CN110041366B - Indenonanthracene derivative compound and application thereof - Google Patents

Indenonanthracene derivative compound and application thereof Download PDF

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CN110041366B
CN110041366B CN201910399348.5A CN201910399348A CN110041366B CN 110041366 B CN110041366 B CN 110041366B CN 201910399348 A CN201910399348 A CN 201910399348A CN 110041366 B CN110041366 B CN 110041366B
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孙军
张宏科
刘凯鹏
田密
杨丹丹
何海晓
李江楠
王小伟
刘骞峰
高仁孝
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Xi'an Manareco New Materials Co ltd
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Abstract

The invention discloses an indenonanthracene derivative compound and application thereof, belonging to the technical field of organic electroluminescent materials; the general structural formula of the compound is shown as the following formula (I): wherein L is1、L2、L3Is phenylene or substituted phenylene, n is any integer between 0 and 3, Ar1、Ar2Same or different, Ar1、Ar2Each independently is an electron-donating group, X can be a C atom, an O atom, an S atom, an N atom or an Si atom, A represents a diphenyl phosphine oxide molecule or a diphenyl boron molecule derivative; the compound provided by the invention can be used as a doping material and/or a main material of an OLED (organic light emitting diode) to realize high brightness, low voltage, high efficiency and long service life of an organic electroluminescent device; the material prepared from the compounds has higher thermal stability, can obviously improve the luminous stability of the light-emitting device, and is widely applied to OLED light-emitting devices and display devices.
Figure DDA0002059229370000011

Description

Indenonanthracene derivative compound and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescent functional materials and devices, and particularly relates to an indenonanthracene derivative compound and application thereof.
Background
The luminous mechanism of an Organic Light Emitting Diode (OLED) display lighting element, which is a self-luminous electronic element, is a novel photoelectric information technology for directly converting electric energy into Light energy by means of an Organic semiconductor functional material under the action of a direct current electric field. The light emission color can be red, green, blue, yellow alone or combined white. The biggest characteristics of the OLED light-emitting display technology are ultrathin, high response speed, ultralight weight, surface light-emitting and flexible display, can be used for manufacturing monochromatic or panchromatic displays, can be used as a novel light source technology, and can also be used for manufacturing lighting products or a novel backlight source technology for manufacturing liquid crystal displays.
Organic electroluminescent elements (organic EL elements) can be classified into two types, i.e., fluorescent type and phosphorescent type, according to the principle of light emission. When a voltage is applied to the organic EL element, holes from the anode and electrons from the cathode are injected, and they are recombined in the light-emitting layer to form excitons. According to the electron spin statistical method, singlet excitons and triplet excitons are 25%: a proportion of 75% was produced. The fluorescent type uses singlet excitons to emit light, and thus its internal quantum efficiency can only reach 25%. The phosphorescent material is composed of heavy metal elements, and can utilize singlet state energy and triplet state energy simultaneously through interstitial penetration, and the internal quantum efficiency can reach 100%. A Thermally Active Delayed Fluorescence (TADF) material is a third generation organic light emitting material developed after organic fluorescent materials and organic phosphorescent materials. The material generally has smaller singlet-triplet energy level difference (delta Est), triplet excitons can be converted into singlet excitons through reverse gap crossing to emit light, the singlet excitons and the triplet excitons formed under electric excitation can be fully utilized, the internal quantum efficiency of the device can reach 100%, and meanwhile, the material has controllable structure, stable property, low price, no need of precious metal and wide application prospect in the field of OLEDs. The research results in recent years show that: the TADF material can be used not only as a luminescent material (dopant) in a luminescent layer, but also as a host material in the luminescent layer to sensitize the dopant, which is helpful for improving the efficiency of conventional devices, improving the color purity of the devices, and increasing the service life of the devices, and is an organic electroluminescent functional material with a wide application prospect.
An organic electroluminescent device is required to have improved luminous efficiency, reduced driving voltage, improved durability, and the like. Wherein, it is a major subject in the industry to improve the efficiency and the device lifetime. In order to prepare a high-performance OLED light-emitting device, a high-performance OLED functional material needs to be selected and used, and for OLED functional materials with different functions, the basic requirements needed to be met are as follows:
1. the material has good thermal stability, namely, the material can not be decomposed in the long-time evaporation process, and meanwhile, the material is required to have good process reproducibility;
2. the OLED light-emitting device manufactured by matching with the OLED functional material has good performance, namely, better efficiency, longer service life and lower voltage are required. This requires materials with the appropriate highest molecular occupied orbital (HOMO), lowest molecular unoccupied orbital (LUMO), and appropriate triplet energies.
3. As the TADF material, firstly, the material has small singlet state and triplet state energy difference delta Est (generally < 0.1eV), and in addition, the TADF material has proper phosphorescence lifetime.
4. In the face of increasingly urgent market demands, the cost of the material is an important index for judging whether the industrialization can be realized, so that the synthesis route is simple, and the low cost of the raw material plays an important role in rapidly introducing the OLED terminal material into the market.
In recent years, although the development of OLED functional materials has made some breakthrough, as lighting or display applications, there is a need to develop and innovate materials with better performance, especially organic functional materials with longer lifetime and higher efficiency that can be applied to host materials of phosphorescent OLED systems and TADF systems.
Disclosure of Invention
The invention aims to provide an indenonanthracene derivative compound which is applied to an organic electroluminescent device as a luminescent layer material and can obviously improve the device performance of the organic electroluminescent device.
The first purpose of the invention is to provide an indenonanthracene derivative compound, the structural general formula of which is shown as the following formula (I):
Figure BDA0002059229350000031
in the formula (I), L1、L2、L3Are each phenylene or substituted phenylene; when L is1、L2、L3In the case of substituted phenylene radicals, these substituents are methyl, ethyl or cyano; n is any integer between 0 and 3;
x is oxygen atom, sulfur atom, Si-m1m2、C-m1m2Or N-m3Wherein: m is1、m2Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, phenyl or biphenyl; m is3Is aryl;
Ar1、Ar2are electron donating groups, and are respectively and independently selected from substituted or unsubstituted carbazolyl, formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII):
Figure BDA0002059229350000032
when Ar is1、Ar2When the substituents are respectively and independently selected from substituted carbazolyl, the substituents are C1-C6 alkyl, phenyl and biphenyl;
in the formula (II), Ar3、Ar4Each independently selected from any one of substituted or unsubstituted aryl or condensed ring aryl of C6-C30, substituted or unsubstituted condensed heterocyclic group of C6-C30, five-membered heterocyclic ring, six-membered heterocyclic ring or substituted heterocyclic ring, and substituted or unsubstituted amino;
in the formula (III), R1、R2Are respectively and independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, cyano, trifluoromethyl or fluoro;
R3、R4are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, alkoxy groups of C1-C6, substituted or unsubstituted amine groups, substituted or unsubstituted condensed heterocyclic groups of C6-C30, five-membered, six-membered or substituted heterocyclic rings, cyano groups, trifluoromethyl or fluoro groups;
in the formula (IV), T is oxygen atom, sulfur atom, C-m4m5、Si-m4m5Or N-m6；
Wherein: m is4、m5Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, phenyl or biphenyl;
m6is any one of substituted or unsubstituted aryl or condensed ring aryl of C6-C30, substituted or unsubstituted condensed heterocyclic group of C6-C30, five-membered, six-membered heterocyclic ring or substituted heterocyclic ring, substituted or unsubstituted amino;
in the formulae (V) and (VI), Y is a carbon atom or a silicon atom;
a is a group of formula (VIII) or (IX):
Figure BDA0002059229350000041
wherein R is5-R10Alkyl of C1-C6, preferably methyl, ethyl, tert-butyl.
Preferably, in the formula (II), Ar3、Ar4Are respectively independentSelected from phenyl, biphenyl, terphenyl, naphthyl, amine, carbazolyl, furanyl, dibenzofuranyl, thienyl, dibenzothienyl, fluorenyl, dibenzopyridyl, dibenzooxazinyl, or pheno oxazinyl;
when Ar is3、Ar4When substituted, the substituent is one of methyl, isopropyl, tert-butyl, methoxy, phenyl, cyano, biphenyl, naphthyl, amino, carbazolyl, furyl, dibenzofuryl, thienyl, dibenzothienyl, fluorenyl, dibenzopyridyl, dibenzooxazinyl, or pheno oxazinyl.
More preferably, the group represented by formula (ii) is selected from one of the following structural formulae:
Figure BDA0002059229350000051
preferably, R1、R2Each independently selected from hydrogen atom, methyl, isopropyl, tert-butyl, methoxy, cyano, trifluoromethyl or fluoro;
R3、R4each independently selected from any one of a hydrogen atom, a cyano group, a trifluoromethyl group, a fluoro group, a carbazolyl group, an N-phenylcarbazolyl group, a dianilino group, a dibenzofuranyl group, a dibenzothienyl group, a dibenzopyridyl group, a dibenzooxazinyl group, a fluorenyl group and a 9, 9-dimethylfluorenyl group.
More preferably, the group represented by formula (iii) is selected from one of the following structural formulae:
Figure BDA0002059229350000061
preferably, in the formula (IV), m1、m2Each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a tert-butyl group, a phenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzopyridinyl group, a dibenzooxazinyl group, a carbazolyl group, an N-phenylcarbazolyl group, a triphenylamine group, a fluorenyl group and a 9, 9-dimethylfluorenyl group;
m3selected from the group consisting of a hydrogen atom, a phenyl group, an amine group, a biphenyl group, a naphthyl group, a carbazolyl group, a furyl group, a thienyl group, a fluorenyl group, a dibenzofuryl group, a dibenzothienyl group, an N-phenylcarbazolyl group, a triphenylamine group, a 9, 9-dimethylfluorenyl group, a dibenzofuran-4-yl- (9, 9-dimethyl-9H-fluoren-2-yl) -amine, a 3, 9-diphenyl-9H-carbazolyl group, a 3-dibenzofuran-4-yl-9-phenyl-9H-carbazolyl group, a 3- (9, 9-dimethyl-9H-fluoren-1-yl) -9-phenyl-9H-carbazolyl group, a 12, 12-dimethyl-12H-10-oxa-indeno [2,1-B]Fluorenyl, spirobifluorenyl.
More preferably, the group represented by formula (iv) is selected from one of the following structural formulae:
Figure BDA0002059229350000071
preferably, the indenonanthracene derivative compound is specifically one of the following compounds:
Figure BDA0002059229350000081
Figure BDA0002059229350000091
Figure BDA0002059229350000101
Figure BDA0002059229350000111
the second purpose of the invention is to provide the application of the indenonanthracene derivative compound in an organic electroluminescent device.
It is a third object of the present invention to provide an organic electroluminescent device comprising a light-emitting layer, the light-emitting layer material comprising the indenonanthracene derivative compound described in any one of the above.
A fourth object of the present invention is to provide an application of the above organic electroluminescent device in an organic electroluminescent display device.
Compared with the prior art, the invention has the following beneficial effects: the indenonanthracene derivative compound provided by the invention has a proper HOMO/LUMO value, can realize high brightness, low voltage, high efficiency and long service life of an organic EL element, and meanwhile, the material prepared from the compound has higher thermal stability, can remarkably improve the luminous stability of a light-emitting device, and can be widely applied to OLED light-emitting devices and display devices as a main material of a light-emitting layer or a thermal activity delayed fluorescence light-emitting material.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device provided in an embodiment of the present invention.
Description of reference numerals:
1. the cathode layer comprises a substrate, 2, an anode layer, 3, a hole injection layer, 4, a first hole transport layer, 5, a second hole transport layer, 6, a light emitting layer, 7, a hole blocking layer, 8, an electron transport layer, 9, an electron injection layer, 10 and a cathode layer.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The invention provides an indenonanthracene derivative compound, which has a structural general formula as shown in the following formula (I):
Figure BDA0002059229350000121
Figure BDA0002059229350000131
L1、L2、L3are each phenylene or substituted phenylene; when L is1、L2、L3In the case of substituted phenylene radicals, these substituents are methyl, ethyl or cyano; n is any integer between 0 and 3;
preferably, n is 0, 1 or 2;
x is oxygen atom, sulfur atom, Si-m1m2、C-m1m2Or N-m3Wherein: m is1、m2Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, phenyl or biphenyl; m is3Is aryl;
Ar1、Ar2are electron donating groups, and are respectively and independently selected from substituted or unsubstituted carbazolyl, formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII):
Figure BDA0002059229350000132
when Ar is1、Ar2When the substituents are respectively and independently selected from substituted carbazolyl, the substituents are C1-C6 alkyl, phenyl and biphenyl;
in the formula (II), Ar3、Ar4Each independently selected from any one of substituted or unsubstituted aryl or condensed ring aryl of C6-C30, substituted or unsubstituted condensed heterocyclic group of C6-C30, five-membered heterocyclic ring, six-membered heterocyclic ring or substituted heterocyclic ring, and substituted or unsubstituted amino;
in the formula (III), R1、R2Are respectively and independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, cyano, trifluoromethyl or fluoro;
R3、R4are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, alkoxy groups of C1-C6, substituted or unsubstituted amine groups, substituted or unsubstituted condensed heterocyclic groups of C6-C30, five-membered, six-membered or substituted heterocyclic rings, cyano groups, trifluoromethyl or fluoro groups;
in the formula (IV), T is oxygen atom, sulfur atom, C-m4m5、Si-m4m5Or N-m6；
Wherein: m is4、m5Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, phenyl or biphenyl;
m6is any one of substituted or unsubstituted aryl or condensed ring aryl of C6-C30, substituted or unsubstituted condensed heterocyclic group of C6-C30, five-membered, six-membered heterocyclic ring or substituted heterocyclic ring, substituted or unsubstituted amino;
in the formulae (V) and (VI), Y is a carbon atom or a silicon atom;
a is a group of formula (VIII) or (IX):
Figure BDA0002059229350000141
wherein R is5-R10Alkyl of C1-C6, preferably methyl, ethyl, tert-butyl.
According to the micromolecule compound provided by the invention, the indenonanthracene derivative is connected with groups such as furan, carbazole, thiophene, fluorene, heteroaryl amino, acridine, thiophene oxazine and thia oxazine through a benzene bridge or directly connected with 9 and 10 positions of anthracene, and a diphenyl phosphine oxide ligand or a boron-based ligand is bridged on an anthracene five-membered ring to construct a bipolar compound, so that the compound can be used as a doping material or a main body material of an organic Electroluminescent (EL) diode to realize high brightness, low voltage, high efficiency and long service life of an organic Electroluminescent (EL) element. The parent chain of an indenonanthracene derivative as a core is linked with an oxyphosphorus group or a boron-based ligand to show stronger electron-withdrawing capability, and the parent is connected with an electron-donating group through a phenyl bridge or without the phenyl bridge to construct a bipolar material with an electron-donating receptor, wherein the material has smaller singlet energy and triplet energy difference (delta Est), can realize the reversal from triplet energy to singlet energy, and thus has thermal activity delayed fluorescence property (TADF). The material disclosed by the invention has excellent properties when being used as a main material, on one hand, the bipolar characteristic of the material effectively enriches holes and electrons in a light-emitting layer, increases the recombination zone of excitons, effectively improves the efficiency and the service life of a device, and reduces the attenuation of the efficiency; on the other hand, the TADF material can be used as a main body material with TADF property to effectively sensitize a luminescent material, effectively improve the efficiency and the service life of a device, optimize the spectrum of the TADF material and improve the color purity of the TADF device. As a TADF luminescent material, the material of different luminescent colors can be obtained by modifying the invented material through different substituents, and the internal quantum efficiency is obviously improved.
Next, a specific synthetic method for preparing several intermediates corresponding to the above-mentioned compounds is first provided.
(1) Synthesis of intermediate 1-2
Figure BDA0002059229350000151
Introducing nitrogen into a 2L three-necked bottle, sequentially adding 1L dichloromethane and 53.7g aluminum trichloride, cooling to 0 ℃, then adding 100g of intermediate 1-1, stirring to completely dissolve the raw materials, and then dropwise adding 54.3g of 200ml DCM solution of phthalic anhydride; after the dropwise addition is finished, keeping the temperature for continuously reacting for 6 hours, monitoring the complete consumption of the intermediate 1-1 by TLC, and stopping the reaction; pouring the reaction solution into a cold 6M hydrochloric acid solution, fully stirring, standing, separating liquid, washing an organic phase to be neutral, drying anhydrous sodium sulfate, concentrating to obtain a white solid, adding the white solid into 400ml of phosphoric acid, heating to 130 ℃, and stirring for reaction for 3 hours; cooling to room temperature, pouring the reaction liquid into ice water, adding a sodium hydroxide solution to adjust the pH value to be neutral, filtering, and washing a filter cake to be neutral; and drying the filter cake, and then boiling and washing the filter cake with methanol for purification to obtain 108.6g of light yellow solid, namely the intermediate 1-2 with the yield of 73.6 percent.
Nuclear magnetic spectrum data of intermediates 1-2:1H NMR(400MHz,CDCl3)δ8.38(s,1H),8.09(s,1H),7.80(d,J＝7.6,2H),7.73(m,2H),7.55(d,J＝7.6,3H),1.67(s,6H)。
(2) synthesis of intermediates 1 to 3
Figure BDA0002059229350000152
Adding 1L of isopropanol and 100g of intermediate 1-2 into a 2L three-necked bottle, then adding 93.8g of sodium borohydride in batches, stirring at normal temperature for reaction for 1 hour after the addition is finished, then heating to reflux and continuing the reaction for 5 hours, monitoring by TLC that the intermediate 1-2 is completely consumed, and stopping the reaction; cooling to room temperature, pouring the reaction solution into 3 times of water, stirring to separate out a solid, filtering, and washing a filter cake to be neutral; and adding the filter cake into a 2M hydrochloric acid solution, heating to reflux and react for 3h, cooling to room temperature, filtering, washing the filter cake to be neutral, drying, and recrystallizing with ethanol to obtain 80.7g of yellow solid, namely the intermediate 1-3, wherein the yield is 87.2%.
Nuclear magnetic spectrum data of intermediates 1 to 3:1H NMR(400MHz,CDCl3)δ7.95(d,J＝7.2,1H),7.78-7.83(m,2H),7.61-7.68(m,5H),7.52(s,1H),7.32(d,J＝7.2,2H),1.63(s,6H)；
(3) synthesis of intermediates 1 to 4
Figure BDA0002059229350000161
Introducing nitrogen into a 1L three-necked bottle, sequentially adding 400ml of THF and 40g of intermediate 1-3, cooling to-78 ℃, slowly dropwise adding 47ml of 2.5M butyl lithium, keeping the temperature after dropwise adding, stirring for reaction for 1h, adding 23.6g of diphenyl phosphine chloride, keeping the temperature for continuous reaction for 3h, and adding a saturated ammonium chloride solution for quenching reaction; after the temperature is raised to the room temperature, THF is evaporated under reduced pressure, the mixture is filtered, filter cakes are washed to be neutral and then are added into 50ml of hydrogen peroxide, the mixture is stirred at the temperature of 40 ℃ to react for 3 hours and then is filtered, and the filter cakes are washed to be neutral. And drying the filter cake, and recrystallizing with toluene to obtain light yellow solid 40.4g, namely the intermediate 1-4, with the yield of 76.3%.
Nuclear magnetic spectrum data of intermediates 1 to 4:1H NMR(400MHz,CDCl3)δ8.09(d,J＝7.6,1H),7.83(s,1H),7.64-7.68(m,4H),7.52-7.56(m,3H),7.44-7.47(td,J＝7.6,4H),7.32-7.40(m,8H),1.73(s,6H)。
(4) synthesis of intermediates 1 to 5
Figure BDA0002059229350000162
40g of intermediate 1-4 and 200ml of DMF are added into a 500ml three-necked flask, the mixture is stirred to completely dissolve the raw materials, 28.8g of NBS is added, the mixture is stirred at normal temperature for reaction for 2 hours, then the temperature is raised to 60 ℃, the reaction is continued for 4 hours, and then the temperature is reduced to the room temperature. Pouring the reaction solution into 3 times volume of water, stirring to separate out a solid, filtering, and washing a filter cake to be neutral; adding the filter cake into n-hexane with the volume 8 times that of the filter cake, refluxing, boiling and washing for 3 hours, cooling to room temperature, and filtering to obtain light yellow solid 50.5g, wherein the yield is 95.8%.
Nuclear magnetic spectrum data of intermediates 1 to 5:1H NMR(400MHz,CDCl3)δ8.34(s,1H),8.06(d,J＝7.6,1H),7.67(d,J＝7.2,2H),7.52-7.56(m,3H),7.44-7.47(td,J＝7.6,4H),7.32-7.40(m,8H),1.73(s,6H)。
(5) synthesis of intermediate 2-1
Figure BDA0002059229350000171
The synthesis steps are the same as those of the intermediates 1 to 4, except that: replacing diphenylphosphine chloride with 46.8g of bis (2,4, 6-triisopropylphenyl) boron fluoride gave 52.3g of intermediate 2-1 in 68.7% yield.
Nuclear magnetic spectrum data of intermediate 2-1:1H NMR(400MHz,CDCl3)δ8.12(d,J＝7.6,1H),7.83(s,1H),7.61-7.68(m,5H),7.52(s,1H),7.40(d,J＝7.6,1H),7.32(d,J＝7.2,2H),6.80(s,4H),3.12(m,6H),1.73(s,6H),1.29(d,J＝8.4,36H)。
(6) synthesis of intermediate 2-2
Figure BDA0002059229350000172
The synthesis steps are the same as those of the intermediates 1 to 5, except that: intermediate 1-4 was replaced with 50g of intermediate 2-1, and NBS was used in an amount of 25.0g, to give 56.6g of intermediate 2-2, yield 92.6%.
Nuclear magnetic spectrum data of intermediate 2-2:1H NMR(400MHz,CDCl3)δ8.34(s,1H),8.12(d,J＝7.6,1H),7.58-7.67(m,4H),7.40(d,J＝7.6,1H),7.32(d,J＝7.2,2H),6.80(s,4H),3.12(m,6H),1.73(s,6H),1.29(d,J＝8.4,36H)。
(7) synthesis of intermediate 3-2
Figure BDA0002059229350000181
The synthesis steps are the same as the intermediates 1-2, except that: the amount of aluminum trichloride was 59.4g, intermediate 1-1 was replaced with 100g of intermediate 3-1 and the amount of the DCM solution of phthalic anhydride was 60.1g of 200ml of DCM solution of phthalic anhydride to give 117.2g of intermediate 3-2 with a yield of 76.9%.
Nuclear magnetic spectrum data of intermediate 3-2:1H NMR(400MHz,CDCl3)δ8.03(s,1H),7.96(s,1H),7.80(d,J＝7.6,2H),7.55-7.58(m,3H),7.38(d,J＝7.2,1H),7.30(d,J＝7.2,1H)。
(8) synthesis of intermediate 3-3
Figure BDA0002059229350000182
The synthesis steps are the same as those of the intermediates 1 to 3, except that: intermediate 1-2 was replaced with 110g of intermediate 3-2, and the amount of sodium borohydride used was 110.3g, yielding 93.2g of intermediate 3-3 in 92.1% yield.
Nuclear magnetic spectrum data of intermediate 3-3:1H NMR(400MHz,CDCl3)δ7.67(m,4H),7.59(s,1H),7.49(s,1H),7.38-7.42(m,2H),7.30-7.32(m,3H)。
(9) synthesis of intermediates 3-4
Figure BDA0002059229350000183
The synthesis steps are the same as the intermediates 1 to 4, except that: intermediate 1-3 was replaced with intermediate 3-3, butyl lithium was used in an amount of 50ml and diphenyl phosphine chloride was used in an amount of 25.4g to give 43.9g of intermediate 3-4 with a yield of 81.3%.
Nuclear magnetic spectrum data of intermediates 3-4:1H NMR(400MHz,CDCl3)δ7.68(m,4H),7.46-7.48(m,4H),7.38-7.41(m,6H),7.32-7.35(m,6H),7.12(d,J＝7.6,1H)。
(10) synthesis of intermediates 3-5
Figure BDA0002059229350000191
The synthesis steps are the same as those of the intermediates 1 to 5, except that: intermediates 1-4 were replaced with intermediates 3-4 and the amount of NBS used was 30.4g, yielding 47.9g of intermediates 3-5 in 89.6% yield.
Nuclear magnetic spectrum data of intermediates 3 to 5:1H NMR(400MHz,CDCl3)δ7.67(d,J＝7.2,2H),7.46-7.48(m,4H),7.38-7.41(m,6H),7.32-7.35(m,6H),7.12(d,J＝7.6,1H)。
(11) synthesis of intermediate 4-1
Figure BDA0002059229350000192
The synthesis steps are the same as those of the intermediate 2-1, except that: intermediate 1-3 was replaced with intermediate 3-3, butyllithium was used in an amount of 51ml, and bis (2,4, 6-triisopropylphenyl) boron fluoride was used in an amount of 50.3g, to give 58.2g of intermediate 4-1 with a yield of 73.8%.
Nuclear magnetic spectrum data of intermediate 4-1:1H NMR(400MHz,CDCl3)δ7.67(m,4H),7.49-7.51(m,2H),7.40-7.42(m,2H),7.32(d,J＝7.2,2H),7.12(d,J＝7.6,1H),6.80(s,4H),3.12(m,6H),1.29(d,J＝8.4,36H)。
(12) synthesis of intermediate 4-2
Figure BDA0002059229350000193
The synthesis steps are the same as those of the intermediate 2-2, except that: intermediate 2-1 was replaced with intermediate 4-1 and the amount of NBS used was 26.0g, yielding 58.9g of intermediate 4-2 with a yield of 95.8%.
Nuclear magnetic spectrum data of intermediate 4-2:1H NMR(400MHz,CDCl3)δ7.67(d,J＝7.6,2H),7.49-7.51(m,2H),7.40-7.42(m,2H),7.32(d,J＝7.2,2H),7.12(d,J＝7.6,1H),6.80(s,4H),3.12(m,6H),1.29(d,J＝8.4,36H)。
(13) synthesis of intermediate 5-1
Figure BDA0002059229350000201
Introducing nitrogen into a 1L three-necked bottle, sequentially adding 400ml of THF and 35.2g of 9- (4-bromophenyl) carbazole, stirring to completely dissolve the raw materials, cooling to-78 ℃, slowly dropwise adding 44ml of 2.5M butyl lithium, keeping the temperature after dropwise adding, stirring to react for 1h, then adding 20g of intermediate 1-2, keeping the temperature, continuing to react for 3h, and adding a saturated ammonium chloride solution to quench the reaction. And (3) heating to room temperature, evaporating THF under reduced pressure, filtering, washing a filter cake to be neutral, adding the filter cake into 180ml of acetic acid, adding 30ml of concentrated hydrochloric acid, stirring at room temperature for reacting for 4 hours, pouring into ice water with the volume of 3 times of that of the mixture, stirring to separate out a solid, filtering, and washing the filter cake to be neutral. The filter cake was dried and then chromatographed using toluene to obtain 29.6g of intermediate 5-1 as a white solid in 69.7% yield.
Nuclear magnetic spectrum data of intermediate 5-1:1H NMR(400MHz,CDCl3)δ7.95(d,J＝7.6,1H),7.83(s,1H),7.78(s,1H),7.68(d,J＝7.2,2H),7.52-7.61(m,10H),7.40(d,J＝7.2,4H),7.32-7.35(m,6H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H),1.73(s,6H)。
(14) synthesis of intermediate 6-1
Figure BDA0002059229350000211
The synthesis steps are the same as the intermediate 5-1, except that: the amount of 9- (4-bromophenyl) carbazole was 37.6g, the amount of butyllithium was 47ml, and intermediate 1-2 was replaced with intermediate 3-2 to give 31.9g of intermediate 6-1 with a yield of 72.6%.
Nuclear magnetic spectrum data of intermediate 6-1:1H NMR(400MHz,CDCl3)δ7.68(d,J＝7.2,2H),7.52-7.58(m,10H),7.38-7.42(m,6H),7.30-7.32(m,7H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H)。
we now provide methods for synthesizing these compounds, particularly taking the partial indenonanthracene derivative compounds as examples.
Example 1
Figure BDA0002059229350000212
Introducing nitrogen into a 1L three-necked bottle, sequentially adding 12.8g of carbazole, 20g of intermediate 1-5, 16.9g of potassium carbonate, 0.81g of 18-crown-6 ether and 400ml of DMF, stirring until the raw materials are completely dissolved, adding 0.58g of cuprous iodide, heating to 130 ℃, stirring for reaction for 10 hours, monitoring the complete consumption of the compound 1-5 by TLC, stopping the reaction, cooling to room temperature, pouring the reaction solution into 3 times of volume of water, stirring to separate out a solid, filtering, washing a filter cake to be neutral, drying the filter cake, dissolving the filter cake with toluene, passing through an insulating column, concentrating and recrystallizing the eluent to obtain 20.8g of white solid, namely the compound 1, wherein the yield is 82.3%.
Nuclear magnetic spectroscopy data for compound 1:1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.6,1H),7.67-7.71(m,4H),7.52-7.55(m,6H),7.46(td,J＝7.6,4H),7.32-7.40(m,12H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H),1.73(s,6H)。
example 2
Figure BDA0002059229350000221
Introducing nitrogen into a 1L three-necked bottle, sequentially adding 11.8g of sodium tert-butoxide, 16.0g of 9, 9-dimethylacridine, 20g of intermediate 1-5 and 400ml of toluene, stirring until the raw materials are completely dissolved, adding 69mg of palladium acetate and 0.3ml of tri-tert-butylphosphine toluene solution, heating until the mixture is refluxed and stirred for reaction for 12 hours, monitoring the complete consumption of the compound 1-5 by TLC, stopping the reaction, cooling to 60-70 ℃, filtering, washing the filtrate to be neutral by hot water, refluxing to remove water, passing through an insulating column, concentrating and recrystallizing the eluent to obtain 21.9g of white solid, namely the compound 3, wherein the yield is 78.5%.
Nuclear magnetic spectroscopy data for compound 3:1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.6,1H),7.68(d,J＝7.2,4H),7.52(td,J＝7.6,2H),7.46(td,J＝7.6,4H),7.32-7.40(m,8H),6.88(d,J＝7.2,8H),6.83(td,J＝7.2,4H),6.54(td,J＝7.2,4H),1.73(s,6H),1.67(s,12H)。
example 3
Figure BDA0002059229350000222
The synthesis steps are the same as the intermediates 1-4, except that the intermediates 1-3 are replaced by the intermediates 5-1, the consumption of butyl lithium is 10.3ml, the consumption of diphenyl phosphine chloride is 5.2g, and the consumption of hydrogen peroxide is 20ml, so that 17.5g of the compound 8 is obtained, and the yield is 76.8%.
Nuclear magnetic spectroscopy data for compound 8:1H NMR(400MHz,CDCl3)δ8.13(d,J＝7.6,1H),7.83(s,1H),7.65-7.68(m,3H),7.52-7.61(m,12H),7.40-7.46(m,8H),7.32-7.35(m,10H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H),1.73(s,6H)。
example 4
Figure BDA0002059229350000231
The synthesis procedure was the same as in example 1, except that: the amount of carbazole was 13.3g, intermediates 1-5 were replaced with intermediates 3-5, the amount of potassium carbonate was 17.6g, the amount of 18-crown-6 ether was 0.84g, and the amount of cuprous iodide was 0.61g, giving 20.2g of compound 20 with a yield of 79.2%.
Nuclear magnetic spectroscopy data for compound 20:1H NMR(400MHz,CDCl3)δ7.67(d,J＝7.2,2H),7.55(d,J＝7.2,4H),7.46-7.48(m,4H),7.38-7.41(m,10H),7.32-7.35(m,6H),7.08-7.10(d,J＝7.6,5H),7.00(td,J＝7.2,4H)。
example 5
Figure BDA0002059229350000232
The synthesis procedure was the same as in example 1, except that: the amount of carbazole was 9.9g, intermediates 1-5 were replaced with intermediates 4-2, the amount of potassium carbonate was 13.1g, the amount of 18-crown-6 ether was 0.63g, and the amount of cuprous iodide was 0.45g, yielding 17.3g of compound 54 with a yield of 71.8%.
Nuclear magnetic spectroscopy data for compound 54:1H NMR(400MHz,CDCl3)δ7.67(d,J＝7.2,2H),7.49-7.55(m,6H),7.40-7.42(m,6H),7.32(d,J＝7.2,2H),7.08-7.12(m,5H),7.00(t,J＝7.2,4H),6.80(s,4H),3.12(m,6H),1.29(d,J＝8.4,36H)。
example 6
Figure BDA0002059229350000241
The synthesis steps are the same as those of the intermediates 1 to 4, except that: the intermediate 1-3 was replaced with 20g of the intermediate 6-1, the amount of butyllithium used was 10.6ml, diphenylphosphinochloride was replaced with 10.5g of bis (2,4, 6-triisopropylphenyl) boron fluoride and the amount of hydrogen peroxide used was 20ml, to give 19.2g of the compound 55 with a yield of 68.2%.
Nuclear magnetic spectroscopy data for compound 55:1H NMR(400MHz,CDCl3)δ7.67(d,J＝7.2,2H),7.53-7.58(m,10H),7.40-7.43(m,6H),7.30-7.32(m,7H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H),6.80(s,4H),3.12(m,6H),1.29(d,J＝8.4,36H)。
example 7
Figure BDA0002059229350000242
The synthesis procedure was the same as in example 2, except that: sodium tert-butoxide was used in an amount of 8.8g, 9, 9-dimethylacridine 12.0g, intermediate 1-5 was replaced with intermediate 2-2, palladium acetate was used in an amount of 52mg, 18.5g of compound 56, 71.5% yield.
Nuclear magnetic spectroscopy data for compound 56:1H NMR(400MHz,CDCl3)δ8.11(d,J＝7.6,1H),7.82(s,1H),7.62-7.67(m,3H),7.46(s,1H),7.40(d,J＝7.6,1H),7.32(d,J＝7.2,2H),6.80-6.88(m,12H),6.54(td,J＝7.2,4H),6.38(d,J＝7.2,4H),3.12(m,6H),1.73(s,6H),1.67(s,12H),1.29(d,J＝8.4,36H)。
example 8
Figure BDA0002059229350000251
The synthesis procedure was the same as in example 1, except that: the amount of carbazole was 9.6g, intermediates 1-5 were replaced with intermediates 2-2, the amount of potassium carbonate was 12.7g, the amount of 18-crown-6 ether was 0.61g, and the amount of cuprous iodide was 0.44g, to give 18.3g of compound 57 with a yield of 76.2%.
Nuclear magnetic spectroscopy data for compound 57:1H NMR(400MHz,CDCl3)δ8.11(d,J＝7.6,1H),7.83(s,1H),7.62-7.67(m,4H),7.55(d,J＝7.2,4H),7.40(m,5H),7.32(d,J＝7.2,2H),7.08(td,J＝7.2,4H),7.00(td,J＝7.2,4H),6.80(s,4H),3.12(m,6H),1.73(s,6H),1.29(d,J＝8.4,36H)。
we performed T separately on some of the compounds and existing materials provided in the above examples of the present invention1Energy levels and HOMO, LUMO energy levels were tested and the results are shown in table 1:
TABLE 1 Compounds T of the invention1Energy level and HOMO, LUMO
Figure BDA0002059229350000252
Note: highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) and triplet energy (T)1) The data obtained by simulation calculation of Gaussian 09 software is calculated by adopting a B3LYP hybridization functional with a group 6-31g (d).
As can be seen from table 1, the compounds provided by the present invention have suitable HOMO/LUMO, and are favorable for carrier transport and energy transfer in OLED devices, and these compounds can be used as fluorescent host materials and also as light emitting materials. The above organic electroluminescent device may be a fluorescent device or a device containing a Thermally Active Delayed Fluorescence (TADF) material, without particular limitation. Therefore, after the indenonanthracene derivative compound is used in the light emitting layer of the OLED device, the light emitting efficiency, the service life and other properties of the device can be effectively improved.
In the following, some of the compounds provided by the present invention are used as an example and applied to an organic electroluminescent device as a luminescent layer material (host material and/or doped dye) to verify the excellent effects obtained by the organic electroluminescent device.
The excellent effect of the OLED material applied to the device is detailed through the device performances of device examples 1-5 and comparative example 1. The structure manufacturing processes of the devices of examples 1-5 and comparative example 1 are completely the same, and the same glass substrate and electrode material are adopted, the film thickness of the electrode material is also kept consistent, and the difference is that the material of the light emitting layer is adjusted, which is specifically as follows.
Device application example
Device example 1
The present embodiment provides an organic electroluminescent device, which has a structure as shown in fig. 1, and includes a substrate 1, an anode layer 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode layer 10, which are sequentially stacked.
Wherein, the anode layer 2 is made of Indium Tin Oxide (ITO) with high common function, the hole injection layer 3 is made of HAT-CN with the thickness of 5 nm; NPB is selected as the material of the first hole transport layer 4, and the thickness is 60 nm; TAPC is selected as a material of the second hole transport layer 5, and the thickness is 15 nm; the light-emitting layer 6 used compound 1 as a light-emitting material and Host1 as a Host material, and had a doping ratio of 5% and a thickness of 30 nm; TPBI is selected as the material of the hole blocking layer 7, and the thickness is 10 nm; the material of the electron transport layer 8 is ET-1, and the thickness is 35 nm; liq is selected as the material of the electron injection layer 9, and the thickness is 2 nm; the cathode layer is made of Al and has a thickness of 120 nm.
The structural formula of the basic material used by each functional layer in the device is as follows:
Figure BDA0002059229350000271
the organic electroluminescent device is prepared by the following specific steps:
1) cleaning an ITO anode on a transparent glass substrate, respectively ultrasonically cleaning the ITO anode for 20 minutes by using deionized water, acetone and ethanol, and then carrying out Plasma (Plasma) treatment for 5 minutes in an oxygen atmosphere;
2) evaporating a hole injection layer material HAT-CN on the ITO anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 5nm, and the hole injection layer is used as a hole injection layer;
3) evaporating a hole transport material NPB on the hole injection layer in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 60nm, and the hole transport layer is used as a first hole transport layer;
4) evaporating a hole transport material TAPC (titanium polycarbonate) on the first hole transport layer NPB in a vacuum evaporation mode, wherein the thickness of the hole transport material TAPC is 15nm, and the layer serves as a second hole transport layer;
5) co-evaporating a light-emitting layer on the second hole transport layer by a vacuum evaporation mode, using the compound 1 as a light-emitting material and the Host1 as a Host material, wherein the doping amount ratio is 5%, and the thickness is 30 nm;
6) evaporating a hole blocking material TPBI on the light-emitting layer in a vacuum evaporation mode, wherein the thickness of the hole blocking material TPBI is 10nm, and the layer is used as a hole blocking layer;
7) evaporating an electron transport material ET-1 on the hole blocking layer in a vacuum evaporation mode, wherein the thickness of the electron transport material ET-1 is 35nm, and the electron transport material ET-1 serves as an electron transport layer;
8) evaporating an electron injection material Liq on the electron transport layer in a vacuum evaporation mode, wherein the thickness of the electron injection material Liq is 2nm, and the electron injection layer is used as an electron injection layer;
9) on the electron injection layer, a cathode Al was deposited by vacuum deposition to a thickness of 120nm, and the layer was used as a cathode conductive electrode.
Device example 2
Same as device example 1, except that: compound 3 was used as the dopant in place of compound 1.
Device example 3
Same as device example 1, except that: compound 8 was used as the dopant in place of compound 1.
Device example 4
Same as device example 1, except that: compound 54 was used as a dopant in place of compound 1.
Device example 5
Same as device example 1, except that: compound 55 was used as Host instead of compound Host1, and the dopant was BD 1.
Comparative example 1
Same as device example 1, except that: BD1 as a dopant.
The composition of the devices prepared in inventive device examples 1-4 and comparative example 1 is shown in table 2:
TABLE 2 comparison table of organic electroluminescent element components of each device example
Figure BDA0002059229350000281
Connecting the cathode and the anode of each group of organic electroluminescent devices by using a known driving circuit, and testing the voltage-efficiency-current density relation of the OLED devices by adopting a Keithley2400 power supply and a PR670 photometer through a standard method; the service life of the device is tested by a constant current method under the condition that the constant current density is 10mA/cm2The time for the test luminance to decay to 80% of the initial luminance is defined as the device LT80Lifetime, test results are shown in table 3:
table 3 performance results for each group of organic electroluminescent devices
Figure BDA0002059229350000291
As can be seen from Table 3, the compounds provided by the present invention are excellent in performance when applied to OLED emitters as host materials and light-emitting materials for light-emitting layers. Compared with the comparative example 1BD1, the compound 1 in the device example 1 as the luminescent material has the advantages that the luminescent efficiency and the service life are both remarkably improved, the luminescent efficiency is improved by 12.7%, and the service life is improved by 30%; compared with Host1 in comparative example 1, the compound 55 in device example 5 as the Host material has the advantages of improved luminous efficiency by about 12.7%, improved service life by 50%, and better color coordinate; therefore, the compound provided by the invention is selected as a main material or a luminescent material of the OLED device, and compared with the OLED luminescent device applied by the existing material, the photoelectric properties of the device, such as luminous efficiency, service life, color purity and the like, have good performances, and have great application value and commercial prospect in the application of the OLED device and good industrial prospect.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.

Claims (6)

1. An indenonanthracene derivative compound is characterized in that the structural general formula is shown as the following formula (I):
Figure FDA0003388279960000011
in the formula (I), L1、L2、L3Are both phenylene radicals; n is any integer between 0 and 3;
x is oxygen atom, C-m1m2Wherein: m is1、m2Are respectively and independently selected from hydrogen atoms and alkyl groups of C1-C6;
Ar1、Ar2all are electron-donating groups, and are respectively and independently selected from carbazolyl, groups shown in formula (III) or formula (IV):
Figure FDA0003388279960000012
in the formula (III), R1、R2Are respectively and independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, cyano, trifluoromethyl or fluoro;
R3、R4are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6, alkoxy groups of C1-C6, substituted or unsubstituted amine groups, and substituted or unsubstituted condensed heterocyclic groups of C6-C30Five-membered, six-membered or substituted heterocyclic ring, cyano, trifluoromethyl or fluoro;
in the formula (IV), T is C-m4m5Wherein: m is4、m5Are respectively and independently selected from hydrogen atoms, alkyl groups of C1-C6 or phenyl groups;
a is a group of formula (VIII) or (IX):
Figure FDA0003388279960000021
wherein R is5～R10All are C1-C6 alkyl.
2. The indenonanthracene derivative compound of claim 1, wherein the group represented by formula (iii) is selected from one of the following structural formulae:
Figure FDA0003388279960000022
Figure FDA0003388279960000031
3. a compound selected from the following structures:
Figure FDA0003388279960000032
Figure FDA0003388279960000041
Figure FDA0003388279960000051
4. use of the indenonanthracene derivative compound according to any one of claims 1 to 3 in an organic electroluminescent device.
5. An organic electroluminescent device comprising a light-emitting layer, wherein the light-emitting layer material comprises the indenonanthracene derivative compound according to any one of claims 1 to 3.
6. Use of the organic electroluminescent device as claimed in claim 5 in an organic electroluminescent display device.
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