CN110981860A - Heterocyclic compound, method for synthesizing same, organic electroluminescent device, and electronic apparatus - Google Patents

Heterocyclic compound, method for synthesizing same, organic electroluminescent device, and electronic apparatus Download PDF

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CN110981860A
CN110981860A CN201911379364.4A CN201911379364A CN110981860A CN 110981860 A CN110981860 A CN 110981860A CN 201911379364 A CN201911379364 A CN 201911379364A CN 110981860 A CN110981860 A CN 110981860A
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heterocyclic compound
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王金平
薛震
陈志伟
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Priority to CN202010352148.7A priority patent/CN111320608A/en
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Abstract

The invention provides a heterocyclic compound, a synthetic method thereof, an organic electroluminescent device and an electronic device. The heterocyclic compound has high glass transition temperature and molecular thermal stability; the compound also has a shallow HOMO energy level and high hole mobility, can be used as a hole injection/transport layer material of an OLED device, and can effectively transfer holes to one side of a light-emitting layer, so that the recombination efficiency of the holes and electrons in the light-emitting layer is improved, and the light-emitting efficiency and the service life of the OLED device are improved.

Description

Heterocyclic compound, method for synthesizing same, organic electroluminescent device, and electronic apparatus
Technical Field
The invention relates to an organic material and a device, in particular to a heterocyclic compound and a synthetic method thereof, an organic electroluminescent device and electronic equipment.
Background
An Organic Light Emitting Diode (OLED) is a self-emission device, has advantages such as a wide viewing angle, excellent contrast, fast response, high luminance, and excellent driving voltage characteristics, and can provide a color image.
The basic structure of OLED is a sandwich structure composed of a thin and transparent Indium Tin Oxide (ITO) with semiconductor property, which is connected to the positive electrode of power, and another metal cathode. The entire structure layer includes a Hole Transport Layer (HTL), an Emission Layer (EL), and an Electron Transport Layer (ETL). When power is supplied to a proper voltage, positive holes and negative charges are combined in the light-emitting layer to generate light, and red, green and blue RGB three primary colors are generated according to different formulas to form basic colors.
In a conventional device having a bi-layer or multi-layer structure, the hole transporting material N, N '-di- (1-naphthyl) -N, N' -diphenyl-1, 1-biphenyl-4, 1-a diamine (NPB) has a hole transporting ability 10 to 1000 times higher than that of an electron transporting ability, but this results in a decrease in efficiency and a decrease in lifetime of the device. In addition, the hole transport materials commonly used at present are generally poor in thermal stability. These factors can accelerate the degradation of the device and reduce the lifetime, thereby affecting the industrial application of OLED devices.
Aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, the comprehensive characteristics of high efficiency, long service life and low voltage of the device can be realized only by selecting more suitable OLED functional materials or material combinations with high performance. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise. KR1020110108313A discloses a charge transport material.
Disclosure of Invention
The invention provides a heterocyclic compound, a synthetic method thereof, an organic electroluminescent device and electronic equipment, and aims to solve the problems of low electric efficiency, short service life and the like of a device caused by low charge transmission efficiency of a device material in the prior art. The heterocyclic compound has higher glass transition temperature (Tg) and molecular thermal stability. The heterocyclic compound is used as an electron transport layer/light emitting layer host material of an OLED device, so that the OLED material has high efficiency and brightness, low driving voltage and long service life.
In a first aspect, the present invention provides a heterocyclic compound having the following chemical formula:
Figure BDA0002341868370000011
in the formula 1, R1To R8Each independently selected from hydrogen or C1-C10 alkyl;
Y1and Y2Each independently selected from O, S or N (R)11)，R11Selected from deuterium, a halogen group, cyano, substituted or unsubstituted C6-C18 aryl;
m is selected from the group represented by formula 1-A:
Figure BDA0002341868370000012
in the formula 1-A, X1、X2、X3At least 2 of the N groups are N, and the rest are N or CH;
l is selected from substituted or substituted arylene of C18-C60, substituted or substituted heteroarylene of C6-C60;
Ar1and Ar2The same or different, each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl.
In a second aspect, the present invention provides a method for synthesizing the heterocyclic compound, including the following steps:
s1, adding raw materials Ia, dimethylbenzene, raw materials Ib, potassium carbonate, cuprous bromide and 18-crown ether-6, heating to a reflux state for reaction, cooling reaction liquid after liquid phase monitoring reaction is completed, washing inorganic salt in the reaction, separating liquid, drying obtained organic phase with anhydrous sodium sulfate, filtering, concentrating and drying filtrate, and recrystallizing with methylbenzene to obtain an intermediate Id;
Figure BDA0002341868370000021
s2, under the protection of nitrogen, adding an intermediate Id, pinacol diboron diborate, potassium acetate and 1, 4-dioxane, adding [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride at the temperature of 30-80 ℃, and continuously heating to a reflux state for reacting for 3-9 hours; cooling the reaction liquid, pouring water and toluene for extraction under stirring, standing, separating liquid, extracting the water phase with toluene for one time, separating liquid, combining organic phases, adding anhydrous sodium sulfate into the organic phase, stirring and drying to obtain an intermediate Ie;
Figure BDA0002341868370000022
s3, under the protection of nitrogen, adding toluene, the raw material Ic, the intermediate Ie, potassium carbonate, tetrabutylammonium bromide, ethanol and water, adding tetratriphenylphosphine palladium at 30-100 ℃, continuously heating to a reflux state for reaction, cooling a reaction liquid after the liquid phase monitoring reaction is completed, pouring the reaction liquid into water under stirring, standing for liquid separation, extracting a water phase with toluene, combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating a filtrate until no solvent is evaporated, and recrystallizing with toluene to obtain the heterocyclic compound;
Figure BDA0002341868370000023
in a third aspect, the present invention provides an organic electroluminescent device comprising an anode, a cathode and an organic layer deposited between the anode and the cathode, the organic layer comprising a hole transport layer, a light emitting layer and an electron transport layer; wherein the electron transporting layer or the light-emitting layer comprises the heterocyclic compound according to the present invention.
In a fourth aspect, the present invention provides an electronic device comprising an organic electroluminescent device according to the third aspect of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
the heterocyclic compound material comprises a heterocyclic nucleus represented by a formula 1, wherein the heterocyclic compound is introduced through oxygen or sulfur or nitrogen heterocycle, and the plane structures of the heterocyclic nucleus and the heterocyclic nucleus promote the HOMO energy level of the material, increase the charge transmission efficiency and improve the glass transition temperature (Tg) of the material. Meanwhile, through the connection of special ortho-substitution (namely the structure shown in the formula 1-A), the three-linear-state energy level can meet the requirement of exciton restraint, and simultaneously, the corresponding compound is not easy to crystallize due to the effect of steric hindrance. The heterocyclic compound is successfully applied to an organic electroluminescent device, and can effectively transfer electrons to one side of a light-emitting layer, so that the recombination efficiency of holes and electrons in the light-emitting layer is improved, the light-emitting efficiency of an OLED device is improved, and the service life of the OLED device is prolonged. The organic electroluminescent device containing the material has higher efficiency and brightness and low driving voltage.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of an electronic device in accordance with an embodiment of the invention.
Description of the reference numerals
100. An anode; 200. a cathode; 300. a functional layer; 310. a hole injection layer; 320. a hole transport layer; 321. a first hole transport layer; 322. a second hole transport layer; 330. an organic electroluminescent layer; 340. a hole blocking layer; 350. an electron transport layer; 360. an electron injection layer; 370. an electron blocking layer; 500: and (5) a mobile phone screen.
Detailed Description
In a first aspect, the present invention provides a heterocyclic compound represented by formula 1:
Figure BDA0002341868370000031
in the formula 1, R1To R8The same or different, each independently selected from hydrogen or C1-C10 alkyl;
Y1selected from O, S or N (R)11)，R11Selected from hydrogen, deuterium, halogen groups, cyano, substituted or unsubstituted C6-C18 aryl;
m is selected from the group represented by formula 1-A:
Figure BDA0002341868370000032
in the formula 1-A, X1、X2、X3At least 2 of the N groups are N, and the rest are N or CH;
l is selected from substituted or substituted arylene of C18-C60, substituted or substituted heteroarylene of C6-C60;
Ar1and Ar2The same or different, each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl.
In the present invention, aryl means an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused ring aryl group, two or more monocyclic aryl groups connected by carbon-carbon bond conjugation, a monocyclic aryl group and a fused ring aryl group connected by carbon-carbon bond conjugation, two or more fused ring aryl groups connected by carbon-carbon bond conjugation. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered an aryl group of the present disclosure. Wherein the aryl group does not contain a hetero atom such as B, N, O, S, P, Si. For example, biphenyl, terphenyl, and the like are aryl groups. Specific examples of aryl groups include, but are not limited to, phenyl, naphthyl, fluorenyl, spiro-fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, hexabiphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl, phenanthrenyl, pyrenyl,
Figure BDA0002341868370000033
and the like.
Substituted aryl, meaning that one or more hydrogen atoms in the aryl group are substituted with other groups (i.e., substituents), such as at least one hydrogen atom being substituted with a deuterium atom, a halogen group, -CN, hydroxyl, nitro, amino, alkyl (e.g., C1-C10 alkyl), cycloalkyl (e.g., C3-C10 cycloalkyl), alkoxy (e.g., C1-C10 alkoxy), silyl (e.g., C3-C10 silyl), or other group. It is understood that the number of carbon atoms of the substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group; for example, substituted C6-C40 aryl means that the total number of carbon atoms in the aryl and the substituents on the aryl is from 6 to 40.
In the present invention, the heteroaryl group may be a heteroaryl group including at least one of B, O, N, P, Si and S as a heteroatom. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. Specific examples of heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuryl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzosilyl, dibenzofuryl, phenyl-substituted dibenzofuryl, Dibenzofuranyl-substituted phenyl groups, and the like. Wherein, thienyl, furyl, phenanthroline and the like are heteroaryl of a single aromatic ring system, and N-aryl carbazolyl, N-heteroaryl carbazolyl, phenyl-substituted dibenzofuryl and the like are heteroaryl of a plurality of aromatic ring systems connected by carbon-carbon bond conjugation.
Substituted heteroaryl, means that one or more hydrogen atoms in the heteroaryl are substituted by other groups (i.e., substituents) other than heteroaryl, for example, at least one hydrogen atom is substituted by a deuterium atom, a halogen group, -CN, hydroxyl, nitro, amino, alkyl (e.g., C1-C10 alkyl), cycloalkyl (e.g., C3-C10 cycloalkyl), alkoxy (e.g., C1-C10 alkoxy), silyl (e.g., C3-C10 silyl), or other substituent. It is understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituent on the heteroaryl group. For example, substituted C3-C40 heteroaryl refers to heteroaryl groups and to substituents on heteroaryl groups having a total number of carbon atoms of from 3 to 40.
In the invention, the C1-C10 alkyl comprises C1-C10 straight-chain alkyl and C3-C10 branched-chain alkyl; the number of carbon atoms of the alkyl group is, for example, 1,2, 3, 4, 5, 6, 7, 8, 9,10, and specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, octyl, and the like.
In the present invention, cycloalkyl may be used as a substituent of aryl, heteroaryl, and specific examples include, but are not limited to, cyclohexyl, adamantyl, and the like.
In the present invention, the halogen group may include-F, -Cl, -Br, -I.
In the present invention, when R is11、L、Ar1And Ar2When substituted, according to one exemplary embodiment, R11、L、Ar1And Ar2The substituents on the compound are respectively and independently selected from deuterium, halogen, -CN, C1-C10 alkyl, C3-C10 silane radicalAnd C3-C10 cycloalkyl.
In the present invention, specifically, the structure of the heterocyclic compound is at least one of formula I to formula III:
Figure BDA0002341868370000041
alternatively, R1To R8Each independently selected from hydrogen or C1-C6 alkyl. Further, R1To R8Can be independently selected from hydrogen, methyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl.
According to an exemplary embodiment, R1To R8May both be selected from hydrogen, or R1To R8One or more than two of them are selected from C1-C6 alkyl.
Alternatively, R11Selected from deuterium, substituted or unsubstituted aryl groups of C6-C10. The substituted or unsubstituted C6-C10 aryl group can be, for example, phenyl, alkyl-substituted phenyl, or halogen-substituted phenyl.
According to one embodiment, X1、X2、X3Are all N.
Alternatively, L is selected from substituted or substituted C18-C40 arylene, substituted or substituted C12-C40 heteroarylene. According to a more specific exemplary embodiment, when L is selected from the group consisting of substituted or unsubstituted C18-C40 arylene, L may structurally include at least 3 benzene rings; when the L is selected from substituted or unsubstituted C15-C40 heteroarylene, the L structurally may include at least 2 benzene rings.
According to one embodiment, L is selected from the group represented by formulas 1-A1 through 1-A26:
Figure BDA0002341868370000042
Figure BDA0002341868370000051
in the formulae 1-A1 to 1-A26, Z1To Z3Each independently selected from hydrogen, deuterium, a halogen group, cyano, alkyl (e.g., C1-C4 alkyl), cycloalkyl (e.g., C3-C10 cycloalkyl); or selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, wherein the substituents are halogen, cyano, alkyl, cycloalkyl. Preferably, the substituent is deuterium, a halogen group, cyano, methyl, tert-butyl, cyclohexyl, adamantyl.
When Z is1To Z3When selected from aryl, optionally, Z1To Z3Is fused with the attached benzene ring;
alternatively, at Z1To Z3Wherein said aryl group is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, fluorenyl, spiro-fluorenyl (e.g., spiro dibenzofluorenyl), 9-diphenylfluorenyl;
alternatively, at Z1To Z3Wherein said heteroaryl is represented by: R-Ar3-L2-, in which,
r is phenyl or hydrogen;
L2represents a single bond or phenylene;
Ar3selected from the group consisting of pyridylene, pyrazinylene, pyrimidylene, benzopyrenylene, benzothiazylene, pyridazylene, quinolylene, isoquinolylene, quinoxalylene, quinazolinylene, carbazolyl, triazinylene, piperazinyl, dibenzothienyl, dibenzofuranylene, thienyl, phenanthrylene, 9-diphenylfluorenyl, spirobifluorylene.
Y2Selected from O, S, N (R)12) Or C (R)13R14)，R12To R14The same or different, each independently selected from C6-C12 aryl, C1-C10 alkyl; preferably, R12Is phenyl, R13And R14Are both methyl;
L1represents a single bond or phenylene;
a3is an integer selected from 1 to 3, a4Is an integer selected from 1 to 4, a5Is an integer selected from 1 to 5, a6Is an integer selected from 1 to 6, a8Is selected from 1 to8, and denotes a binding site connected to an adjacent atom.
Alternatively, Ar1、Ar2Each independently selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C6-C25 heteroaryl.
According to one embodiment, Ar1、Ar2Each independently selected from the group consisting of:
Figure BDA0002341868370000061
alternatively, the heterocyclic compound may be selected from the group consisting of compounds 1 to 162 below:
Figure BDA0002341868370000062
Figure BDA0002341868370000071
Figure BDA0002341868370000081
Figure BDA0002341868370000091
Figure BDA0002341868370000101
Figure BDA0002341868370000111
Figure BDA0002341868370000121
Figure BDA0002341868370000131
Figure BDA0002341868370000141
the heterocyclic compound has high glass transition temperature and molecular thermal stability. The heterocyclic compound also has a shallow HOMO energy level and high hole mobility, can be used as an electron transport layer or a main body material of a light-emitting layer of an OLED device, and can effectively transfer electrons to one side of the light-emitting layer, so that the recombination efficiency of the holes and the electrons in the light-emitting layer is improved, and the light-emitting efficiency and the service life of the OLED device are improved.
In a second aspect, the present invention provides a method for synthesizing the heterocyclic compound, comprising the steps of:
s1, adding raw materials Ia, dimethylbenzene, raw materials Ib, potassium carbonate, cuprous bromide and 18-crown ether-6, heating to a reflux state for reaction, cooling reaction liquid after liquid phase monitoring reaction is completed, washing inorganic salt in the reaction, separating liquid, drying obtained organic phase with anhydrous sodium sulfate, filtering, concentrating and drying filtrate, and recrystallizing with methylbenzene to obtain an intermediate Id;
Figure BDA0002341868370000142
s2, under the protection of nitrogen, adding an intermediate Id, pinacol diboron, potassium acetate and 1, 4-dioxane, adding [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride at 30-80 ℃, continuously heating to a reflux state, reacting for 3-9 hours, cooling a reaction liquid, pouring water and toluene for extraction under stirring, standing, separating liquid, extracting a water phase once with the toluene, separating liquid, combining organic phases, adding anhydrous sodium sulfate into the organic phases, stirring and drying to obtain an intermediate Ie;
Figure BDA0002341868370000143
s3, under the protection of nitrogen, adding toluene, the raw material Ic, the intermediate Ie, potassium carbonate, tetrabutylammonium bromide, ethanol and water, adding tetratriphenylphosphine palladium at 30-100 ℃, continuously heating to a reflux state for reaction, cooling a reaction liquid after the liquid phase monitoring reaction is completed, pouring the reaction liquid into water under stirring, standing for liquid separation, extracting a water phase with toluene, combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating a filtrate until no solvent is evaporated, and recrystallizing with toluene to obtain the heterocyclic compound;
Figure BDA0002341868370000151
in step S1, the molar ratio of the raw material Ia to the raw material Ib to the potassium carbonate to the cuprous bromide to the 18-crown ether 6 can be 1 to (1-1.3) to (4-5) to (0.2-0.4) to (0.1-0.3);
in step S2, the molar ratio of the intermediate Id, pinacol diborate, potassium acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride can be 1: 1.2-1.5: 5-8: 0.01-0.05;
in step S3, the molar ratio of the raw material Ic, the intermediate Ie, the potassium carbonate, the tetrabutylammonium bromide and the tetratriphenylphosphine palladium can be 1: 1-1.5: 10-20: 0.125-0.25: 0.62-1.
In each step, heating to reflux means that the heating temperature of the heating device (e.g., heating jacket) used for the reaction is higher than the boiling point of the solvent, and for example, the heating temperature may be 5 to 10 ℃ higher than the boiling point. The starting materials of the present invention are either commercially available or can be synthesized by methods well known in the art.
According to a particular embodiment, the process for the synthesis of said heterocyclic compound comprises the following steps:
(1) under the protection of nitrogen, under stirring, sequentially adding raw materials Ia and xylene into a three-neck flask, then adding raw materials Ib, potassium carbonate, cuprous bromide and 18-crown ether-6, after the addition is finished, heating a reaction system to a reflux state by an electric heating jacket, cooling a reaction liquid to room temperature (15-30 ℃) until the liquid phase monitoring reaction is complete, then washing inorganic salts in the reaction, separating the liquid, drying the obtained organic phase by using anhydrous sodium sulfate, and filtering. The filtrate is concentrated and dried, and the intermediate Id is obtained by toluene recrystallization.
Figure BDA0002341868370000152
(2) Introducing nitrogen into a three-mouth glass bottle provided with a mechanical stirrer, a thermometer and a condenser, and sequentially adding the intermediate Id, the pinacol diboron diboride, the potassium acetate and the 1, 4-dioxane. Stirring is started, the temperature is increased to 30-80 ℃, the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is rapidly added, and the reaction is continued to be heated to a reflux state for 3-9 hours. Cooling the reaction solution to room temperature quickly, adding water and toluene while stirring, extracting, standing for 30min, separating, extracting the water phase with toluene once again, separating, and combining the organic phases. Adding anhydrous sodium sulfate into the organic phase, stirring for 5min, and drying for 0.5h to obtain an intermediate Ie.
Figure BDA0002341868370000153
(3) Introducing nitrogen into a three-neck flask provided with a mechanical stirrer, a thermometer and a condenser, and sequentially adding toluene, the raw material Ic, the intermediate Ie, potassium carbonate, tetrabutylammonium bromide, ethanol and water. Starting stirring, heating to 30-100 ℃, quickly adding palladium tetratriphenylphosphine, continuously heating to a reflux state for reaction, after a liquid phase monitoring reaction is completed, quickly cooling the reaction liquid to room temperature, pouring the reaction liquid into water while stirring, standing for 30min, separating liquid, extracting a water phase with toluene, combining organic phases, drying for 0.5h with anhydrous sodium sulfate, filtering, concentrating a filtrate (65-70 ℃; 0.08-0.09 MPa, about 8h), concentrating until no solvent is evaporated, and recrystallizing with toluene to obtain a heterocyclic compound (namely a compound I).
Figure BDA0002341868370000154
In a third aspect, the present invention provides an organic electroluminescent device comprising an anode, a cathode and an organic layer deposited between the anode and the cathode, wherein the organic layer comprises a hole transport layer, a light emitting layer and an electron transport layer, and the electron transport layer or the light emitting layer comprises the heterocyclic compound of the present invention. The heterocyclic compound may be used to form an organic thin layer in an electron transport layer or a light emitting layer to improve life characteristics, efficiency characteristics, electrochemical stability and thermal stability of an organic electroluminescent device and to reduce driving voltage.
According to one embodiment, the host material of the light-emitting layer contains the above-described heterocyclic compound.
According to another embodiment, the electron transport layer comprises the heterocyclic compound described above.
As shown in fig. 1, the organic electroluminescent device includes an anode 100 and a cathode 200 oppositely disposed, and a functional layer 300 (i.e., an organic layer) disposed between the anode 100 and the cathode 200.
Specifically, the organic electroluminescent device includes an anode 100, a hole transport layer 320, an organic electroluminescent layer 330 (i.e., a light emitting layer), an electron transport layer 350, and a cathode 200, which are sequentially stacked. The hole transport layer 320 may include one layer or two layers.
Optionally, a hole injection layer 310 is provided between the anode 100 and the hole transport layer 320.
Optionally, an electron injection layer 360 is further disposed between the cathode 200 and the electron transport layer 350.
Optionally, a hole blocking layer 340 is further disposed between the organic electroluminescent layer 330 and the electron transport layer 350.
Optionally, an electron blocking layer 370 is disposed between the organic electroluminescent layer 330 and the hole transport layer 320.
Alternatively, the hole transport layer 320 may be composed of a first hole transport layer 321 and a second hole transport layer 322, the first hole transport layer 321 being relatively close to the anode.
According to one embodiment, the electron transport layer 350 comprises a heterocyclic compound provided by the present invention. The electron transport layer 350 may be formed of the heterocyclic compound provided in the present invention, or may be formed of the heterocyclic compound and other materials. Thus, the heterocyclic compound provided by the invention is applied to the electron transport layer 350 of the organic electroluminescent device, and can effectively improve the electronic characteristics of the organic electroluminescent device.
According to another embodiment, the luminescent layer comprises a fused ring compound provided by the present invention. The light-emitting layer may be formed of the heterocyclic compound provided by the present invention, or may be formed of the heterocyclic compound provided by the present invention and another material. Therefore, the heterocyclic compound provided by the invention is applied to the light-emitting layer of the organic electroluminescent device, and can effectively improve the light-emitting characteristic of the organic electroluminescent device.
In the present invention, the anode 100 includes an anode material, which may be selected with reference to the prior art, preferably a material having a large work function (work function) that facilitates hole injection into the functional layer. Specific examples of the anode material include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO: Al or SnO2Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,1-A (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole and polyaniline. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.
In the present invention, the cathode 200 includes a cathode material, which may be selected with reference to the prior art, which is a material having a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material are, but not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multilayer material such as LiF/Al, Liq/Al, LiO2Al, LiF/Ca, LiF/Al and BaF2But not limited thereto,/Ca.
In a fourth aspect, the present invention provides an electronic device comprising the organic electroluminescent device according to the third aspect. The electronic device may be any electronic device including the organic electroluminescent device, such as a mobile phone (as shown in fig. 2), a computer, and the like. The organic electroluminescent device may be applied in a screen of the electronic apparatus.
The present invention will be further described with reference to the following examples.
For the convenience of understanding the present invention, the following raw materials and intermediates correspond to the numbers of the compounds to be prepared, and for example, "raw material 2 a", "raw material 2 b" and "raw material 2 c" respectively refer to raw material Ia, raw material Ib and raw material Ic specifically selected for preparing compound 2; "starting material 18 a", "starting material 18 b", "intermediate 18 d", "starting material 18 c" and "intermediate 18 e" respectively refer to starting material Ia, starting material Ib, intermediate Id, starting material Ic and intermediate Ie, which are specifically selected for the preparation of compound 18; in addition, the invention also describes a preparation method of part of raw material Ib, wherein the compounds involved in the preparation of the raw material Ib are expressed in the form of Ib-number numbers, for example, 5b-1 and 5b-2 refer to two compounds adopted for preparing the raw material 5 b.
Preparation example
Preparation examples are given to illustrate the synthesis of starting material Ib.
1. Synthesis of starting Material 5b
(1)
Figure BDA0002341868370000161
Under the protection of nitrogen, sequentially adding a compound 5b-1(50mmol) and a compound 5b-2(55mmol) and 460.0ml of acetic acid into a three-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a condenser, heating to 80-90 ℃, dropwise adding concentrated sulfuric acid (1mmol), and reacting for 5 hours under heat preservation. Adding 600.0ml of water, cooling to 25 ℃, stirring to separate out a large amount of solid, filtering, and leaching a filter cake by using ethanol to obtain a compound 5b-3(32mmol), wherein the yield is 64%.
(2)
Figure BDA0002341868370000171
Introducing nitrogen (0.100L/min) into a three-neck flask provided with a mechanical stirring, thermometer and constant-pressure dropping funnel for replacement for 15min, adding a compound 5b-3(30mmol) and tetrahydrofuran 120.8mL, starting stirring, cooling liquid nitrogen to-80 ℃ to-90 ℃, dropping 2mol/L n-butyl lithium (32mmol), preserving heat for 1h after dropping, dropping tributyl borate (35mmol), adding 200.0mL of water, 40.0mL of petroleum ether and 5mL of concentrated hydrochloric acid into reaction liquid after preserving heat for 1h after dropping, fully stirring, separating liquid, washing an organic phase for 4 times, filtering an obtained crude product, pulping for 0.5h by using 50.0mL of toluene, filtering, leaching by using toluene, obtaining a compound 5b-4(25mmol), and obtaining the yield of 83.3%.
(3)
Figure BDA0002341868370000172
A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen, and 100.0mL of toluene, compound 5b-4(20mmol), starting material 3-chloro-5-bromoiodobenzene (i.e., compound 5b-5, 21mmol), potassium carbonate (40mmol), 20mL of ethanol and 20mL of water were sequentially added. Stirring, heating to 50 ℃, quickly adding tetratriphenylphosphine palladium (0.2mmol), continuously heating to a reflux state for reaction for 6h, pouring into 100mL of water under stirring, standing, separating liquid, extracting the water phase with 50mL of toluene, combining organic phases, drying with 10g of anhydrous sodium sulfate, filtering, concentrating the filtrate (70 ℃, under-0.09 MPa), concentrating until no solvent is evaporated, adding 50mL of n-heptane, and filtering to obtain a compound 5b-6(17mmol) with the yield of 85%.
(4)
Figure BDA0002341868370000173
Introducing nitrogen (0.100L/min) into a three-neck flask provided with a mechanical stirring, thermometer and constant-pressure dropping funnel for replacement for 15min, adding a compound 5b-6(15mmol) and tetrahydrofuran 80.1mL, starting stirring, cooling liquid nitrogen to-80 ℃ to-90 ℃, dropping 2mol/L n-butyl lithium (17mmol), preserving heat for 1h after dropping, dropping tributyl borate (19mmol), adding 100.0mL of water, 20.0mL of petroleum ether and 3mL of concentrated hydrochloric acid into reaction liquid after preserving heat for 1h after dropping, fully stirring, separating liquid, washing an organic phase for 4 times, filtering an obtained crude product, pulping for 0.5h by using 20.0mL of toluene, filtering, leaching by using toluene, obtaining a compound 5b-7(13mmol), and obtaining the yield of 86.6%.
(5)
Figure BDA0002341868370000174
A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen, and 70.0mL of toluene, compounds 5b to 7(13mmol), compounds 5b to 8(15mmol), potassium carbonate (26mmol), 15mL of ethanol and 15mL of water were sequentially added. Stirring, heating to 50 ℃, quickly adding tetratriphenylphosphine palladium (0.1mmol), continuously heating to a reflux state, reacting for 8h, pouring into 90mL of water while stirring, standing for 30min, separating liquid, extracting the water phase with 35mL of toluene, combining organic phases, drying for 0.5h by using 5g of anhydrous sodium sulfate, filtering, concentrating the filtrate (70 ℃, minus 0.09MPa and about 8h), concentrating until no solvent is evaporated, adding 50mL of ethanol, and filtering to obtain a raw material 5b (10mmol) with a yield of 77%.
2. Synthesis of starting materials 2b, 4b, 12b, 101b, 111b, 134b and 142b
The above starting materials were synthesized according to steps (2) to (5) of the starting material 5b, respectively, except that the compound Ib-3 was substituted, and the main starting materials used and the correspondingly prepared compounds were specifically shown in table 1 below:
TABLE 1
Figure BDA0002341868370000181
3. Synthesis of starting materials 7b, 74b
The starting materials 7b and 74b were synthesized separately with reference to the procedure for starting material 5b, except that the compounds were substituted, the main starting materials used and the correspondingly prepared compounds were as specified in table 2 below:
TABLE 2
Figure BDA0002341868370000182
*: synthesis of starting Material 74b referring to Steps (3), (4), (5) and (1) in sequence
4. Synthesis of starting Material 78b
The starting material 78b was synthesized according to step (3), step (4) and step (5) of starting material 5b, except that compounds Ib-4, Ib-5 and Ib-8 were replaced respectively, and the starting materials used and the compounds prepared accordingly were specifically shown in table 3 below:
TABLE 3
Figure BDA0002341868370000191
5. Synthesis of starting Material 40b
Figure BDA0002341868370000192
Adding 40b-1(50mmol) of raw material and 80.1mL of dichloromethane into a reaction bottle with a mechanical stirring thermometer, starting stirring, cooling liquid nitrogen to-15 ℃ to-10 ℃, adding NCS (51mmol) in 4 batches, preserving heat for 1h after adding, adding 100.0mL of water into the reaction solution, separating, extracting the water phase with 35mL of dichloromethane, combining organic phases, washing with water for 2 times, drying the organic phases with 5g of anhydrous sodium sulfate, filtering, concentrating the filtrate (40 ℃ and-0.06 MPa), concentrating until no solvent is evaporated, adding 20mL of ethanol, and filtering to obtain 40b (45mmol) of raw material and yield of 90%.
6. Synthesis of starting Material 162b
The starting material 162b was synthesized according to the procedure for the starting material 40b, except that the starting material 40b-1 was replaced with an equimolar amount of the starting material 162b-1, and the crude product obtained by filtration was further recrystallized from n-hexane, to synthesize the starting material 162b in a yield of 55%.
Figure BDA0002341868370000193
Example 1: a compound 2 and a synthetic method thereof,
the method comprises the following steps:
(1) under the protection of nitrogen, 1mmol of raw material 2a and 40mL of dimethylbenzene are sequentially added into a three-neck flask under stirring, 1.3mmol of raw material 2b, 4mmol of potassium carbonate, 0.2mmol of cuprous bromide and 0.1mmol of 18-crown ether-6 are added, the reaction system is heated to a reflux state for reaction, the reaction is carried out until the liquid phase monitoring reaction is completed, the reaction liquid is cooled to room temperature, then inorganic salt in the reaction is washed by water, liquid separation is carried out, and the obtained organic phase is dried by anhydrous sodium sulfate and filtered. The filtrate is concentrated and dried, and the toluene is recrystallized to obtain an intermediate 2 d.
Figure BDA0002341868370000194
(2) A three-neck glass bottle provided with a mechanical stirrer, a thermometer and a condenser is filled with nitrogen, and 1mmol of the intermediate 2d, 1.5mmol of pinacol diboron, 5mmol of potassium acetate and 40mL of 1, 4-dioxane are sequentially added. Stirring is started, the temperature is increased to 30 ℃, 0.01mmol of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is rapidly added, and the reaction is continued to be heated to a reflux state for reaction for 3 hours. Quickly cooling the reaction solution to 20 ℃, pouring 50mL of water and 50mL of toluene for extraction under stirring, standing for 30min, separating, extracting the water phase once with 50mL of toluene, separating, and combining organic phases. Adding 10g of anhydrous sodium sulfate into the organic phase, stirring for 5min, drying for 0.5h, filtering, and concentrating until no solvent is evaporated to obtain an intermediate 2 e.
Figure BDA0002341868370000201
(3) A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen, and 50mL of toluene, 0.4mmol of the starting material 2c, 0.5mmol of the intermediate 2e, 5mmol of potassium carbonate, 0.05mmol of tetrabutylammonium bromide, 10mL of ethanol and 5mL of water were sequentially added. Starting stirring, heating to 50 ℃, quickly adding 0.25mmol of tetratriphenylphosphine palladium, continuously heating to a reflux state for reaction until a liquid phase monitoring reaction is completed, cooling the reaction liquid to 20 ℃, pouring the reaction liquid into 100mL of water under stirring, standing for 30min, separating liquid, extracting a water phase with 50mL of toluene, combining organic phases, drying for 0.5h by 10g of anhydrous sodium sulfate, filtering, concentrating the filtrate (70 ℃, minus 0.09MPa and about 8h), and concentrating until no solvent is evaporated. Recrystallization from 20mL of toluene gave 0.28g of Compound 2(0.35mmol, yield 69%). 793.3[ M + H ] M/z]+。
Figure BDA0002341868370000202
Calculated value C of element content (%) of Compound 257H36N4O; wherein C: 86.34, respectively; h: 4.58; n: 7.07; o: 2.02; measured value C57H36N4O: wherein C: 86.31, respectively; h: 4.54; n: 7.09; o: 2.06.
example 2: compound 18 and a method for its synthesis comprising the steps of:
(1) under the protection of nitrogen, 1mmol of raw material 18a and 60mL of dimethylbenzene are sequentially added into a three-neck flask under stirring, 1.2mmol of raw material 18b, 4.5mmol of potassium carbonate, 0.2mmol of cuprous bromide and 0.1mmol of 18-crown ether-6 are added, an electric heating jacket is heated to a reflux state for reaction, the reaction liquid is cooled to room temperature after the liquid phase monitoring reaction is completed, then inorganic salt in the reaction is washed by water, liquid separation is carried out, and the obtained organic phase is dried by anhydrous sodium sulfate and filtered. The filtrate was concentrated to dryness and recrystallized from toluene to give intermediate 18 d.
Figure BDA0002341868370000203
(2) A three-neck glass bottle provided with a mechanical stirrer, a thermometer and a condenser is filled with nitrogen, and 1mmol of intermediate 18d, 1.5mmol of pinacol diboron, 5mmol of potassium acetate and 40mL of 1, 4-dioxane are sequentially added. Stirring is started, the temperature is increased to 80 ℃, 0.01mmol of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is rapidly added, and the reaction is continued to be heated to a reflux state for 6 hours. Cooling the reaction solution to 20 ℃, pouring 50mL of water and 50mL of toluene for extraction while stirring, standing for 30min, separating, extracting the water phase once with 50mL of toluene, separating, and combining organic phases. Adding 10g of anhydrous sodium sulfate into the organic phase, stirring for 5min, drying for 0.5h, filtering, and concentrating until no solvent is evaporated to obtain an intermediate 18 e.
Figure BDA0002341868370000204
(3) A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen, and 50mL of toluene, 0.4mmol of the starting material 18c, 0.5mmol of the intermediate 18e, 5mmol of potassium carbonate, 0.05mmol of tetrabutylammonium bromide, 10mL of ethanol and 5mL of water were sequentially added. Starting stirring, heating to 100 deg.C, rapidly adding 0.25mmol of tetratriphenylphosphine palladium, continuously heating to reflux state, reacting until liquid phase monitoring reaction is completed, cooling reaction solution to 20 deg.C, stirring, pouring into 100mL of water, standing for 30min, separating, extracting water phase with 50mL of toluene, mixingThe organic phase was dried over 10g of anhydrous sodium sulfate for 0.5h, filtered, the filtrate was concentrated (65 ℃ C., -0.08MPa, ca. 8h) and concentrated until no solvent was distilled off. Recrystallization from 20mL of toluene gave 0.28g of compound 18(0.31mmol, yield 61%) M/z 891.3[ M + H ═]+。
Figure BDA0002341868370000211
Calculated value C of element content (%) of Compound 1863H46N4S: wherein, C: 84.91, respectively; h: 5.20; n: 6.29; s: 3.60; measured value C63H46N4S: wherein, C: 84.87, respectively; h: 5.22; n: 6.28; s: 3.63.
example 3: a compound 47 and a method for synthesizing the same,
the method comprises the following steps:
(1) under the protection of nitrogen, 1mmol of raw material 47a and 50mL of dimethylbenzene are sequentially added into a three-neck flask under stirring, 1.3mmol of raw material 47b, 4mmol of potassium carbonate, 0.2mmol of cuprous bromide and 0.1mmol of 18-crown ether-6 are added, the reaction system is heated to a reflux state for reaction, the reaction is carried out until the liquid phase monitoring reaction is completed, the reaction liquid is cooled to room temperature, then inorganic salt in the reaction is washed by water, liquid separation is carried out, and the obtained organic phase is dried by anhydrous sodium sulfate and filtered. The filtrate was concentrated to dryness and recrystallized from toluene to give intermediate 47 d.
Figure BDA0002341868370000212
(2) A three-neck glass bottle equipped with mechanical stirring, a thermometer and a condenser was purged with nitrogen, and 1mmol of intermediate 47d, 1.5mmol of pinacol diboron, 5mmol of potassium acetate and 40mL of 1, 4-dioxane were sequentially added. Stirring is started, the temperature is increased to 80 ℃, 0.01mmol of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride is rapidly added, and the reaction is continued to be heated to a reflux state for 6 hours. Quickly cooling the reaction solution to 20 ℃, pouring 50mL of water and 50mL of toluene for extraction under stirring, standing for 30min, separating, extracting the water phase once with 50mL of toluene, separating, and combining organic phases. The organic phase was added with 10g of anhydrous sodium sulfate, stirred for 5min, dried for 0.5h, filtered, and concentrated until no solvent was evaporated to give intermediate 47 e.
Figure BDA0002341868370000213
(3) A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen, and 50mL of toluene, 0.4mmol of the raw material 47c, 0.5mmol of the intermediate 47e, 5mmol of potassium carbonate, 0.05mmol of tetrabutylammonium bromide, 10mL of ethanol and 5mL of water were sequentially added. Starting stirring, heating to 100 ℃, quickly adding 0.25mmol of tetratriphenylphosphine palladium, continuously heating to a reflux state for reaction until a liquid phase monitoring reaction is completed, after the reaction is completed, quickly cooling the reaction liquid to 20 ℃, pouring the reaction liquid into 100mL of water under stirring, standing for 30min, separating liquid, extracting the water phase with 50mL of toluene, combining organic phases, drying for 0.5h by 10g of anhydrous sodium sulfate, filtering, concentrating the filtrate (70 ℃, minus 0.08MPa, about 8h), and concentrating until no solvent is evaporated. Recrystallization from 20mL of toluene gave 0.49g of compound 47(0.27mmol, yield 54%) with M/z of 978.5[ M + H ═]+。
Figure BDA0002341868370000221
Examples 4 to 7
Compound 4, compound 5, compound 7 and compound 12 were synthesized according to the method of example 1, except that the raw materials 1a, 1b and 1c in example 1 were replaced with the corresponding raw materials, and the raw materials used, the compounds prepared accordingly and the mass spectrum data are specifically shown in table 2.
Examples 8 to 17
Compound 40, compound 74, compound 78, compound 96, compound 101, compound 111, compound 142, compound 155, compound 161, compound 162 were synthesized according to the methods of example 2, except that the raw materials 18a, 18b, and 18c in example 2 were replaced with the corresponding raw materials, and the raw materials used, the compounds prepared accordingly, and the mass spectrum data are specifically shown in table 2.
Examples 18 to 20
Compound 85, compound 115 and 134 were synthesized according to the procedure of example 3, except that the raw materials 47a, 47b and 47c in example 3 were respectively replaced with corresponding raw materials, and the raw materials used, the compounds prepared accordingly and the mass spectrum data are specifically shown in table 4.
TABLE 4
Figure BDA0002341868370000222
Figure BDA0002341868370000231
Figure BDA0002341868370000241
The following application examples 1 to 10 are intended to illustrate the use of the heterocyclic compound of the present invention in an electron transport layer in an organic electroluminescent device.
Application example 1
The manufacturing method of the organic electroluminescent device comprises the following steps:
(1) firstly, distilled water and methanol are sequentially used for ultrasonic cleaning
Figure BDA0002341868370000242
Drying a glass bottom plate of an Indium Tin Oxide (ITO) electrode;
(2) cleaning the anode base plate for 5 minutes by using oxygen plasma, and then loading the cleaned anode base plate into vacuum deposition equipment;
(3) depositing a hole injection layer compound 2-TNATA (the structure is shown as formula A) on an ITO electrode in vacuum to form HIL of a hole injection layer with the thickness of 50nm, then depositing NPB (N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) on the hole injection layer in vacuum to form a hole transport layer HTL with the thickness of 60nm, and depositing TCTA (the structure is shown as formula B) on the hole transport layer in vapor deposition to form
Figure BDA0002341868370000256
Electron blocking of thicknessA layer EBL. Then, the host luminescent material BPO (with the structure shown in the formula C) and the dopant EM (with the structure shown in the formula D) are mixed with 96: 4, co-depositing the mixture on a hole transport region to form a light emitting layer EML with the thickness of 30 nm;
(4) depositing a hole blocking layer DPVBi (with the structure shown as the formula E) with the thickness of 20nm on the light-emitting layer in a vacuum manner to form the hole blocking layer;
(5) vacuum depositing Compound 2 on the hole-blocking layer to a thickness of 30nm to form an electron-transporting layer and evaporating LiQ (8-Hydroxyquinoline-lithium) on the electron-transporting layer to form
Figure BDA0002341868370000253
An electron injection layer EIL with a thickness of 1: 9, mixing magnesium (Mg) and silver (Ag) at a vapor deposition rate, and vacuum-evaporating on the electron injection layer to form
Figure BDA0002341868370000254
A cathode of thickness. Further, the cathode is deposited with a thickness of
Figure BDA0002341868370000255
Forming a capping layer (CPL) to complete the fabrication of the organic light emitting device, the fabricated organic light emitting device is denoted as a 1.
Figure BDA0002341868370000251
Comparative example 1
An organic electroluminescent device was produced in the same manner as in application example 1, except that Compound 2 as the electron transport layer was replaced with Compound A (Alq)3) Instead, an organic electroluminescent device D1 was thus produced. Alq3The structure of (a) is as follows:
Figure BDA0002341868370000252
comparative example 2
An organic electroluminescent device was produced in the same manner as in application example 1, except that compound 2 as the electron transport layer was replaced with compound B, to thereby produce organic electroluminescent device D2. The structural formula of compound B is shown below:
Figure BDA0002341868370000261
application example 2 to application example 10
Organic electroluminescent devices were produced in the same manner as in application example 1, except that in application examples 2 to 10, compound 2 as the electron transport layer was replaced with compound 4, compound 5, compound 18, compound 40, compound 74, compound 85, compound 96, compound 111, and compound 155, respectively, to produce organic electroluminescent devices a2 to a 10.
The organic electroluminescent devices A1 to A10, D1 and D2 prepared as above were subjected to performance tests in which the driving voltage, efficiency and color coordinates were 10mA/cm at a constant current density2The test is carried out, and the service life of the T95 device is 15mA/cm at constant current density2The following tests were carried out to analyze the electron luminescence characteristics, and the results are shown in Table 5.
TABLE 5
Figure BDA0002341868370000262
Combining the results of Table 2, the heterocyclic compound of the present invention as an electron transport layer and the use of an electron transport material Alq3Comparative example 1, comparative example 2 using compound B compared:
the driving voltages of the organic electroluminescent devices a1 to a10 prepared in application examples 1 to 10 were between 3.83 to 4.02V, which were respectively reduced by about 15% to 18% and 2.7% to 7.3% compared with the driving voltages of the organic electroluminescent devices D1 and D2 of comparative example 1 and comparative example 2; the luminous efficiencies of the organic electroluminescent devices A1-A10 are 6.1-6.8 Cd/A, and are respectively increased by about 48-66% and 7-19% compared with the luminous efficiencies of the organic electroluminescent devices D1 and D2 of comparative example 1 and comparative example 2. The external quantum efficiency of A1-A10 is 12.3-13.8%, which is respectively improved by 45-62% and 10-23% compared with the external quantum efficiency of D1 and D2. The service life of T95 of A1-A10 is 193-223 h, which is 89-118% and 20-28% longer than that of T95 of D1 and D2 of comparative example 1. In addition, the glass transition temperatures of the heterocyclic compounds of the application examples 1 to 10 were respectively: 156 ℃, 127 ℃, 164 ℃, 137 ℃, 147 ℃, 137 ℃, 126 ℃, 138 ℃, 154 ℃, 149 ℃, has good thermal stability.
It can be seen that the organic electroluminescent devices a1 to a10 of application examples 1 to 10 have lower driving voltage, higher luminous efficiency, higher external quantum efficiency, and luminance, compared to the devices D1, D2 of comparative example 1 and comparative example 2. Has excellent performances in the aspects of chromaticity, glass transition temperature, half-life period and the like, and has good thermal stability. That is, as an electron transport layer, compared with Alq3And a compound B, the heterocyclic compound of the present invention has better luminous efficiency, better electrical stability and longer life, and can significantly improve the performance of an organic electroluminescent device when used in an electron transport layer of the organic electroluminescent device.
The following application examples 11 to 20 are intended to illustrate the use of the fused ring compound of the present invention in the light-emitting layer of an organic electroluminescent device.
Application example 11
The manufacturing method of the organic electroluminescent device comprises the following steps:
(1) firstly, distilled water and methanol are sequentially used for ultrasonic cleaning
Figure BDA0002341868370000271
Drying a glass substrate with a thick Indium Tin Oxide (ITO) electrode;
(2) cleaning the anode base plate for 5 minutes by using oxygen plasma, and then loading the cleaned anode base plate into vacuum deposition equipment;
(3) vacuum depositing hole injection layer compound 2-TNATA onto ITO electrode to form hole injection layer HIL with thickness of 50nm, vacuum depositing NPB onto hole injection layer to form hole transport layer HTL with thickness of 60nm, and vapor plating TCTA on the hole transport layer to form
Figure BDA0002341868370000272
Electron blocking layer EBL of thickness. Then co-depositing a host luminescent material, namely the compound 7 and the dopant EM on the hole transport region in a mass ratio of 96: 4 to form a luminescent layer EML with the thickness of about 30 nm;
(4) vacuum deposition of DPVBi on light emitting layer to form
Figure BDA0002341868370000275
A hole blocking layer of thickness;
(5) vacuum depositing Alq3 on the hole blocking layer to a thickness of 30nm to form an electron transport layer and evaporating LiQ on the electron transport layer to form
Figure BDA0002341868370000277
An electron injection layer EIL with a thickness of 1: 9, mixing magnesium (Mg) and silver (Ag) at a vapor deposition rate, and vacuum-evaporating on the electron injection layer to form
Figure BDA0002341868370000276
A cathode of thickness. Further, the cathode is deposited with a thickness of
Figure BDA0002341868370000278
Forming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device. The organic electroluminescent device thus produced was denoted as B1.
Application example 12 to application example 20
Organic electroluminescent devices were produced in the same manner as in application example 11, except that compound 7 as a light-emitting host material was replaced with compound 12, compound 47, compound 78, compound 101, compound 115, compound 134, compound 142, compound 161, and compound 162, respectively, to produce organic electroluminescent devices B2 to B10.
Comparative example 3
An organic electroluminescent device was produced in the same manner as in application example 11, except that compound 7 as a light-emitting host material was replaced with compound C, thereby producing an organic electroluminescent device D3. The structural formula of compound C is shown below:
Figure BDA0002341868370000273
the organic electroluminescent devices B1 to B10 prepared as above were subjected to performance tests in which the driving voltage, efficiency, color coordinates were 10mA/cm at a constant current density2The test is carried out, and the service life of the T95 device is 15mA/cm at constant current density2The following tests were conducted to analyze the performance of the devices, and the results are shown in table 6. In addition, for convenience of comparison, table 6 also shows the electron emission characteristics of the organic light emitting device of comparative example 1 (comparative example 1 is different from application examples 10 to 20 in that the light emitting host material is BPO).
TABLE 6
Figure BDA0002341868370000274
Combining the results of table 3, the heterocyclic compound of the present invention as a light emitting host material was compared with comparative examples 1,2 using the already light emitting host material BPO, compound C:
the driving voltages of the organic electroluminescent devices B1 to B10 prepared in application examples 11 to 20 were between 3.82 to 4.04V, which were reduced by 14 to 19% and 3.3 to 8.6% from those of the organic electroluminescent devices D1 and D3 of comparative example 1 and comparative example 3. The luminous efficiencies of the organic electroluminescent devices B1-B10 are 6.1-6.8 Cd/A, and are respectively increased by 48-65% and 5-17% compared with the luminous efficiencies of the devices D1 and D3. The external quantum efficiency of B1-B10 is between 12.1-13.8%, and is improved by 42-62% and 14-30% compared with the external quantum efficiency of devices D1 and D3. The service life of T95 of B1-B10 is 182-193 h, which is 78% -89% higher than that of T95 of D1 and D3, and is 14% -21%. In addition, the glass transition temperatures of the heterocyclic compounds of the host materials of the light-emitting layers of application examples 11 to 20 were respectively: has good thermal stability at 134 ℃, 112 ℃, 134 ℃, 128 ℃, 134 ℃, 127 ℃, 129 ℃, 117 ℃, 121 ℃ and 132 ℃.
It can be seen that the organic electroluminescent devices prepared in application examples 11 to 20 have lower driving voltage, higher luminous efficiency, higher external quantum efficiency and brightness, compared to comparative examples 1 and 3. Has excellent performances in the aspects of chromaticity, glass transition temperature, half-life period and the like, and has good thermal stability. That is, compared to BPO and compound C, the compound provided by the present invention has better luminous efficiency, better electrical stability and longer lifetime, is good in thermal stability, and can significantly improve the performance of an organic electroluminescent device when used in a light emitting layer of the organic electroluminescent device.
In conclusion, the heterocyclic compound provided by the invention provides a heterocyclic derivative compound with high heat resistance, excellent chemical stability, excellent charge mobility and the like, and the material serving as an organic layer of the heterocyclic derivative compound has excellent electron mobility in an organic electroluminescent device.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (12)

1. A heterocyclic compound characterized by the following chemical structure:
Figure FDA0002341868360000011
in the formula 1, R1To R8The same or different, each independently selected from hydrogen or C1-C10 alkyl;
Y1selected from O, S or N (R)11)，R11Selected from deuterium, a halogen group, cyano, substituted or unsubstituted C6-C18 aryl;
m is selected from the group represented by formula 1-A:
Figure FDA0002341868360000012
in the formula 1-A, X1、X2、X3At least 2 of the N groups are N, and the rest are N or CH;
l is selected from substituted or substituted arylene of C18-C60, substituted or substituted heteroarylene of C6-C60;
Ar1and Ar2The same or different, each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl.
2. The heterocyclic compound according to claim 1, wherein R is11、L、Ar1And Ar2The substituents on the compound are respectively and independently selected from deuterium, halogen, -CN, C1-C10 alkyl, C3-C10 silyl and C3-C10 cycloalkyl.
3. The heterocyclic compound according to claim 1, wherein R in formula 1 is1To R8Each independently selected from hydrogen or C1-C6 alkyl; preferably, R11Selected from deuterium, substituted or unsubstituted aryl groups of C6-C10.
4. The heterocyclic compound according to claim 1, wherein in formula 1-a, X1、X2、X3Are all N.
5. The heterocyclic compound according to claim 1, wherein L in formula 1-a is selected from a substituted or substituted arylene group having C18-C40, a substituted or substituted heteroarylene group having C12-C40.
6. The heterocyclic compound according to claim 1, wherein in formula 1-a, L is selected from the group consisting of groups represented by formulae 1-a1 to 1-a 26:
Figure FDA0002341868360000013
Figure FDA0002341868360000021
in the formulae 1-A1 to 1-A26, Z1To Z3Each independently selected from hydrogen, deuterium, a halogen group, cyano, alkyl, cycloalkyl; or is selected from substituted or unsubstituted aryl or heteroaryl, wherein the substituents are halogen, cyano, alkyl, cycloalkyl, preferably deuterium, a halogen group, cyano, methyl, tert-butyl, cyclohexyl, adamantyl;
when Z is1To Z3When selected from aryl, Z1To Z3Is fused with the attached benzene ring;
the aryl is phenyl, biphenyl, terphenyl, naphthyl, anthryl, fluorenyl, spiro-fluorenyl or 9, 9-diphenylfluorenyl;
the heteroaryl group is: R-Ar3-L2-, in which,
r is phenyl or hydrogen, L2Represents a single bond or phenylene group, Ar3Selected from the group consisting of pyridylene, pyrazinylene, pyrimidylene, benzopyrenylene, benzothiazylene, pyridazinylene, quinolylene, isoquinolylene, quinoxalylene, quinazolinylene, carbazolyl, triazinylene, piperazinyl, dibenzothienyl, dibenzofuranylene, thienyl, phenanthrylene, spiro-fluorenyl, 9-diphenylfluorenyl;
Y2selected from O, S, N (R)12) Or C (R)13R14)，R12To R14The same or different, each independently selected from C6-C12 aryl, C1-C10 alkyl; preferably, R12Is phenyl, R13And R14Are both methyl;
L1represents a single bond or phenylene;
a3is an integer selected from 1 to 3, a4Is an integer selected from 1 to 4, a5Is an integer selected from 1 to 5, a6Is an integer selected from 1 to 6, a8Is an integer selected from 1 to 8, and denotes a binding site connected to an adjacent atom.
7. The heterocyclic compound according to claim 1, characterized in that Ar is Ar1、Ar2Each independently selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C6-C25 heteroaryl.
8. The heterocyclic compound according to claim 1, characterized in that Ar is Ar1、Ar2Each independently selected from the group consisting of:
Figure FDA0002341868360000031
9. the heterocyclic compound according to claim 1, characterized in that the heterocyclic compound is selected from the group consisting of:
Figure FDA0002341868360000041
Figure FDA0002341868360000051
Figure FDA0002341868360000061
Figure FDA0002341868360000071
Figure FDA0002341868360000081
Figure FDA0002341868360000091
Figure FDA0002341868360000101
Figure FDA0002341868360000111
10. a process for the synthesis of a heterocyclic compound according to any of the claims 1 to 9, characterized in that it comprises the following steps:
s1, adding raw materials Ia, dimethylbenzene, raw materials Ib, potassium carbonate, cuprous bromide and 18-crown ether-6, heating to a reflux state for reaction, cooling reaction liquid after liquid phase monitoring reaction is completed, washing inorganic salt in the reaction, separating liquid, drying obtained organic phase with anhydrous sodium sulfate, filtering, concentrating and drying filtrate, and recrystallizing with methylbenzene to obtain an intermediate Id;
Figure FDA0002341868360000112
s2, under the protection of nitrogen, adding an intermediate Id, pinacol diboron diborate, potassium acetate and 1, 4-dioxane, adding [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride at the temperature of 30-80 ℃, and continuously heating to a reflux state for reacting for 3-9 hours; cooling the reaction liquid, pouring water and toluene for extraction under stirring, standing, separating liquid, extracting the water phase with toluene for one time, separating liquid, combining organic phases, adding anhydrous sodium sulfate into the organic phase, stirring and drying to obtain an intermediate Ie;
Figure FDA0002341868360000113
s3, under the protection of nitrogen, adding toluene, the raw material Ic, the intermediate Ie, potassium carbonate, tetrabutylammonium bromide, ethanol and water, adding tetratriphenylphosphine palladium at 30-100 ℃, continuously heating to a reflux state for reaction, cooling a reaction liquid after the liquid phase monitoring reaction is completed, pouring the reaction liquid into water under stirring, standing for liquid separation, extracting a water phase with toluene, combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating a filtrate until no solvent is evaporated, and recrystallizing with toluene to obtain the heterocyclic compound;
Figure FDA0002341868360000114
in step S1, the molar ratio of the raw material Ia to the raw material Ib to the potassium carbonate to the cuprous bromide to the 18-crown-6 is 1: 1-1.3: 4-5: 0.2-0.4: 0.1-0.3;
in step S2, the molar ratio of the intermediate Id to the pinacol diboron, potassium acetate and [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium is 1: 1.2-1.5: 5-8: 0.01-0.05;
in step S3, the molar ratio of the raw material Ic, the intermediate Ie, the potassium carbonate, the tetrabutylammonium bromide and the tetratriphenylphosphine palladium is 1: 1-1.5: 10-20: 0.125-0.25: 0.62-1.
11. An organic electroluminescent device comprising an anode, a cathode and organic layers deposited between the anode and the cathode, the organic layers comprising a hole transport layer, a light emitting layer and an electron transport layer; wherein the electron transport layer or the light-emitting layer comprises the heterocyclic compound according to any one of claims 1 to 9.
12. An electronic device characterized by comprising the organic electroluminescent device according to claim 11.
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