CN110964019B - Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof - Google Patents

Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof Download PDF

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CN110964019B
CN110964019B CN201911278007.9A CN201911278007A CN110964019B CN 110964019 B CN110964019 B CN 110964019B CN 201911278007 A CN201911278007 A CN 201911278007A CN 110964019 B CN110964019 B CN 110964019B
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phenyl
electron
quinoxaline
indolo
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孙军
杨燕
张宏科
刘凯鹏
田密
何海晓
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 a compound of 6-phenyl-6H-indolo [2,3-b]Quinoxaline is a compound of an acceptor, belonging to the technical field of organic electroluminescent materials. The structural general formula of the compound is shown as a formula (I), wherein R1Is deuterated phenyl or triazine; a is an electron donating group or an electron accepting group. The invention introduces specific donor group or acceptor group to modify 6-phenyl-6H-indolo [2,3-b ] through specific position]Quinoxaline constitutes a brand new compound, has better energy transmission capability and charge transmission capability, can obviously improve the luminous stability of the luminous device, and can be widely applied to OLED luminous devices and display devices as a luminous layer main material, a hole blocking material, an electron transmission material or a Thermal Activity Delayed Fluorescence (TADF) luminous material. The structural general formula is shown as formula (I):

Description

Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescent functional materials and devices, and particularly relates to a compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor and application thereof.
Background
The luminous mechanism of display and lighting elements of Organic Light Emitting Diodes (OLEDs), which are self-luminous electronic elements, is a novel optoelectronic information technology that converts electrical energy directly into Light energy with the help of Organic semiconductor functional materials 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 illumination and display 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 electroluminescent 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 crossing, 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 percent, meanwhile, the material has controllable structure and stable property, is low in price, does not need noble metals such as iridium, platinum and the like, and has 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 (emitter) in a luminescent layer, but also as a host material or an auxiliary host material in the luminescent layer to sensitize the emitter, which is helpful for improving the efficiency of a conventional device, improving the color purity of the device, and prolonging the service life of the device, and is an organic electroluminescent functional material with a wide application prospect. The TADF material is structurally formed by connecting an electron donating group and an electron withdrawing group through a pi bond, but the types of the electron withdrawing groups which can be utilized at present are few, so that the design and the invention of the novel electron withdrawing group for developing the novel TADF material are very important.
At present, 6-phenyl-6H-indolo [2,3-b ] quinoxaline has higher thermal stability and electron affinity potential energy due to a specific molecular conjugated structure in a molecule, can be used as a hole transport type material of an OLED (organic light emitting diode) by connecting donor group modification, and can be used as an electron transport type material by connecting an acceptor group.
In the prior art, 6-phenyl-6H-indolo [2,3-b ] quinoxaline is connected with amine derivatives through a phenyl bridge to form a hole transport material, and compared with the conventional hole transport material NPB, the service life of the hole transport material NPB is obviously prolonged. However, the 6-phenyl-6H-indolo [2,3-b ] quinoxaline is modified only by the amino derivative, and electron-withdrawing groups such as triazine, benzimidazole and the like are not directly introduced to study the electron transport performance of the whole compound, and the Thermal Activity Delayed Fluorescence (TADF) characteristic or the main body property of a bipolar material formed by introducing other donor groups such as carbazole, acridine and the like are not studied. In addition, the TWI567075B patent is used for phosphorescent host materials by connecting donor or acceptor groups on N of 6-phenyl-6H-indolo [2,3-b ] quinoxaline basic structure indole, and has excellent device performance, but the substituted position of the indole N in the patent does not contain triazine ligand or deuterated benzene ligand, and other positions of quinoxaline or indole are all hydrogen atoms, and TADF luminescence property or hole blocking and electron transmission property is not researched in the aspect of application. Therefore, the 6-phenyl-6H-indolo [2,3-b ] quinoxaline is used as a core structure, and a specific donor group or an acceptor group is introduced into a specific position to develop an organic electroluminescent material with better performance, so that the organic electroluminescent material has important economic value and social value for promoting the application and development of an organic electroluminescent device.
Disclosure of Invention
The invention aims to provide a compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor, which can be used as a main material or a luminescent material in a luminescent layer or a hole blocking material or an electron transport material through modification of different groups, and the material can be applied to an organic electroluminescent device to remarkably improve the device performance of the organic electroluminescent device.
The invention provides a compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor, which has a structural general formula shown in formula (I):
Figure BDA0002313971050000031
wherein R is1Is deuterated phenyl or triazinyl, represented by the formula (II-1) and the formula (II-2) respectively;
Figure BDA0002313971050000032
a is an electron donating group or an electron accepting group,
when A is an electron donating group, selected from substituted or unsubstituted carbazolyl, acridinyl, pheno oxazinyl or carbazolofluorenyl;
when A is an electron accepting group, it is selected from substituted or unsubstituted triazinyl, pyrimidinyl, imidazolyl, benzimidazolyl or phenanthrolinyl.
Preferably, when a is an electron donating group, it is selected from one of the following structural formulas:
Figure BDA0002313971050000041
Figure BDA0002313971050000051
preferably, when a is an electron-accepting group, it is selected from one of the following structural formulae:
Figure BDA0002313971050000052
Figure BDA0002313971050000061
preferably, in particular, one of the following compounds:
Figure BDA0002313971050000062
Figure BDA0002313971050000071
Figure BDA0002313971050000081
Figure BDA0002313971050000091
the second purpose of the invention is to provide the application of the compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor in an organic electroluminescent device.
The third purpose of the invention is to provide an organic electroluminescent device, which comprises a luminescent layer, wherein at least one of the host material and/or luminescent dye of the luminescent layer is the compound which takes 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor and is any one of the above compounds.
The fourth purpose of the invention is to provide an organic electroluminescent device, which comprises a light-emitting layer and a hole blocking layer, wherein the material used for the hole blocking layer is any one of the compounds which take 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor.
The fifth purpose of the invention is to provide an organic electroluminescent device, which comprises a luminescent layer and an electron transport layer, wherein the material used in the electron transport layer is any one of the compounds which take 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor.
A sixth object of the present invention is to provide the use of the above organic electroluminescent device in an organic electroluminescent display device.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a brand new compound is formed by introducing a specific donor group or an acceptor group into a specific position to modify 6-phenyl-6H-indolo [2,3-b ] quinoxaline;
1. by introducing a high triplet energy triazine ligand on N of indole, the triplet energy of a 6-phenyl-6H-indolo [2,3-b ] quinoxaline core structure is improved, and the electron transmission capability is improved;
2. the introduction of deuterated benzene on indole N improves the stability and the thermal activity delayed fluorescence property of the material;
the series of compounds are used as a main material or a hole blocking material or a TADF material or an electron transport material in an organic electroluminescent (OLED) device to show excellent performance.
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 compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor is prepared by linking an electron donating group or an electron accepting group on a 6-phenyl-6H-indolo [2,3-b ] quinoxaline molecule.
The invention provides a compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor, which has a structural general formula shown in formula (I):
Figure BDA0002313971050000111
wherein R is1Is deuterated phenyl or triazinyl, represented by the formula (II-1) and the formula (II-2) respectively;
Figure BDA0002313971050000112
a is an electron donating group or an electron accepting group;
when A is an electron donating group, selected from substituted or unsubstituted carbazolyl, acridinyl, pheno oxazinyl or carbazolofluorenyl;
when A is an electron accepting group, it is selected from substituted or unsubstituted triazinyl, pyrimidinyl, imidazolyl, benzimidazolyl or phenanthrolinyl.
According to the invention, a brand new compound is formed by introducing a specific donor group or an acceptor group into a specific position to modify 6-phenyl-6H-indolo [2,3-b ] quinoxaline; by introducing a high triplet energy triazine ligand on N of indole, the triplet energy of a 6-phenyl-6H-indolo [2,3-b ] quinoxaline core structure is improved, and the electron transmission capability is improved; the introduction of deuterated benzene on indole N improves the stability and the thermal activity delayed fluorescence property of the material; the series of compounds are used as a main material or a hole blocking material or a TADF material or an electron transport material in an organic electroluminescent (OLED) device to show excellent performance.
In the following, we provide specific synthetic methods for the preparation of several intermediates corresponding to the above compounds.
(1) Synthesis of intermediates 1-2:
Figure BDA0002313971050000121
adding 350ml of N, N-dimethylformamide and 50g of intermediate 1-1 into a 1L three-necked bottle, stirring and dissolving, cooling to 0-5 ℃ in an ice water bath, dropwise adding 150ml of N, N-dimethylformamide solution dissolved with 41.4g N-bromobutyrylimine, reacting in the ice water bath at 0-5 ℃ for 2 hours, then heating to room temperature, monitoring by TLC (thin layer chromatography) that the raw materials are completely reacted, distilling the reaction liquid under reduced pressure to remove most of the solvent, pouring the precipitated solid and the remaining small amount of solvent into water, stirring to precipitate the solid, filtering, washing the filter cake with ethanol, and drying to obtain 65.8g of off-white intermediate 1-2, wherein the yield is 96.8%.
Nuclear magnetic spectrum data of intermediates 1-2:1H NMR(400MHz,CDCl3)δ10.1(br,1H),8.07(d,J＝8.8,2H),7.68-7.72(m,2H),7.26-7.29(m,2H)。
(2) synthesis of intermediate 1:
Figure BDA0002313971050000122
30g of intermediate 1-2, 300ml of toluene, 32.0g of sodium carbonate, 17.9g of deuterated bromobenzene, nitrogen gas introduction for 10min, 0.36g of phenanthroline and 0.29g of CuBr are sequentially added into a 500ml three-necked flask, the mixture is stirred for 10min, the reaction solution is heated to reflux and stirred for reaction for 8h, and the reaction is stopped after TLC monitors that the raw materials are completely reacted. And cooling the reaction solution to room temperature, washing the reaction solution to be neutral, drying the reaction solution by using anhydrous sodium sulfate, filtering, concentrating the filtrate, passing the obtained crude product through a column, and recrystallizing toluene to obtain 27.9g of the intermediate 1 with the yield of 73.2%.
Nuclear magnetic spectrum data of intermediate 1:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.68-7.72(m,2H),7.33(d,J＝8.0,1H),7.27(d,J＝8.0,1H)。
(3) synthesis of intermediate 2:
Figure BDA0002313971050000131
adding 30g of intermediate 1-2, 300ml of toluene, 32.0g of sodium carbonate and 34.5g of intermediate 2-1 into a 500ml three-mouth bottle in sequence, introducing nitrogen for 10min, adding 0.36g of phenanthroline and 0.29g of CuBr, stirring for 10min, heating the reaction solution to reflux, stirring and reacting for 8h, and stopping the reaction after TLC monitors that the raw materials are completely reacted. And cooling the reaction liquid to room temperature, washing the reaction liquid to be neutral, drying the reaction liquid by using anhydrous sodium sulfate, filtering, concentrating the filtrate, passing the obtained crude product through a column, and recrystallizing toluene to obtain 41.6g of the intermediate 2, wherein the yield is 78.2%.
Nuclear magnetic spectrum data of intermediate 2:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.75(s,1H),7.68(d,J＝8.8,2H),7.48(d,J＝6.4,4H),7.32-7.35(m,5H),7.22-7.26(m,3H)。
we now provide specific examples of compounds, some of which take 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor, and methods for their synthesis.
Example 1: preparation of Compound 2
Figure BDA0002313971050000141
10g of intermediate 1, 8.8g of compound 2-1, 5.1g of sodium tert-butoxide and 200ml of toluene are added into a 500ml three-necked bottle, a nitrogen protection reaction system is introduced, 1.2g of tris (dibenzylideneacetone) dipalladium and 1.3g of 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropyl biphenyl are added continuously, the reaction system is heated to reflux and stirred for reaction for 8 hours, the reaction is stopped after TLC monitoring is completed, the reaction system is cooled to room temperature and washed to neutrality, an organic phase is dried by anhydrous sodium sulfate and concentrated and dried, the obtained solid is recrystallized by toluene to obtain 12.6g of compound 2, and the yield is 82.6%.
Nuclear magnetic spectroscopy data for compound 2:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.68(d,J＝8.8,2H),7.62(s,1H),7.58(s,2H),7.40(d,J＝6.8,1H),7.32(d,J＝6.8,2H),7.09-7.11(m,3H),1.34(s,18H)。
example 2: preparation of Compound 6
Figure BDA0002313971050000142
10g of intermediate 1, 9.6g of compound 6-1, 5.1g of sodium tert-butoxide and 300ml of toluene are added into a 500ml three-necked bottle, a nitrogen protection reaction system is introduced, 1.2g of tris (dibenzylideneacetone) dipalladium and 1.3g of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl are added continuously, the reaction system is heated to reflux and stirred for reaction for 8 hours, the reaction is stopped after the TLC monitoring reaction is completed, the reaction system is cooled to room temperature and washed to neutrality, an organic phase is dried by anhydrous sodium sulfate and then concentrated and dried, and the toluene is recrystallized to obtain 11.9g of compound 6, wherein the yield is 71.9%.
Nuclear magnetic spectroscopy data for compound 6:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.84(d,J＝6.8,2H),7.68(d,J＝8.8,2H),7.55(d,J＝7.2,2H),7.38(t,J＝6.8,2H),7.28(t,J＝6.8,2H),7.15(d,J＝8.0,1H),6.81-6.83(m,4H),6.75(s,1H),6.50(t,J＝7.2,2H),6.34(d,J＝7.2,2H),6.28(d,J＝8.0,1H)。
example 3: preparation of Compound 12
Figure BDA0002313971050000151
10g of intermediate 1, 200ml of toluene, 7.3g of potassium carbonate and 1.7g of tetrabutylammonium bromide are sequentially added into a 500ml three-necked bottle, nitrogen is introduced for 10min, then 0.6g of tetrakis (triphenylphosphine) palladium is added, 100ml of toluene solution containing 9.5g of compound 12-1 is dropwise added after heating to 78-80 ℃, sampling is carried out after 6h of reaction, TLC (thin layer chromatography) detection is carried out on the raw materials, the reaction is stopped after the TLC detection is carried out on the raw materials, the temperature is reduced to room temperature, water washing is carried out to be neutral, anhydrous sodium sulfate is used for drying, filtrate is concentrated, the obtained crude product passes through a column, toluene is recrystallized to obtain 10.6g of compound 12, and the.
Nuclear magnetic spectroscopy data for compound 12:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.77(s,1H),7.68(d,J＝8.8,2H),7.46(d,J＝8.0,1H),7.30(d,J＝8.0,1H),7.23(d,J＝6.4,2H),6.88(d,J＝7.2,2H),6.83(t,J＝7.2,2H),6.52-6.54(m,4H),6.38(d,J＝7.2,2H),1.67(s,6H)。
example 4: preparation of Compound 25
Figure BDA0002313971050000161
10g of intermediate 2, 5.9g of compound 25-1, 3.6g of sodium tert-butoxide and 300ml of toluene are added into a 500ml three-necked bottle, a nitrogen protection reaction system is introduced, 0.9g of tris (dibenzylideneacetone) dipalladium and 0.9g of 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropyl biphenyl are added continuously, the reaction system is heated to reflux and stirred for reaction for 8 hours, the reaction is stopped after the TLC monitoring reaction is completed, the temperature is reduced to room temperature, the organic phase is washed to be neutral by water, concentrated and dried by spinning after being dried by anhydrous sodium sulfate, and the toluene is recrystallized to obtain 11.0g of compound 25, the yield is 79.6%.
Nuclear magnetic spectroscopy data for compound 25:1H NMR(400MHz,CDCl3)δ8.06(d,J＝8.8,3H),7.68(d,J＝8.8,3H),7.61(m,J＝8.4,3H),7.55(d,J＝6.8,1H),7.40-7.48(m,6H),7.32(m,5H),7.22-7.24(m,3H),7.08(m,2H),7.00(t,J＝6.8,1H),1.67(s,6H)。
example 5: preparation of Compound 29
Figure BDA0002313971050000162
10g of intermediate 2, 5.8g of compound 29-1, toluene 200ml, ethanol 80ml, water 40ml, 5.2g of potassium carbonate and 1.2g of tetrabutylammonium bromide are sequentially added into a 500ml three-necked flask, nitrogen is introduced for 10min, then 0.4g of tetrakis (triphenylphosphine) palladium is added, the mixture is heated to 78-80 ℃ for reaction for 6h, sampling is carried out, TLC (thin layer chromatography) is used for monitoring the reaction to be complete, the reaction is stopped after the reaction is monitored, the temperature is reduced to room temperature, the organic phase is washed to be neutral, the organic phase is dried by anhydrous sodium sulfate, concentrated and dried, toluene is recrystallized to obtain 9.8g of compound 29, and the yield is 76.2%.
Nuclear magnetic spectroscopy data for compound 29:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.77(s,1H),7.68(d,J＝8.8,2H),7.48(d,J＝6.4,9H),7.32(t,J＝6.4,8H),7.30(d,J＝7.6,1H),7.22(t,J＝6.4,4H)。
example 6: preparation of Compound 43
Figure BDA0002313971050000171
10g of the intermediate 2, 7.0g of the compound 43-1, 200ml of toluene, 80ml of ethanol, 40ml of water, 5.2g of potassium carbonate and 1.2g of tetrabutylammonium bromide are sequentially added into a 500ml three-necked flask, nitrogen is introduced for 10min, then 0.4g of tetrakis (triphenylphosphine) palladium is added, the mixture is heated to 78-80 ℃ for reaction for 6h, sampling is carried out, the reaction is stopped after TLC monitoring reaction is completed, the mixture is cooled to room temperature and washed to be neutral by water, an organic phase is dried by anhydrous sodium sulfate and then concentrated and dried, toluene is recrystallized to obtain 10.3g of the compound 43, and the yield is 73.9%.
Nuclear magnetic spectroscopy data for compound 43:1H NMR(400MHz,CDCl3)δ8.93(d,J＝8.4,2H),8.12(d,J＝8.4,2H),8.07(d,J＝8.8,2H),7.88(t,J＝8.4,2H),7.82(t,J＝8.4,2H),7.77(s,1H),7.68(d,J＝8.8,2H),7.48(m,5H),7.30-7.35(m,10H),7.22(t,J＝6.4,2H)。
example 7: preparation of Compound 46
Figure BDA0002313971050000172
10g of intermediate 2, 7.5g of compound 46-1, toluene 200ml, ethanol 80ml, water 40ml, 5.2g of potassium carbonate and 1.2g of tetrabutylammonium bromide are sequentially added into a 500ml three-necked flask, nitrogen is introduced for 10min, then 0.4g of tetrakis (triphenylphosphine) palladium is added, the mixture is heated to 78-80 ℃ for reaction for 6h, sampling is carried out, TLC (thin layer chromatography) is used for monitoring the reaction to be complete, the reaction is stopped after the reaction is monitored, the temperature is reduced to room temperature, the organic phase is washed to be neutral, the organic phase is dried by anhydrous sodium sulfate and then concentrated and dried, toluene is recrystallized to obtain 12.0g of compound 46, and the yield is 82.8.
Nuclear magnetic spectroscopy data for compound 46:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.8,2H),7.84(d,J＝6.8,2H),7.77(s,1H),7.72(d,J＝6.8,1H),7.68(d,J＝8.8,2H),7.55(d,J＝6.8,2H),7.48(d,J＝6.4,5H),7.28-7.41(m,12H),7.16-7.22(m,5H)。
example 8: preparation of Compound 55
Figure BDA0002313971050000181
10g of intermediate 2, 6.1g of compound 55-1, 3.6g of sodium tert-butoxide and 300ml of toluene are added into a 500ml three-necked flask, nitrogen is introduced to protect the reaction system, 0.9g of tris (dibenzylideneacetone) dipalladium and 0.9g of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl are added continuously, and the reaction system is heated to reflux and stirred for reaction for 8 hours. Stopping the reaction after TLC monitoring reaction is completed, cooling to room temperature, washing with water to be neutral, drying an organic phase with anhydrous sodium sulfate, concentrating and spin-drying, and recrystallizing with toluene to obtain 12.1g of a compound 55, wherein the yield is 86.3%.
Nuclear magnetic spectroscopy data for compound 55:1H NMR(400MHz,CDCl3)δ8.07(d,J＝8.4,2H),7.68(m,4H),7.48(d,J＝6.4,4H),7.40(m,3H),7.26-7.32(m,10H),7.22(t,J＝6.4,2H),7.08(d,J＝8.4,2H),7.00(d,J＝8.4,2H)。
t was performed on some of the compounds provided in the above examples and the existing materials, respectively1Energy 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 BDA0002313971050000191
Note: the data obtained by simulation calculation of the triplet energy (T1) of the occupied highest molecular orbital (HOMO) and the unoccupied lowest molecular orbital (LUMO) and delta Est are obtained by Gaussian 09 software, and the calculation method adopts a B3LYP hybridization functional, the basis set is 6-31g (d, P).
From table 1, the organic compounds of the present invention have higher triplet energy and more suitable HOMO/LUMO, which are favorable for carrier transport and energy transfer in OLED devices, and can be used as phosphorescent host material, fluorescent host material or TADF host material, and also can be used as TADF light emitting material. The organic electroluminescent device may be, without particular limitation, a phosphorescent device, a fluorescent device or a device containing a Thermally Active Delayed Fluorescence (TADF) material. Therefore, the compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor can effectively improve the performances of the device such as luminous efficiency, service life and the like after being applied to a luminous layer or a hole blocking or electron transport layer of an OLED device.
In the following, some of the compounds provided by the present invention are taken as examples, and are applied to an organic electroluminescent device as a light emitting layer material (host material and/or doped dye), a hole blocking material, and an electron transport material, respectively, to verify the excellent effects obtained by the compounds.
The excellent effect of the OLED material applied to the device is detailed through the device performances of device examples 1-8 and comparative examples 1-2. The structure manufacturing processes of the device examples 1-8 and the comparative examples 1-2 are completely the same, the same glass substrate and electrode material are adopted, the film thickness of the electrode material is 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; TCTA is selected as the material of the second hole transport layer 5, and the thickness is 15 nm; the light-emitting layer 6 used the compound 25 as a host material and RD01 as a light-emitting material, and had a doping ratio of 3% 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 100 nm.
The structural formula of the basic material used by each functional layer in the device is as follows:
Figure BDA0002313971050000201
Figure BDA0002313971050000211
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 TCTA on the first hole transport layer NPB in a vacuum evaporation mode, wherein the thickness of the TCTA is 15nm, and the TCTA 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, wherein the compound 25 is used as a host material, the RD01 is used as a light-emitting material, the doping amount ratio is 3%, 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 100nm, and the layer was used as a cathode conductive electrode.
Device example 2
Same as device example 1, except that: compound 46 was used as the host material in place of compound 25.
Device example 3
Same as device example 1, except that: compound 55 was used as the host material in place of compound 25.
Device example 4
Same as device example 1, except that: CBP is used as a host material, and compound 2 is used as a luminescent material.
Device example 5
Same as device example 1, except that: CBP was used as the host material and compound 6 was used as the light emitting material.
Device example 6
Same as device example 1, except that: CBP was used as the host material and compound 12 was used as the light emitting material.
Device example 7
Same as device example 1, except that: CBP was used as the host material, RD01 as the light emitting material, and compound 29 as the hole blocking material instead of TPBI.
Device example 8
Same as device example 1, except that: CBP is taken as a host material, RD01 is taken as a luminescent material, and compound 43 is taken as an electron transport material to replace ET-1.
Comparative example 1
Same as device example 1, except that: CBP was used as the host material in place of compound 25.
Comparative example 2
Same as comparative example 1 except that: RD02 is used as luminescent material instead of RD 01.
The components of the devices prepared in examples 1 to 8 and comparative examples 1 to 2 of the present invention are shown in table 2:
TABLE 2 comparison table of organic electroluminescent element components of each device example
Figure BDA0002313971050000231
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 50mA/cm2The time for the test brightness to decay to 95% of the initial brightness is the device LT95Lifetime, test results are shown in table 3:
table 3 performance results for each group of organic electroluminescent devices
Figure BDA0002313971050000232
Figure BDA0002313971050000241
As can be seen from Table 3, the compound provided by the invention is used as a host material of a light-emitting layer to be applied to an OLED red light emitter, and has excellent performance. Compared with the CBP of the comparative example 1, the compound 55 in the device example 3 serving as the phosphorescent main body material has the advantages that the luminous efficiency and the service life are both remarkably improved, the luminous efficiency is improved by 19.4%, and the service life is improved by more than 42%; the compounds as in device examples 3-5 perform well as TADF phosphors, such that compound 12 has about 33% higher luminous efficiency, 52% higher lifetime, and good color coordinates compared to RD02 in comparative example 2. The core structure can be used as a hole blocking material after being modified, for example, after the compound 29 replaces TPBI in the embodiment 7, the device efficiency is improved by 5.9%, and the service life is improved by 23.8%; compared with ET-1 in comparative example 1, the compound 43 as an electron transport material in example 8 has the advantages that the device efficiency is improved by 9.5 percent, and the device service life is prolonged by 35 percent. Compared with the prior material applied to the OLED light-emitting device, the compound provided by the invention has good photoelectric properties such as luminous efficiency, service life, color purity and the like, and the material has a simple synthesis process, has a great application value in the application of the OLED device, and has a 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 (7)

1. A compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as an acceptor is characterized in that the structural general formula is shown as the formula (I):
Figure FDA0002910547040000011
wherein R is1Is deuterated phenyl or triazinyl, represented by the formula (II-1) and the formula (II-2) respectively;
Figure FDA0002910547040000012
a is an electron donating group or an electron accepting group,
when A is an electron-donating group, the A is selected from any one of the following structural formulas:
Figure FDA0002910547040000013
Figure FDA0002910547040000021
Figure FDA0002910547040000031
Figure FDA0002910547040000041
when A is an electron accepting group, the A is selected from any one of the following structural formulas:
Figure FDA0002910547040000042
Figure FDA0002910547040000051
2. a compound selected from the following structures:
Figure FDA0002910547040000052
Figure FDA0002910547040000061
Figure FDA0002910547040000071
Figure FDA0002910547040000081
Figure FDA0002910547040000091
Figure FDA0002910547040000101
Figure FDA0002910547040000111
Figure FDA0002910547040000121
Figure FDA0002910547040000131
3. use of a compound according to claim 1 or 2 in an organic electroluminescent device.
4. An organic electroluminescent device comprising a light-emitting layer, characterized in that a host material and/or a light-emitting dye of the light-emitting layer is the compound of claim 1 or 2.
5. An organic electroluminescent device comprising a light-emitting layer and a hole-blocking layer, wherein the hole-blocking layer is made of a compound according to claim 1 or 2.
6. An organic electroluminescent device comprising a light-emitting layer and an electron transport layer, wherein the electron transport layer is made of the compound according to claim 1 or 2.
7. Use of the organic electroluminescent device of claim 4 in an organic electroluminescent display device.
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