and the compound is applied to an organic electroluminescent element, so that the driving voltage can be obviously reduced, the luminous efficiency can be improved, and the service life of the organic electroluminescent element can be prolonged.
Drawings
Fig. 1 is a schematic view of an organic light emitting device 100;
in fig. 1: 101-substrate, 102-anode, 103-hole injection layer, 104-hole transport layer, 105-electron blocking layer, 106-light emitting layer, 107-hole blocking layer, 108-electron transport layer, 109-electron injection layer, 110-cathode, 111-capping layer (CPL);
fig. 2 is a schematic diagram of an organic light emitting device 200 with two light emitting layers;
in fig. 2: 201-substrate, 202-anode, 203-hole injection, 204-hole transport layer, 205-first light emitting layer, 206-electron transport layer, 207-charge generating layer, 208-hole injection layer, 209-hole transport layer, 210-second light emitting layer, 211-electron transport layer, 212-electron injection layer, 213-cathode.
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 process for the preparation of compound J385 comprising the steps of:
the first step: preparation of intermediate Int-1
Under the protection of nitrogen, 22.0mmol of p-dibromobenzene is dissolved in 40mL of dry THF, the temperature is reduced to minus 78 ℃, 9.6mL of 2.5M n-butyllithium n-hexane solution is added dropwise, stirring reaction is carried out for 30 minutes, 20.0mmol of SM-1 dissolved in the THF is added dropwise, stirring reaction is carried out for 1 hour at room temperature, 50mL of water, 30.0mmol of iodine and 60.0mmol of potassium carbonate are added, heating reflux reaction is carried out for 2 hours at room temperature, cooling is carried out, 50mL of saturated sodium sulfite aqueous solution is added, ethyl acetate is used for extraction, an organic phase is dried, filtration is carried out, filtrate is concentrated to dryness under reduced pressure, and silica gel column separation and purification are carried out, thus obtaining an intermediate Int-1.
And a second step of: preparation of intermediate Int-2
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 50mL of THF, the temperature is reduced to minus 78 ℃, 9.5mL of 2.5M N-butyllithium N-hexane solution is added dropwise, the mixture is stirred for 30 minutes, 30.0mmol of trimethyl borate is added dropwise, the mixture is stirred for 1 hour at room temperature, 50mL of 1N diluted hydrochloric acid aqueous solution is added, the mixture is extracted by EA, the organic phase is dried, filtered, concentrated under reduced pressure to dryness, and the mixture is dispersed and filtered by N-hexane to obtain an intermediate Int-2.
And a third step of: preparation of Compound J385
Under the protection of nitrogen, 12.0mmol of intermediate Int-2, 10.0mmol of triazine derivatives such as 2-chloro-4- (dibenzofuran) -6-diphenyl-1, 3, 5-triazine or 2-chloro-4- (dibenzothiophene) -6-diphenyl-1, 3, 5-triazine or 4- (4-chloro-6-phenyl-1, 3, 5-triazin-2-yl) -9-phenylcarbazole or 2-chloro-4- (9, 9-dimethylfluoren-4-yl) -6-phenyl-1, 3, 5-triazine or 2-chloro-4- (5, 5-dimethyldibenzo [ b, d ] silol) -6-phenyl-1, 3, 5-triazine, 36.0mmol of potassium phosphate hexahydrate and 40mL of toluene are mixed, then 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, the mixture is cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried, and the mixture is concentrated and then dried to obtain a dry J compound;
Y＝O，T 3 =o, yield 82%, MS (MALDI-TOF): m/z=591.1835 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )： 8.65～8.58(3H,m)；8.52～8.49(2H,m)；8.42～8.39(2H,m)；7.98～7.85(4H,m)；7.70～7.62 (3H,m)；7.58～7.45(6H,m)；7.42～7.38(1H,m)；7.29～7.26(1H,m)。
Y＝S，T 3 =o, yield 83%, MS (MALDI-TOF): m/z=607.1606 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：8.65～8.58(3H,m)；8.52～8.49(2H,m)；8.42～8.39(2H,m)；7.96～7.93(1H,m)；7.81～7.76 (3H,m)；7.68～7.57(5H,m)；7.52～7.39(5H,m)；7.36～7.33(1H,m)。
Y＝S，T 3 =s, yield 83%, MS (MALDI-TOF): m/z=623.1368 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )： 8.68～8.65(2H,m)；8.42～8.39(1H,m)；8.37～8.34(2H,m)；8.01～7.90(8H,m)；7.65～7.61 (1H,m)；7.58～7.53(3H,m)；7.49～7.43(4H,m)；7.41～7.38(1H,m)。
Y＝O，T 3 =s, yield 85%, MS (MALDI-TOF): m/z=607.1606 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )： 8.68～8.65(2H,m)；8.42～8.39(1H,m)；8.37～8.34(2H,m)；8.01～7.91(8H,m)；7.66～7.63 (1H,m)；7.59～7.54(3H,m)；7.52～7.44(4H,m)；7.42～7.39(1H,m)。
Y＝CH 2 ，T 3 =o, yield 81%, MS (MALDI-TOF): m/z= 589.2032[M+H] + ； 1 HNMR(δ、 CDCl 3 )：8.68～8.65(2H,m)；8.35～8.32(2H,m)；7.96～7.92(3H,m)；7.80～7.74(4H,m)； 7.71～7.68(1H,m)；7.56～7.44(6H,m)；7.41～7.37(2H,m)；7.31～7.27(2H,m)；3.79(2H,s)。
Y＝NPh，T 3 =o, yield 84%, MS (MALDI-TOF): m/z=666.2232 [ m+h ]] + ； 1 HNMR(δ、 CDCl 3 )：8.68～8.65(2H,m)；8.35～8.32(2H,m)；8.01～7.92(6H,m)；7.89～7.81(2H,m)； 7.68～7.65(1H,m)；7.63～7.55(6H,m)；7.53～7.48(6H,m)；7.38～7.35(1H,m)；7.33～7.30 (1H,m)。
Y＝SiPh 2 ，T 3 =o, yield 84%, MS (MALDI-TOF): m/z=757.2427 [ m+h ]] + ； 1 HNMR(δ、 CDCl 3 )：8.68～8.65(2H,m)；8.35～8.32(2H,m)；8.08～8.03(2H,m)；8.01～7.94(4H,m)； 7.83～7.78(2H,m)；7.71～7.65(3H,m)；7.55～7.52(2H,m)；7.50～7.43(7H,m)；7.41～7.30 (7H,m)；7.28～7.25(1H,m)。
Referring to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Wherein-y—isselected from-O-, S-, or one of the following structures:
*—T 3 -O-, S-, or one of the following structures:
* And- (ii) is a bond.
Example 2
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, which are not necessarily drawn to scale; the device 100 may be fabricated by sequentially depositing the layers described. The preparation method of the OLED element comprises the following steps:
1) Ultrasonic treating the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, flushing in deionized water, ultrasonic treating in an acetone/ethanol mixed solvent for 30 minutes, baking in a clean environment until the glass substrate is completely dried, irradiating for 10 minutes by an ultraviolet cleaning machine, and bombarding 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 anode layer on the anode layer film, the thickness of deposited film isContinuing to vapor-deposit the compounds 2-TNATA and F4TCNQ as hole injection layers respectively, wherein F4TCNQ is 3% of the mass of 2-TNATA, and the vapor-deposited film thickness is +.>
3) Continuously evaporating a compound HTM101 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) Continuously evaporating a compound H102 as a main material and GD05 as a doping material on the electron blocking layer, wherein GD05 is 3% of the mass of the formula H102, and the film thickness of the organic light-emitting layer obtained by evaporation is
6) Continuously evaporating a layer of LiQ and the compound formula (I) as an electron transport layer of the element on the organic light-emitting layer, wherein the compound formula (I) is 50% of the mass of LiQ, and the evaporation 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 2 above is as follows:
example 3
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. 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.
Comparative example 1
Following the same procedure as in example 2 substituting ET01 for compound formula (I) in step 6) to give comparative element 1;
the organic electroluminescent element prepared by the above process was subjected to the following performance test:
the driving voltage and current efficiency of the organic electroluminescent elements prepared in example 2 and comparative example 1 and the lifetime of the elements were measured using a digital source meter and a luminance meter at the same luminance. 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; LT95% life test is as follows: at 1000cd/m using a luminance meter 2 The luminance decay of the organic electroluminescent element was measured to be 950cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 2 are relative data compared to comparative element 1.
TABLE 2
In the above table, me is methyl, ph is phenyl, phPh is biphenyl, and Nap is naphthyl.
As can be seen from Table 2, the driving voltage of the element prepared from the compound of the present invention was lower than ET01 at the same brightness, the current efficiency was significantly improved by up to 1.2 times as much as that of the comparative element, and the LT95% lifetime of the element was significantly improved.
The compound ET01 in comparative example 1 is different from the compound of the present invention in that the single phenanthridine ring has weak plane conjugation ability, resulting in high voltage and low efficiency. The compound of the invention introduces hetero atoms such as oxygen, sulfur, nitrogen, silicon and the like on the basis of phenanthridine ring, improves the conjugation capability of the parent nucleus, so that the compound has excellent performance in molecular film formation and charge transmission, more balance charge transmission in the element and improved element 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 (5)

1. A phenanthridine derivative, characterized in that the phenanthridine derivative is selected from the group of compounds represented by the following formulae J383-J474:
wherein, -Y-, is selected from the group consisting of, -O-, or one of the following structures:
、、、、、、、、、；
*—T 3 -O-, S-, or one of the following structures:
、、、、、、、、、、；
* A- (3) and — represents a bond.
2. An organic electroluminescent material, characterized in that the raw material of the organic electroluminescent material comprises the phenanthridine derivative according to claim 1.
3. Use of the phenanthridine derivative according to claim 1 for the preparation of an organic electroluminescent element.
4. An organic electroluminescent element, characterized by comprising a first electrode, a second electrode, a sealing layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer comprises the phenanthridine derivative according to claim 1.
5. The organic electroluminescent element according to claim 4, wherein the organic layer comprises 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.
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