CN111689962A - Compound with benzimidazole pyridine as receptor and application thereof - Google Patents

Compound with benzimidazole pyridine as receptor and application thereof Download PDF

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CN111689962A
CN111689962A CN202010544503.0A CN202010544503A CN111689962A CN 111689962 A CN111689962 A CN 111689962A CN 202010544503 A CN202010544503 A CN 202010544503A CN 111689962 A CN111689962 A CN 111689962A
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organic electroluminescent
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孙军
李启贵
霍东升
李飞
胡华院
张宏科
刘凯鹏
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Xi'an Manareco New Materials Co ltd
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Abstract

The invention provides a compound taking benzimidazole pyridine as a receptor, belonging to the technical field of organic electroluminescent functional materials. The structural general formula is shown as formula (I): in formula (I): l is1、L2Each independently is C4-C30 arylene or C4-C30 heteroarylene; ar (Ar)1、Ar2Each independently is an electron donating group or H, and Ar1And Ar2Not H at the same time; the electron donating group is one of diphenylamine group, carbazolyl, phena oxazinyl, phenothiazinyl, phenoxazinyl, phenazine and acridinyl; the invention also provides a benzeneApplication of a compound taking imidazopyridine as an acceptor in an organic electroluminescent device. The organic luminescent material prepared from the compound taking benzimidazole pyridine as the acceptor through introducing a brand new compound modified by a specific electron-donating group has higher thermal stability, and can remarkably improve the luminescent stability of a luminescent device. The general structural formula is shown as the following formula (I):
Figure DDA0002540236940000011

Description

Compound with benzimidazole pyridine as receptor and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescent functional materials, and particularly relates to a compound taking benzimidazole pyridine as a receptor and application thereof.
Background
The luminous mechanism of display and lighting elements of Organic electroluminescent Diodes (OLEDs), which are self-luminous electronic elements, is a novel optoelectronic information technology that converts electrical energy directly into light energy by means 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 green light and red light phosphorescent materials can meet the industrialization requirement, but the problem of high price still exists, the service life of the blue light phosphorescent materials can not meet the application requirement, so the industrialization can not be realized, and the blue light materials in the OLED product are still traditional fluorescent materials at present.
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 electron withdrawing groups which can be utilized at present are few in types, particularly, a high-quality TADF blue light material 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 design of the novel electron withdrawing group for developing the novel blue light TADF material is very important.
Two nitrogen atoms on a nitrogen ring of the benzimidazole pyridine have special properties, and a compound obtained by selecting a proper group modification can realize blue light emission, so that the benzimidazole pyridine nitrogen ring has been a research hotspot at present. The research results of the task group of the horseshoe atractylodes rhizome and the like in recent years show that: the phenanthroimidazole ligand has certain hybridization between a local state and a charge transport state of a compound constructed by triphenylamine group modification, so that a new excited state is formed, namely the local hybridization charge transfer excited state, a channel of thermal exciton exists in the excited state, the triplet exciton can pass through a back gap to reach a singlet state, and the utilization rate of the singlet exciton is improved. In addition, molecules of imidazole modified by the modified imidazole have distortion, which can inhibit intramolecular aggregation and block intramolecular charge transfer, thereby ensuring deep blue light emission, so how to select proper groups for substitution to realize efficient blue light emission of imidazole derivatives becomes a hotspot of current research.
Disclosure of Invention
The invention aims to provide a compound taking benzimidazole pyridine as a receptor, which can be used as a sensitized main material or a luminescent material in a luminescent layer by fully utilizing a local hybrid charge transfer excited state and modifying different electron-donating groups, and the material is applied to an organic electroluminescent device, so that the device performance of the organic electroluminescent device can be obviously improved.
The first purpose of the invention is to provide a compound taking benzimidazole pyridine as an acceptor, and the structural general formula is shown as the formula (I):
Figure BDA0002540236920000031
in formula (I):
L1、L2each independently is C4-C30 arylene or C4-C30 heteroarylene;
Ar1、Ar2each independently is an electron donating group or H, and Ar1And Ar2Not H at the same time;
the electron donating group is one of substituted or unsubstituted diphenylamine group, carbazolyl, pheno oxazinyl, phenothiazinyl, phenoxazinyl, phenazine and acridinyl;
the substituent is one or more of methyl, ethyl, isopropyl, tert-butyl, phenyl, carbazolyl, amine, acridine group, thiophene oxazine group, fluorenyl, dibenzofuran and dibenzothiophene.
Preferably, said L1、L2The same or different, are selected from one of the following structural formulas:
Figure BDA0002540236920000032
preferably, Ar is1、Ar2The same or different electron donating groups are selected from one of the following structural formulas:
Figure BDA0002540236920000033
Figure BDA0002540236920000041
preferably, specifically, any one of the following compounds:
Figure BDA0002540236920000042
Figure BDA0002540236920000051
Figure BDA0002540236920000061
Figure BDA0002540236920000071
the second purpose of the invention is to provide the application of the compound taking benzimidazolopyridine as the receptor in the organic electroluminescent device.
The third object of the present invention is to provide an organic electroluminescent device, comprising a light-emitting layer, wherein the light-emitting material of the light-emitting layer comprises a compound with benzimidazolopyridine as an acceptor.
The invention also provides an organic electroluminescent device, which comprises a luminescent layer, wherein the sensitized main body material of the luminescent layer comprises a compound which takes the benzimidazole pyridine as an acceptor.
A fifth 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 beneficial effects that:
according to the invention, a specific donor group is introduced to modify a benzimidazole pyridine ligand to form a brand-new donor-receptor molecular structure compound, the modification improves the orbital energy level and triplet state energy of the material, so that the material has a local hybrid charge transfer excited state, has bipolar characteristics and TADF (TADF) properties, and can be used as a luminescent layer sensitized main body material or a luminescent dye;
the series of compounds are used as sensitized main materials or TADF materials in organic electroluminescent (OLED) devices 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 benzimidazole pyridine ligand provided by the invention is modified by electron-donating groups bridged by arylene or heteroarylene.
The invention provides a compound taking benzimidazole pyridine as a receptor, which has a structural general formula shown as a formula (I):
Figure BDA0002540236920000091
in formula (I):
L1、L2each independently is C4-C30 arylene or C4-C30 heteroarylene;
Ar1、Ar2each independently is an electron donating group or H, and Ar1And Ar2Not H at the same time;
the electron donating group is one of substituted or unsubstituted diphenylamine group, carbazolyl, pheno oxazinyl, phenothiazinyl, phenoxazinyl, phenazine and acridinyl;
the substituent is one or more of methyl, ethyl, isopropyl, tert-butyl, phenyl, carbazolyl, amine, acridine group, thiophene oxazine group, fluorenyl, dibenzofuran and dibenzothiophene.
According to the invention, a specific donor group is introduced to modify a benzimidazole pyridine ligand to form a brand-new donor-receptor molecular structure compound, the modification improves the orbital energy level and triplet state energy of the material, so that the material has a local hybrid charge transfer excited state, has bipolar characteristics and TADF (TADF) properties, and can be used as a luminescent layer sensitized main body material or a luminescent dye;
the series of compounds are used as sensitized main materials or TADF materials in organic electroluminescent (OLED) devices to show excellent performance.
Specific examples of the benzimidazolopyridine receptor compound of the present invention are shown below.
Figure BDA0002540236920000092
Figure BDA0002540236920000101
Figure BDA0002540236920000111
Figure BDA0002540236920000121
In the following, we provide specific synthetic methods for the preparation of the above compounds and several intermediates corresponding thereto.
(1) Intermediate 1:
Figure BDA0002540236920000131
introducing nitrogen into a three-neck flask, adding 200g of intermediate 1-1, 146.4g of intermediate 1-2, 685.0g of cesium carbonate, 12.6g of 1, 10-phenanthroline and 3L of xylene, stirring until the raw materials are completely dissolved, adding 6.8g of cuprous iodide, heating to 120 ℃, stirring for reacting for 8 hours, and stopping the reaction after TLC monitors that the compound 1-1 is completely consumed. Cooling to room temperature, filtering the reaction solution, washing the organic phase to be neutral, drying the organic phase by using anhydrous sodium sulfate, and purifying the organic phase by using a silica gel column to obtain 111.0g of the intermediate 1 with the yield of 56.3 percent.
(2) Intermediate 2:
Figure BDA0002540236920000132
into a three-necked flask were charged 60g of intermediate 1, 26.0g of intermediate 2-1, 44.2g of potassium carbonate, 13.8g of tetra-t-butylammonium bromide, 600ml of toluene, 200ml of ethanol, 100ml of water, nitrogen gas was introduced, and then 6.2g of tetrakis (triphenylphosphine) palladium was added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography) that the raw materials are completely reacted, cooling to room temperature, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, and purifying by using a silica gel column to obtain 43.2g of an intermediate 2 with the yield of 72.9%.
(3) Intermediate 3:
Figure BDA0002540236920000133
a three-necked flask was charged with 40g of intermediate 1, 40.8g of intermediate 3-1, 29.5g of potassium carbonate, 9.2g of tetra-tert-butylammonium bromide, 400ml of toluene, 120ml of ethanol, 60ml of water, nitrogen gas was introduced, and then 4.1g of tetrakis (triphenylphosphine) palladium was added. The reaction solution is heated to 80 ℃, refluxed and stirred for reaction for 6 hours, TLC monitors that the raw materials are completely reacted and then cooled to room temperature, the reaction solution is washed to be neutral, and an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to obtain 47.8g of an intermediate 3 with a yield of 75.8 percent.
(4) Intermediate 4:
Figure BDA0002540236920000141
in a three-necked flask were charged 10g of intermediate 1, 13.3g of intermediate 4-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 180ml of toluene, 40ml of ethanol, 20ml of water, nitrogen gas was introduced, and then 1.0g of tetrakis (triphenylphosphine) palladium was added. The reaction solution is heated to 80 ℃, refluxed and stirred for reaction for 6 hours, TLC monitors that the raw materials are completely reacted and then cooled to room temperature, the reaction solution is washed to be neutral, and an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to obtain 12.9g of an intermediate 4 with the yield of 68.5 percent.
(5) Intermediate 5:
Figure BDA0002540236920000142
introducing nitrogen into a three-neck flask, adding 100g of intermediate 5-1, 73.2g of intermediate 1-2, 342.5g of cesium carbonate, 6.3g of 1, 10-phenanthroline and 1.5L of xylene, stirring until the raw materials are completely dissolved, adding 3.4g of cuprous iodide, heating to 120 ℃, stirring for reaction for 8 hours, and stopping the reaction after TLC monitors that the compound 5-1 is completely consumed. Cooling to room temperature, filtering the reaction solution, washing the organic phase to be neutral, drying the organic phase by using anhydrous sodium sulfate, and purifying the organic phase by using a silica gel column to obtain 46.8g of intermediate 5 with the yield of 47.5 percent.
(6) Intermediate 6:
Figure BDA0002540236920000143
30g of intermediate 5, 13.0g of intermediate 2-1, 22.1g of potassium carbonate, 6.9g of tetra-tert-butylammonium bromide, 300ml of toluene, 100ml of ethanol, 50ml of water, nitrogen gas introduction and then 3.1g of tetrakis (triphenylphosphine) palladium were added to a three-necked flask. The reaction solution is heated to 80 ℃, refluxed and stirred for reaction for 6 hours, TLC monitors that the raw materials are completely reacted and then cooled to room temperature, the reaction solution is washed to be neutral, and an organic phase is dried by anhydrous sodium sulfate and then purified by a silica gel column to obtain 22.6g of intermediate 6 with the yield of 76.3%.
(7) Compound 4:
Figure BDA0002540236920000151
in a three-necked flask were charged 10g of intermediate 2, 16.2g of compound 4-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 240ml of toluene, 60ml of ethanol, 30ml of water, nitrogen gas was introduced, and then 1.0g of tetrakis (triphenylphosphine) palladium was added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 14.6g of a compound 4, wherein the yield is 62.7%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.14(s,1H),7.94(s,1H),7.90(d,j＝6.8Hz,2H),7.55(m,4H),7.50(d,j＝8.4Hz,1H),7.37-7.41(m,5H),7.28(t,j＝6.4Hz,2H),7.17-7.21(m,9H),7.14(d,j＝6.4Hz,2H),6.95(t,j＝6.4Hz,2H),6.86(t,j＝8.4Hz,1H)。
(8) Compound 10:
Figure BDA0002540236920000152
10g of intermediate 2, 19.4g of compound 10-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 300ml of toluene, 80ml of ethanol, 40ml of water, introduction of nitrogen and then addition of 1.0g of tetrakis (triphenylphosphine) palladium were introduced into a three-necked flask. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 19.0g of a compound 4, wherein the yield is 71.8%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.21(d,j＝6.0Hz,4H),8.19(d,j＝6.8Hz,2H),8.14(s,1H),7.94(s,1H),7.92(m,4H),7.58(d,j＝6.4Hz,2H),7.50(d,j＝8.4Hz,1H),7.41(d,j＝6.4Hz,1H),7.36(m,6H),7.19-7.25(m,9H),7.16(t,j＝6.4Hz,2H),6.86(t,j＝8.4Hz,1H)。
(9) Compound 18
Figure BDA0002540236920000161
10g of intermediate 2, 19.4g of compound 18-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 300ml of toluene, 80ml of ethanol, 40ml of water, introduction of nitrogen and then addition of 1.0g of tetrakis (triphenylphosphine) palladium were introduced into a three-necked flask. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 17.3g of a compound 18, wherein the yield is 65.3%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.21(d,j＝6.0Hz,5H),8.19(d,j＝6.8Hz,2H),8.14(s,1H),7.94(s,2H),7.73(t,j＝6.4Hz,1H),7.68(t,j＝6.4Hz,1H),7.58-7.61(m,5H),7.50(d,j＝8.4Hz,1H),7.47(d,j＝6.8Hz,1H),7.41(d,j＝6.4Hz,1H),7.36(m,6H),7.19-7.21(m,5H),7.16(t,j＝6.4Hz,2H),6.86(t,j＝8.4Hz,1H)。
(10) Compound 30
Figure BDA0002540236920000171
10g of intermediate 2, 23.6g of compound 30-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 360ml of toluene, 80ml of ethanol, 40ml of water are charged in a three-necked flask, nitrogen is passed through, and then 1.0g of tetrakis (triphenylphosphine) palladium is added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 23.4g of a compound 30, wherein the yield is 76.1%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.21(d,j＝6.0Hz,4H),8.14(s,1H),7.94(s,1H),7.90(d,j＝6.8Hz,1H),7.86(d,j＝6.8Hz,1H),7.55(m,3H),7.50(d,j＝8.4Hz,1H),7.37-7.41(m,8H),7.33(s,1H),7.24-7.28(m,7H),7.16-7.21(m,6H),7.08(d,j＝6.8Hz,2H),7.00(t,j＝6.4Hz,1H),6.86(t,j＝8.4Hz,1H),1.69(s,6H)。
(11) Compound 47
Figure BDA0002540236920000172
10g of intermediate 1, 20.4g of compound 3-1, 14.8g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 300ml of toluene, 80ml of ethanol, 40ml of water, introduction of nitrogen and then addition of 2.1g of tetrakis (triphenylphosphine) palladium were introduced into a three-necked flask. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 17.8g of a compound 47 with the yield of 76.9%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.19(d,j＝6.8Hz,4H),8.14(s,1H),7.94(s,1H),7.92(d,j＝6.8Hz,4H),7.91(d,j＝6.8Hz,4H),7.58(d,j＝6.4Hz,4H),7.50(d,j＝8.4Hz,1H),7.35(t,j＝6.4Hz,4H),7.21(t,j＝8.4Hz,1H),7.16(d,j＝6.4Hz,4H),6.86(t,j＝8.4Hz,1H)。
(12) Compound 51
Figure BDA0002540236920000181
10g of intermediate 3, 8.2g of compound 50-1, 4.7g of potassium carbonate, 1.4g of tetra-tert-butylammonium bromide, 180ml of toluene, 60ml of ethanol, 30ml of water, introduction of nitrogen and then addition of 0.65g of tetrakis (triphenylphosphine) palladium were introduced into a three-necked flask. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 11.3g of a compound 51, wherein the yield is 69.2%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.19(d,j＝6.8Hz,4H),8.14(s,1H),7.94(s,1H),7.92(d,j＝6.8Hz,4H),7.91(d,j＝6.8Hz,4H),7.58(d,j＝6.4Hz,4H),7.50(d,j＝8.4Hz,1H),7.35(t,j＝6.4Hz,4H),7.25(d,j＝6.4Hz,4H),7.21(t,j＝8.4Hz,1H),7.16(d,j＝6.4Hz,4H),6.86(t,j＝8.4Hz,1H)。
(13) Compound 56
Figure BDA0002540236920000182
10g of intermediate 3, 8.4g of compound 4-1, 4.7g of potassium carbonate, 1.4g of tetra-tert-butylammonium bromide, 180ml of toluene, 60ml of ethanol, 30ml of water, introduction of nitrogen and then addition of 0.65g of tetrakis (triphenylphosphine) palladium were introduced into a three-necked flask. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 12.0g of a compound 56, wherein the yield is 72.3%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.21(d,j＝6.0Hz,4H),8.19(d,j＝6.8Hz,4H),8.14(s,1H),7.94(s,1H),7.92(d,j＝6.8Hz,2H),7.91(d,j＝6.8Hz,2H),7.58(d,j＝6.4Hz,4H),7.50(d,j＝8.4Hz,1H),7.37(t,j＝6.0Hz,4H),7.25(d,j＝6.4Hz,4H),7.21(t,j＝8.4Hz,1H),7.16(d,j＝6.4Hz,4H),6.86(t,j＝8.4Hz,1H)。
(14) Compound 64
Figure BDA0002540236920000191
In a three-necked flask were charged 10g of intermediate 4, 5.4g of compound 3-1, 4.7g of potassium carbonate, 1.4g of tetra-tert-butylammonium bromide, 180ml of toluene, 60ml of ethanol, 30ml of water, nitrogen gas was introduced, and then 0.65g of tetrakis (triphenylphosphine) palladium was added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 10.5g of a compound 64, wherein the yield is 75.9%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.21(d,j＝6.0Hz,4H),8.19(d,j＝6.8Hz,2H),8.14(s,1H),7.94(s,1H),7.92(d,j＝6.8Hz,2H),7.91(d,j＝6.8Hz,2H),7.65(d,j＝6.4Hz,2H),7.56(m,4H),7.50(d,j＝8.4Hz,1H),7.41(d,j＝6.4Hz,1H),7.37(t,j＝6.0Hz,4H),7.35(t,j＝6.4Hz,2H),7.25(d,j＝6.4Hz,4H),7.21(t,j＝8.4Hz,1H),7.16(d,j＝6.4Hz,2H),6.86(t,j＝8.4Hz,1H)。
(15) Compound 71
Figure BDA0002540236920000192
In a three-necked flask were charged 10g of intermediate 2, 21.3g of compound 71-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 240ml of toluene, 60ml of ethanol, 30ml of water, nitrogen gas was introduced, and then 1.0g of tetrakis (triphenylphosphine) palladium was added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 17.8g of a compound 71, wherein the yield is 65.2%.
1H NMR(400MHz,CDCl3)8.48(d,j＝8.8Hz,1H),8.19-8.21(m,6H),8.14(m,2H),8.04(s,1H),7.91-7.94(m,6H),7.58(d,j＝6.8Hz,1H),7.50-7.53(m,3H),7.35-7.41(m,6H),7.16-7.21(m,7H),6.86(t,j＝8.4Hz,1H)；
(16) Compound 74
Figure BDA0002540236920000201
In a three-necked flask were charged 10g of intermediate 6, 21.3g of compound 74-1, 7.4g of potassium carbonate, 2.3g of tetra-tert-butylammonium bromide, 240ml of toluene, 60ml of ethanol, 30ml of water, nitrogen gas was introduced, and then 1.0g of tetrakis (triphenylphosphine) palladium was added. Heating the reaction solution to 80 ℃, refluxing and stirring for reaction for 6h, monitoring by TLC (thin layer chromatography), cooling to room temperature after the raw materials are completely reacted, washing the reaction solution to be neutral, drying an organic phase by using anhydrous sodium sulfate, purifying by using a silica gel column, concentrating an eluent, and recrystallizing a crude product obtained by concentrating the eluent by using toluene to obtain 19.8g of a compound 74 with the yield of 72.3%.
1H NMR(400MHz,CDCl3)8.71(d,j＝8.8Hz,2H),8.48(d,j＝8.8Hz,1H),8.33(s,1H),8.19-8.21(m,6H),8.14(m,3H),7.75(d,j＝6.4Hz,2H),7.94(d,j＝6.4Hz,2H),7.47-7.50(m,9H),7.41(t,j＝6.4Hz,1H),7.29(d,j＝8.8Hz,2H),7.21(m,3H),6.86(t,j＝8.8Hz,1H)；
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 BDA0002540236920000211
Note: highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and triplet energy (T)1) And calculating by adopting simulation software to obtain data.
From table 1, the organic compounds of the present invention have suitable HOMO/LUMO, which is favorable for carrier transport and energy transfer in OLED devices, and can be used as sensitizer materials for light emitting layers and TADF light emitting materials. The organic electroluminescent device may be either an undoped light emitting layer device or a doped light emitting layer device without particular limitation. The material can be used as a sensitizer of a light-emitting layer and can also be used as a light-emitting material, and the compound taking the benzimidazole pyridine ligand as the core can effectively improve the light-emitting efficiency, the service life and other properties of the device after being applied to the light-emitting layer of the 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 luminescent layer material (host material and/or doped dye) respectively to verify the excellent effects obtained by the compounds.
The excellent effect of the OLED material in the invention applied to the device is detailed by the device performances of device examples 1-11 and comparative examples 1-2. The structure manufacturing processes of the device examples 1-11 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 as follows.
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 work 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 BH01 as a host material and the compound 4 as a light-emitting 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 100 nm.
The structural formula of the basic material used by each functional layer in the device is as follows:
Figure BDA0002540236920000221
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, using a compound BH01 as a host material and a compound 4 as a light-emitting material, wherein the doping content 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 100nm, and the layer was used as a cathode conductive electrode.
Device example 2
Same as device comparative example 1 except that: compound 10 was used as the dopant in place of compound 4.
Device example 3
Same as device example 1, except that: compound 18 was used as the dopant in place of compound 4.
Device example 4
Same as device example 1, except that: compound 30 was used as the dopant in place of compound 4.
Device example 5
Same as device example 1, except that: compound 47 is used as a luminescent material instead of compound 4, and no doping, i.e. no BH01 material, is required.
Device example 6
Same as comparative example 1 except that: compound 51 as a luminescent material instead of compound 4 requires no doping, i.e. no BH01 material.
Device example 7
Same as comparative example 1 except that: compound 56, as a luminescent material, replaces compound 4, without doping, i.e., without the BH01 material.
Device example 8
Same as comparative example 1 except that: compound 64 as a luminescent material instead of compound 4 does not require doping, i.e. no BH01 material is required.
Device example 9
Same as comparative example 1 except that: compound 71 as a luminescent material instead of compound 4 does not require doping, i.e. no BH01 material is required.
Device example 10
Same as comparative example 1 except that: compound 74 replaces compound 4 as a luminescent material and does not require doping, i.e., the BH01 material is not required.
Device example 11
Same as device example 1, except that: compound 51 as a luminescent layer sensitizing host material, and BD01 as a luminescent material instead of compound 4; the light-emitting layer comprises BH01, a compound 51 and BD01, wherein the mass percentages of BH01, the compound 51 and the BD01 are 50-75%: 20-45%: 5 percent.
Comparative example 1
Same as device example 1, except that: BH01 was used as the host material and BD01 was used as the light emitting material.
Comparative example 2
Same as comparative example 1 except that: BD02 replaces BD01 as a luminescent material, without doping, i.e. without the BH01 material.
The components of the devices prepared in examples 1 to 9 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 BDA0002540236920000251
Using known drivers for groups of organic electroluminescent devicesThe cathode and the anode are connected by a circuit, and the voltage-efficiency-current density relation of the OLED device is tested 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 brightness to decay to 90% of the initial brightness is the device LT90Lifetime, test results are shown in table 3:
table 3 performance results for each group of organic electroluminescent devices
Figure BDA0002540236920000252
Figure BDA0002540236920000261
As can be seen from Table 3, the compound provided by the invention is used as a luminescent material to be applied to an OLED blue light emitter, and has excellent performance. Compared with the conventional fluorescent blue-light material BD01 in comparative example 1, the luminescent efficiency and the service life of the luminescent material, such as the compound 30 in the device example 4, are both significantly improved, the luminescent efficiency is improved by 30.3%, and the service life is improved by 27%; as shown in device example 6, the compound 51 has excellent performance as a TADF material, and compared with comparative example 2, the device efficiency is improved by 25%, and the device life is improved by 32%; the compound 51 serving as the luminescent layer sensitizing material has excellent performance, and compared with the comparative example 1, in the device example 11, the luminous efficiency of the device is improved by 7.6% after the sensitizing main body is added, the service life is improved by 16.4%, and the device performance of the luminescent material is improved mainly because the sensitizing main body material can transfer all self energy and the main body material energy to the luminescent material. Compared with the prior material applied to an OLED light-emitting device, the compound provided by the invention has good photoelectric properties such as luminous efficiency, service life 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.
The compound with a donor-acceptor type molecular structure is obtained by connecting substituted or unsubstituted carbazolyl, acridinyl and other donor group modifications on the basis of a benzimidazole pyridine ligand. The modified compound has a proper front line orbital energy level and triplet state energy, and the innovative series of compounds have excellent performance when being used as a sensitized main body material or a luminescent material in an organic electroluminescent (OLED) device.
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 (8)

1. A compound with benzimidazole pyridine as a receptor is characterized in that the structural general formula is shown as the formula (I):
Figure FDA0002540236910000011
in formula (I):
L1、L2each independently is C4-C30 arylene or C4-C30 heteroarylene;
Ar1、Ar2each independently is an electron donating group or H, and Ar1And Ar2Not H at the same time;
the electron donating group is one of substituted or unsubstituted diphenylamine group, carbazolyl, pheno oxazinyl, phenothiazinyl, phenoxazinyl, phenazine and acridinyl;
the substituent is one or more of methyl, ethyl, isopropyl, tert-butyl, phenyl, carbazolyl, amine, acridine group, thiophene oxazine group, fluorenyl, dibenzofuran and dibenzothiophene.
2. The benzimidazolopyridine receptor compound of claim 1, wherein L is1、L2Each independently selected from one of the following structural formulas:
Figure FDA0002540236910000012
3. the benzimidazolopyridines of claim 1, wherein Ar is selected from the group consisting of1、Ar2The electron donating groups can be the same or different and are selected from one of the following structural formulas:
Figure FDA0002540236910000013
Figure FDA0002540236910000021
4. the compound of claim 1, which is a benzimidazole receptor, and is specifically any one of the following compounds:
Figure FDA0002540236910000022
Figure FDA0002540236910000031
Figure FDA0002540236910000041
Figure FDA0002540236910000051
5. use of a compound having a benzimidazolopyridine as an acceptor according to any one of claims 1 to 4 in an organic electroluminescent device.
6. An organic electroluminescent device comprising a light-emitting layer, wherein a light-emitting material of the light-emitting layer comprises the compound having the benzimidazolopyridine as an acceptor according to any one of claims 1 to 4.
7. An organic electroluminescent device comprising a light-emitting layer, wherein a sensitized host material of the light-emitting layer comprises the compound having the benzimidazolopyridine as an acceptor according to any one of claims 1 to 4.
8. Use of the organic electroluminescent device according to claim 6 or 7 in an organic electroluminescent display device.
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CN112358480A (en) * 2020-11-09 2021-02-12 西安瑞联新材料股份有限公司 Compound based on imidazo-cyclopent-isoquinoline as receptor and application thereof
CN112707894A (en) * 2020-12-29 2021-04-27 西安瑞联新材料股份有限公司 Acenaphthene imidazole compound and application thereof in organic electroluminescent device

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CN111606859A (en) * 2020-05-22 2020-09-01 西安瑞联新材料股份有限公司 Novel compound taking imidazole as receptor and application thereof
CN112358480A (en) * 2020-11-09 2021-02-12 西安瑞联新材料股份有限公司 Compound based on imidazo-cyclopent-isoquinoline as receptor and application thereof
CN112707894A (en) * 2020-12-29 2021-04-27 西安瑞联新材料股份有限公司 Acenaphthene imidazole compound and application thereof in organic electroluminescent device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112358480A (en) * 2020-11-09 2021-02-12 西安瑞联新材料股份有限公司 Compound based on imidazo-cyclopent-isoquinoline as receptor and application thereof
CN112661752A (en) * 2020-12-23 2021-04-16 吉林奥来德光电材料股份有限公司 Phenanthroimidazole condensed ring compound, preparation method thereof and organic electroluminescent device
CN112707894A (en) * 2020-12-29 2021-04-27 西安瑞联新材料股份有限公司 Acenaphthene imidazole compound and application thereof in organic electroluminescent device
CN113105451A (en) * 2021-04-16 2021-07-13 吉林省元合电子材料有限公司 Derivative containing N-cyclized benzimidazole structure and organic light-emitting device thereof
CN113105450A (en) * 2021-04-16 2021-07-13 吉林省元合电子材料有限公司 Derivative containing benzimidazole structure and organic light-emitting device prepared from derivative
CN113105451B (en) * 2021-04-16 2022-03-11 吉林省元合电子材料有限公司 Derivative containing N-cyclized benzimidazole structure and organic light-emitting device thereof
CN113105450B (en) * 2021-04-16 2022-06-17 吉林省元合电子材料有限公司 Derivative containing benzimidazole structure and organic light-emitting device prepared from derivative

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