CN111454251A - Pyrazine derivative and application thereof in O L ED device - Google Patents

Pyrazine derivative and application thereof in O L ED device Download PDF

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CN111454251A
CN111454251A CN202010279992.1A CN202010279992A CN111454251A CN 111454251 A CN111454251 A CN 111454251A CN 202010279992 A CN202010279992 A CN 202010279992A CN 111454251 A CN111454251 A CN 111454251A
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substituted
independently selected
pyrazine derivative
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孙军
张宏科
刘凯鹏
杨丹丹
李江楠
田密
何海晓
高仁孝
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Xi'an Manareco New Materials Co ltd
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Abstract

The invention discloses a pyrazine derivative and application thereof in an O L ED device, belongs to the technical field of organic synthesis, and has a structural general formula shown in formula (I)(ii) a The invention provides a method for preparing a compound with 2-methyl diindeno [1, 2-b: 1', 2' -e]The compound taking pyrazine-6, 12-dione as a core has good charge transmission capability, a proper HOMO/L UMO value and good thermal stability, can realize high brightness, low voltage, high efficiency and long service life when used in an organic electroluminescent device, and can be widely applied to an O L ED luminescent device and a display device as a blue light emitting layer main body material or a thermal activity delayed fluorescence luminescent material;
Figure DDA0002446210950000011

Description

Pyrazine derivative and application thereof in O L ED device
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a pyrazine derivative and application thereof in an O L ED device.
Background
The luminous mechanism of display and lighting element of Organic electroluminescent diode (O L ED: Organic L luminance Diodes) as a self-luminous electronic element is a novel photoelectric information technology which directly converts electric energy into light energy by means of Organic semiconductor functional material under the action of DC electric field, the luminous color of the display element can be independent red, green, blue and yellow lights or combined white light, the O L ED luminous display technology has the biggest characteristics of ultra-thin, fast response speed, ultra-light weight, surface light emission and flexible display, can be used for manufacturing monochromatic or full color displays, can be used as a novel light source technology, and can also be used for manufacturing lighting, display products or a novel backlight technology for manufacturing liquid crystal displays.
According to the principle of light emission, organic electroluminescent devices (organic E L devices) can be divided into two types, i.e., fluorescent and phosphorescent, and a voltage is applied to the organic electroluminescent devices to inject holes from the anode and electrons from the cathode, which are combined again in the light emitting layer to form excitons, according to the electron spin statistics, singlet excitons and triplet excitons are generated at a ratio of 25% to 75%.
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. TADF material is generally formed by connecting electron donating groups and electron withdrawing groups through a pi bond in structure, but the electron withdrawing groups which can be utilized at present are few in variety, particularly, TADF blue light material with high quality is few, the color purity of the blue light material reported at present has defects, the service life of a device is not ideal enough, and the practical requirement cannot be met, so that the development of novel blue light TADF material is very important.
Disclosure of Invention
In order to solve the problems, the invention discloses a pyrazine derivative and application thereof in an O L ED device.
The invention provides a pyrazine derivative, which has a structural general formula shown in formula (I):
Figure BDA0002446210930000021
wherein Ar is1、Ar2Each independently selected from a donor group or a fused ring aryl group;
the donor group is a group shown in a formula (II), a formula (III), a formula (IV), a formula (V), a formula (VI), a formula (VII), a formula (VIII), a formula (IX) or a formula (X):
Figure BDA0002446210930000031
in the formula (II), Ar3、Ar4Each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
in the formula (III), R1、R2Each independently selected from a hydrogen atom or a C1-C6 alkyl group;
in the formula (IV), X3Is C-m1m2O or S, m1、m2Each independently selected from substituted or unsubstituted aryl or C1-C6 alkyl;
in the formulas (V) and (VI), Y is C or Si;
the formula (IX) is a condensed heterocyclic group of C18-C24 and contains 2 five-membered rings;
in the formula (X), Z is C-m3m4、N-m5O or S, m3、m4Each independently selected from C1-C6 alkyl, m5Is substituted or unsubstituted aryl;
the condensed ring aryl is a group represented by formula (B1), formula (B2), formula (B3), formula (B4) or formula (B5):
Figure BDA0002446210930000041
preferably, in the formula (II), Ar3、Ar4Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted fluorenyl; when substituted phenyl, these substituents are C1-C6 alkyl, phenyl, halogen, -CF3or-CN; when substituted dibenzofuranyl, these substituents are C1-C6 alkyl groups, and when substituted fluorenyl, these substituents are C1-C6 alkyl groups.
Preferably, in the formula (II), Ar3、Ar4Each independently selected from phenyl, methylphenyl, isopropylphenyl, biphenyl, trifluoromethylphenyl, fluorophenyl, cyanophenyl, dibenzofuranyl, isopropyldibenzofuranyl, fluorenyl or dimethylfluorenyl.
Preferably, in said formula (III), R1And R2Each independently from a hydrogen atom or a tert-butyl group.
Preferably, in the formula (IV), m1、m2Each independently selected from methyl or phenyl.
Preferably, the formula (IX) is selected from one of the following structural formulae:
Figure BDA0002446210930000042
Figure BDA0002446210930000051
preferably, the pyrazine derivatives include the following compounds:
Figure BDA0002446210930000052
Figure BDA0002446210930000061
Figure BDA0002446210930000071
the second purpose of the invention is to provide the application of the pyrazine derivatives in organic electroluminescent devices.
Preferably, the organic electroluminescent device comprises a light-emitting layer, and is characterized in that the material of the light-emitting layer comprises the pyrazine derivative.
A third 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 following beneficial effects:
the invention modifies 2-methyl diindeno [1, 2-b: 1', 2' -e ] pyrazine-6, 12-diketone forms a brand new compound, and the indanone ligands are incorporated at the two sides of the pyrazine, so that the triplet state energy of the pyrazine is improved, and the electron transmission capability of a core framework is optimized; through introducing various electron donating groups for modification, the compound has the bipolar characteristic of an electron donating-acceptor, the front-line orbital energy level distribution of the material is improved, the energy difference between a singlet state and a triplet state is reduced, and the compound has TADF (TADF) property; the stability and band gap of the material are improved by connecting condensed ring molecules such as anthracene, pyrene and the like, so that the compound is suitable for being used as a blue light main body material, and the series of compounds show excellent performance as the blue light main body material or a luminescent material in an organic electroluminescent device.
Drawings
FIG. 1 is a schematic structural diagram of an organic electroluminescent device provided by the present invention;
FIG. 2 is a graph of voltage-efficiency-current density for the device of example 6;
FIG. 3 shows L T of the device of example 690A life test curve graph;
description of reference numerals:
1. 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. 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 conventional methods unless otherwise specified; the reagents and raw materials are commercially available, unless otherwise specified.
The invention provides a pyrazine derivative, which has a structural general formula shown in a formula (I):
Figure BDA0002446210930000091
wherein Ar is1、Ar2Each independently selected from a donor group or a fused ring aryl group;
the donor group is a group shown in a formula (II), a formula (III), a formula (IV), a formula (V), a formula (VI), a formula (VII), a formula (VIII), a formula (IX) or a formula (X):
Figure BDA0002446210930000092
in the formula (II), Ar3、Ar4Each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
in the formula (III), R1、R2Each independently selected from a hydrogen atom or a C1-C6 alkyl group;
in the formula (IV), X3Is C-m1m2O or S, m1、m2Each independently selected from substituted or unsubstituted aryl or C1-C6 alkyl;
in the formulas (V) and (VI), Y is C or Si;
the formula (IX) is a condensed heterocyclic group of C18-C24 and contains 2 five-membered rings;
in the formula (X), Z is C-m3m4、N-m5The oxygen, the oxygen or the sulfur is selected from the group consisting of O and S,m3、m4each independently selected from C1-C6 alkyl, m5Is substituted or unsubstituted aryl;
the condensed ring aryl is a group represented by formula (B1), formula (B2), formula (B3), formula (B4) or formula (B5):
Figure BDA0002446210930000101
in the following, we provide specific synthetic methods for preparing the above compounds and several intermediates corresponding thereto.
The intermediate 1-1 and the intermediate 1-2 are synthesized according to the prior method.
(1) Synthesis of intermediates 1 to 3:
Figure BDA0002446210930000102
60g of intermediate 1-1 and 600ml of toluene are added into a 1L three-neck flask, the mixture is heated to 40 ℃ and slowly dropped with 36.6g of intermediate 1-2 80ml of concentrated hydrochloric acid solution, the mixture is kept warm and stirred for 5h at the temperature, then sampling is carried out to monitor the reaction progress, the stirring is stopped after the raw materials are completely reacted, the mixture is cooled to room temperature, the reaction liquid is extracted by dichloromethane, the combined organic phase is adjusted to be neutral by saturated sodium bicarbonate solution, then the organic phase is washed by saturated common salt, dried by sodium sulfate, and purified by a silica gel column to obtain 38.8g of intermediate 1-3, and the yield is 56.8%.
1H NMR(400MHz,CDCl3)7.58(d,J＝7.6,1H),7.43(m,2H),2.61(s,2H),2.03(br,1H)；
(2) Synthesis of intermediates 1 to 4:
Figure BDA0002446210930000111
38g of intermediate 1-3, 96.5g of sodium thiosulfate, 400ml of ethanol and 300ml of ammonia water (25%) are added into a 1L three-necked bottle, the mixture is heated to 80 ℃ for reflux reaction for 8 hours, then sampling is carried out to monitor the reaction process, stirring is stopped after the raw materials are completely reacted, the reaction system is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed to be neutral, anhydrous sodium sulfate is used for drying, 21.4g of intermediate 1-4 is obtained after silica gel column purification, and the yield is 32.6%.
1H NMR(400MHz,CDCl3)7.30(m,4H),7.25(d,J＝8.8,2H),3.81(s,4H)；
(3) Synthesis of intermediate 1:
Figure BDA0002446210930000112
adding 150ml of water into a 500ml three-neck flask, slowly adding a mixed solution of 50.7g of sodium dichromate and 43.3ml of concentrated sulfuric acid under the condition of stirring, then adding 20g of intermediate 1-4, heating to 80 ℃, stirring for reacting for 6 hours, sampling, monitoring the reaction progress, stopping stirring after the raw materials completely react, and cooling to room temperature. The reaction mixture was poured into ice water, extracted with dichloromethane, and the organic phase was adjusted to neutrality with a saturated sodium bicarbonate solution, washed with saturated brine, and dried over anhydrous sodium sulfate. The organic phase was purified on a silica gel column and recrystallized from toluene to give 5.5g of intermediate 1 with a yield of 25.7%.
1H NMR(400MHz,CDCl3)8.04(s,2H),7.77(d,J＝8.8,2H),7.56(d,J＝8.8,2H)；
(4) Synthesis of Compound 1:
Figure BDA0002446210930000121
10g of intermediate 1, 8.3g of compound 1-1, 8.6g of sodium carbonate, 0.91g of 1, 10-phenanthroline and 300ml of toluene are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 0.64g of cuprous bromide is added, the system is heated to 110 ℃ for reflux reaction for 6h, then T L C is sampled to monitor the reaction, when the raw materials are completely reacted, the temperature is reduced to room temperature, the reaction solution is filtered, washed to pH 7, the organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 11.6g of compound 1, wherein the yield is 83.6%.
1H NMR(400MHz,CDCl3)7.9(s,2H),7.7(d,J＝8.0,2H),7.55-7.60(m,6H),7.40(d,J＝6.8,4H),7.00-7.08(m,8H)；
(5) Synthesis of Compound 3:
Figure BDA0002446210930000122
10g of intermediate 1, 10.4g of compound 3-1, 8.6g of sodium carbonate, 0.91g of 1, 10-phenanthroline and 300ml of toluene are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 0.64g of cuprous bromide is added, the system is heated to 110 ℃ for reflux reaction for 6h, then T L C is sampled to monitor the reaction, when the raw materials are completely reacted, the temperature is reduced to room temperature, the reaction solution is filtered, washed to pH 7, the organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 10.6g of compound 3, wherein the yield is 67.2%.
1H NMR(400MHz,CDCl3)7.42(d,J＝8.8,2H),7.07(s,2H),6.80-6.88(m,10H),6.54(t,J＝7.2,4H),6.38(d,J＝7.2,4H),1.67(s,12H)；
(6) Synthesis of compound 11:
Figure BDA0002446210930000131
10g of intermediate 1, 14.1g of compound 11-1, 8.6g of sodium carbonate, 0.91g of 1, 10-phenanthroline and 300ml of toluene are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 0.64g of cuprous bromide is added, the system is heated to 110 ℃ for reflux reaction for 6h, then T L C is sampled to monitor the reaction, when the raw materials are completely reacted, the heating is stopped, the temperature is reduced to room temperature, the reaction solution is filtered, washed with water to pH 7, the organic phase is dried by anhydrous sodium sulfate and purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 14.1g of compound 11, wherein the yield is 73.8%.
1H NMR(400MHz,CDCl3)8.06(d,J＝6.8,2H),7.93(s,2H),7.55-7.70(m,10H),7.24-7.44(m,8H),7.00-7.08(m,4H),1.67(s,12H)；
(7) Synthesis of compound 28:
Figure BDA0002446210930000132
10g of intermediate 1, 16.7g of compound 28-1, 8.6g of sodium carbonate, 0.91g of 1, 10-phenanthroline and 300ml of toluene are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 0.64g of cuprous bromide is added, the system is heated to 110 ℃ for reflux reaction for 6h, then T L C is sampled to monitor the reaction, heating is stopped when the raw materials are completely reacted, the temperature is reduced to room temperature, the reaction solution is filtered and washed with water until the pH value is 7, an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and crude products obtained by concentrating eluent are recrystallized by toluene to obtain 18.7g of compound 28, wherein the yield is 86.8%.
1H NMR(400MHz,CDCl3)7.48(d,J＝6.4,6H),7.42(d,J＝7.2,4H),7.32(t,J＝6.4,4H),7.19-7.24(m,8H),7.13(d,J＝6.8,2H),7.07(s,2H),6.85-6.88(m,4H),6.80(d,J＝8.8,2H),6.52(d,J＝6.4,4H),6.39(d,J＝6.8,2H)；
(8) Synthesis of compound 37:
Figure BDA0002446210930000141
10g of intermediate 1, 14.1g of compound 3-1, 8.6g of sodium carbonate, 0.91g of 1, 10-phenanthroline and 300ml of toluene are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 0.64g of cuprous bromide is added, the system is heated to 110 ℃ for reflux reaction for 6h, then T L C is sampled to monitor the reaction, when the raw materials are completely reacted, the temperature is reduced to room temperature, the reaction solution is filtered, washed to pH 7, the organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 14.5g of compound 37, wherein the yield is 75.6%.
1H NMR(400MHz,CDCl3)7.49(d,J＝6.8,2H),7.42(d,J＝8.8,2H),7.26-7.29(m,4H),7.19(t,J＝6.8,2H),7.13(t,J＝6.8,2H),7.07(s,2H),6.85-6.88(m,4H),6.80(m,4H),6.64(d,J＝6.8,2H),6.39(d,J＝6.8,2H)；
(9) Synthesis of compound 47:
Figure BDA0002446210930000142
10g of the intermediate 1, 11.1g of the compound 47-1, 12.5g of potassium carbonate, 0.7g of tetrabutylammonium bromide, 200ml of toluene, 60ml of ethanol and 40ml of water are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 1.3g of tetrakis (triphenylphosphine) palladium is added, the system is heated to 80 ℃ for reaction for 6h, then T L C is sampled for monitoring the reaction, when the raw materials are completely reacted, the heating is stopped, the temperature is reduced to room temperature, the reaction solution is filtered and washed with water to pH 7, an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 10.4g of the compound 47, and the yield is 72.2%.
1H NMR(400MHz)8.27(s,2H),8.09(s,2H),7.91(d,J＝7.2,8H),7.82(d,J＝8.0,2H),7.73(d,J＝8.8,2H),7.39(t,J＝7.2,8H)；
(10) Synthesis of compound 52:
Figure BDA0002446210930000151
10g of intermediate 1, 12.4g of compound 52-1, 12.5g of potassium carbonate, 0.7g of tetrabutylammonium bromide, 200ml of toluene, 60ml of ethanol and 40ml of water are added into a 500ml three-neck flask, nitrogen is introduced for 5min to discharge oxygen in the system, 1.3g of tetrakis (triphenylphosphine) palladium is added, the system is heated to 80 ℃ for reaction for 6h, then T L C is sampled for monitoring the reaction, when the raw materials are completely reacted, the heating is stopped, the temperature is reduced to room temperature, the reaction solution is filtered and washed with water to pH 7, an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to remove insoluble impurities, and the crude product obtained by concentrating the eluent is recrystallized by toluene to obtain 11.8g of compound 52, and the yield is 75.9%.
1H NMR(400MHz)8.12(d,J＝7.2,2H),8.09(s,2H),8.04(d,J＝7.2,2H),7.94(d,J＝7.2,2H),7.88(d,J＝6.8,2H),7.82(m,4H),7.73(d,J＝8.8,2H),7.71(s,8H)。
T was performed on some of the compounds provided in the above examples and the existing materials, respectively1Energy levels and HOMO, L UMO energy level tests, the results are shown in Table 1:
TABLE 1 Compounds T of the invention1Energy level and HOMO, L UMO
Figure BDA0002446210930000152
Note that the highest molecular occupied orbital (HOMO) and the lowest molecular unoccupied orbital (L UMO) triplet energies (T)1) And delta Est is data obtained by simulation calculation of Gaussian 09 software, and the calculation method adopts a B3L YP hybridization functional, and the group is 6-31g (d, P).
From table 1, the organic compound of the present invention has a suitable HOMO/L UMO, which is favorable for carrier transport and energy transfer in an O L ED device, and can be used as a fluorescent host material or a TADF host material, or as a TADF light-emitting material, and without specific limitation, the organic electroluminescent device can be a phosphorescent device, a fluorescent device, or a device containing a Thermally Active Delayed Fluorescence (TADF) material.
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 material (host material and/or doped dye) of a luminescent layer, respectively, to verify the excellent effects obtained by the compounds.
The excellent effect of the O L ED material applied to the device is described in detail through the device performances of device examples 1-7 and comparative example 1. the structure manufacturing processes of the device examples 1-7 and comparative example 1 are completely the same, 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.
The anode layer 2 is made of Indium Tin Oxide (ITO) with a high work function, the hole injection layer 3 is made of HAT-CN and is 5nm thick, the first hole transport layer 4 is made of NPB and is 60nm thick, the second hole transport layer 5 is made of TCTA and is 15nm thick, the light emitting layer 6 is made of a compound 47 serving as a main body material, the BD01 serving as a light emitting material is doped with 5% of impurities and is 30nm thick, the hole blocking layer 7 is made of TPBI and is 10nm thick, the electron transport layer 8 is made of ET-1 and is 35nm thick, the electron injection layer 9 is made of L iq and is 2nm thick, and the cathode layer is made of Al and is 100nm thick.
The structural formula of the basic material used by each functional layer in the device is as follows:
Figure BDA0002446210930000171
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 vacuum evaporation, using the compound 47 as a host material and the BD01 as a light-emitting material, with a doping ratio of 5% and a thickness of 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 L iq on the electron transport layer in a vacuum evaporation mode, wherein the thickness of the electron injection material is 2nm, and the electron injection layer is formed on the electron transport 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 52 was used as the host material in place of compound 47.
Device example 3
Same as device example 1, except that: the main material is BH01, and the luminescent material is compound 1.
Device example 4
The same as device example 3 except that the light emitting material was compound 3.
Device example 5
The same as in device example 3, except that the light-emitting material was compound 11.
Device example 6
The same as device example 3, except that the light-emitting material was compound 28.
Device example 7
The same as device example 3 except that the light-emitting material was compound 37.
Comparative example 1
Same as device example 1, except that: BH01 was used as the host material instead of compound 47.
The components of the devices prepared in examples 1 to 7 and comparative example 1 of the present invention are shown in table 2:
TABLE 2 comparison table of organic electroluminescent element components of each device example
Figure BDA0002446210930000181
Figure BDA0002446210930000191
Each group of organic electroluminescent devices was connected between the cathode and the anode by a known drive circuit, and the voltage-efficiency-current density relationship of O L ED devices was measured by a standard method using a Keithley2400 power supply in combination with a PR670 photometer, as shown in the test data of device example 6 (compound 28 is a light-emitting material) in FIG. 2, and the lifetime of the devices was measured by a constant current method under a constant current density of 10mA/cm2The test time for the luminance to decay to 90% of the initial luminance is L T90The lifetime is shown in fig. 3, taking a lifetime test data chart of the device in device example 6 as an example, the test methods of the other devices are the same, and the test results of device examples 1 to 7 and comparative example 1 are shown in table 3:
table 3 performance results for each group of organic electroluminescent devices
Figure BDA0002446210930000192
As can be seen from table 3, the series of compounds provided by the present invention, as a blue host material or a blue light emitting material of a light emitting layer, are applied to an O L ED device, and have excellent performance, for example, the compound 47 in the device example 1, as a blue host material, is significantly improved in both light emitting efficiency and service life, increased by 21.2%, and increased by 30% as compared to the comparative example 1BH01, for example, the compound in the device examples 3-7, as a blue light emitting material, is excellent in performance, for example, the compound 3 in the embodiment 4, as compared to the BD01 in the comparative example 1, is improved in light emitting efficiency by about 40%, is improved in service life by 52%, and has more excellent color coordinates.
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 (10)

1. A pyrazine derivative is characterized in that the structural general formula is shown as formula (I):
Figure FDA0002446210920000011
wherein Ar is1、Ar2Each independently selected from a donor group or a fused ring aryl group;
the donor group is a group shown in a formula (II), a formula (III), a formula (IV), a formula (V), a formula (VI), a formula (VII), a formula (VIII), a formula (IX) or a formula (X):
Figure FDA0002446210920000012
in the formula (II), Ar3、Ar4Each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
in the formula (III), R1、R2Each independently selected from a hydrogen atom or a C1-C6 alkyl group;
in the formula (IV), X3Is C-m1m2O or S, m1、m2Each independently selected from substituted or unsubstituted aryl or C1-C6 alkyl;
in the formulas (V) and (VI), Y is C or Si;
the formula (IX) is a condensed heterocyclic group of C18-C24 and contains 2 five-membered rings;
in the formula (X), Z is C-m3m4、N-m5O or S, m3、m4Each independently selected from C1-C6 alkyl, m5Is substituted or unsubstituted aryl;
the condensed ring aryl is a group represented by formula (B1), formula (B2), formula (B3), formula (B4) or formula (B5):
Figure FDA0002446210920000021
2. a pyrazine derivative according to claim 1, wherein in the formula (II), Ar3、Ar4Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted fluorenyl; when substituted phenyl, these substituents are C1-C6 alkyl, phenyl, halogen, -CF3or-CN; when substituted dibenzofuranyl, these substituents are C1-C6 alkyl groups, and when substituted fluorenyl, these substituents are C1-C6 alkyl groups.
3. A pyrazine derivative according to claim 2, wherein in the formula (II), Ar3、Ar4Each independently selected from phenyl, methylphenyl, isopropylphenyl, biphenyl, trifluoromethylphenyl, fluorophenyl, cyanophenyl, dibenzofuranyl, isopropyldibenzofuranyl, fluorenyl or dimethylfluorenyl.
4. A pyrazine derivative according to claim 1, wherein in the formula (III), R1And R2Each independently from a hydrogen atom or a tert-butyl group.
5. A pyrazine derivative according to claim 1, wherein in the formula (IV), m1、m2Each independently selected from methyl or phenyl.
6. A pyrazine derivative according to claim 1, characterized in that formula (IX) is selected from one of the following structural formulas:
Figure FDA0002446210920000031
7. a pyrazine derivative according to claim 1, characterized by comprising the following compounds:
Figure FDA0002446210920000032
Figure FDA0002446210920000041
Figure FDA0002446210920000051
Figure FDA0002446210920000061
8. use of a pyrazine derivative according to any of claims 1 to 7 in organic electroluminescent devices.
9. An organic electroluminescent device comprising a light-emitting layer, wherein the material of the light-emitting layer comprises the pyrazine derivative according to any one of claims 1 to 7.
10. Use of the organic electroluminescent device according to claim 9 in an organic electroluminescent display device.
CN202010279992.1A 2020-04-10 2020-04-10 Pyrazine derivative and application thereof in O L ED device Pending CN111454251A (en)

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CN114044778A (en) * 2021-11-24 2022-02-15 西安瑞联新材料股份有限公司 Tris (1, 2-phenyl) diamine derivative organic photoelectric material and its use
CN114315695A (en) * 2021-12-06 2022-04-12 安徽秀朗新材料科技有限公司 Indole fused ring unit-based thermal activity delayed fluorescence molecular material and application thereof
CN114874224A (en) * 2022-06-06 2022-08-09 西安瑞联新材料股份有限公司 Bipolar compound with 5,10- [1,2] phenazine derivative as core and application thereof

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CN101874021A (en) * 2007-11-30 2010-10-27 出光兴产株式会社 Azaindenofluorenedione derivative, material for organic electroluminescent element, and organic electroluminescent element
CN110615783A (en) * 2019-09-23 2019-12-27 大连理工大学 Electroluminescent material with pyrazinoindenone as electron acceptor and application thereof

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CN101874021A (en) * 2007-11-30 2010-10-27 出光兴产株式会社 Azaindenofluorenedione derivative, material for organic electroluminescent element, and organic electroluminescent element
CN110615783A (en) * 2019-09-23 2019-12-27 大连理工大学 Electroluminescent material with pyrazinoindenone as electron acceptor and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114044778A (en) * 2021-11-24 2022-02-15 西安瑞联新材料股份有限公司 Tris (1, 2-phenyl) diamine derivative organic photoelectric material and its use
CN114315695A (en) * 2021-12-06 2022-04-12 安徽秀朗新材料科技有限公司 Indole fused ring unit-based thermal activity delayed fluorescence molecular material and application thereof
CN114315695B (en) * 2021-12-06 2023-09-08 安徽秀朗新材料科技有限公司 Thermal activity delayed fluorescence molecular material based on indole condensed ring unit and application thereof
CN114874224A (en) * 2022-06-06 2022-08-09 西安瑞联新材料股份有限公司 Bipolar compound with 5,10- [1,2] phenazine derivative as core and application thereof

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