CN108191766B - Benzimidazole organic electroluminescent material and preparation method and application thereof - Google Patents

Benzimidazole organic electroluminescent material and preparation method and application thereof Download PDF

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CN108191766B
CN108191766B CN201711394616.1A CN201711394616A CN108191766B CN 108191766 B CN108191766 B CN 108191766B CN 201711394616 A CN201711394616 A CN 201711394616A CN 108191766 B CN108191766 B CN 108191766B
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班全志
杭德余
马天凯
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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Abstract

The invention relates to the field of organic electroluminescence (OLED) display, in particular to a benzimidazole organic electroluminescent material and application thereof in an organic electroluminescent device. Crystallization is not easy to occur during evaporation, and the OLED device can effectively improve the OLED yield, reduce the driving voltage, improve the luminous efficiency and prolong the service life when being applied to the OLED device.

Description

Benzimidazole organic electroluminescent material and preparation method and application thereof
Technical Field
The invention relates to a novel benzimidazole organic material and application thereof in an organic electroluminescent device, belonging to the technical field of organic electroluminescent display.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
The electron transport material reported at present has the defects that the molecular weight is generally small, the glass transition temperature of the material is low, the material is easy to crystallize after repeated charging and discharging in the use process of the material, and the uniformity of a thin film is damaged, so that the service life of the material is influenced. Therefore, the stable and efficient electron transport material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the method has important practical application value.
Disclosure of Invention
The purpose of the present invention is to provide an OLED element that can be driven at low voltage, has a long lifetime, and has high efficiency, and a compound that can provide such an OLED element.
In order to develop a compound having the above-mentioned properties and an OLED device using the compound, it has been found that the above-mentioned object can be achieved by using the compound represented by the general formula (1).
Namely, the invention provides a novel benzimidazole organic electroluminescent material, which has the following structural general formula:
Figure BDA0001518238200000021
in the above formula, Ar is selected from:
Figure BDA0001518238200000022
m is an integer selected from 1 to 4;
Figure BDA0001518238200000023
representing the substituted bit.
Preferably, in formula I:
ar is selected from:
Figure BDA0001518238200000031
Figure BDA0001518238200000032
and/or, m is 1 or 2 or 3;
further preferably, when m is 1, the structure shown in formula I is selected from one of the following:
Figure BDA0001518238200000033
Figure BDA0001518238200000041
when m is 2, the structure shown in the general formula I is selected from one of the following structures:
Figure BDA0001518238200000042
Figure BDA0001518238200000051
when m is 3, the structure shown in the general formula I is selected from one of the following structures:
Figure BDA0001518238200000052
as a further preferred technical solution, the organic electroluminescent material is selected from one of the following compounds:
Figure BDA0001518238200000061
Figure BDA0001518238200000071
Figure BDA0001518238200000081
Figure BDA0001518238200000091
Figure BDA0001518238200000101
Figure BDA0001518238200000111
Figure BDA0001518238200000121
Figure BDA0001518238200000131
Figure BDA0001518238200000141
Figure BDA0001518238200000151
Figure BDA0001518238200000161
Figure BDA0001518238200000171
Figure BDA0001518238200000181
Figure BDA0001518238200000191
the organic electroluminescent material contains methyl on the terminal benzimidazole, so that the distance between molecules can be increased, association between compounds can be prevented, and the probability of stacking molecules is reduced. Crystallization is not easy to occur during evaporation, and the OLED device can effectively improve the OLED yield, reduce the driving voltage, improve the luminous efficiency and prolong the service life when being applied to the OLED device.
The invention also provides a preparation method of the organic electroluminescent material, which comprises two parallel schemes:
as one of the schemes, when Ar is:
Figure BDA0001518238200000201
Figure BDA0001518238200000202
when the temperature of the water is higher than the set temperature,
the reaction process is as follows:
Figure BDA0001518238200000203
the method specifically comprises the following steps:
(a) reacting a compound I-1 serving as a starting material with n-butyllithium to obtain a lithiation reagent, then performing lithiation reaction with unsaturated cyclic diketone, acidifying, and performing conventional treatment to obtain a compound I-2 under the action of sodium hypophosphite and potassium iodide;
(b) compound I-2 and
Figure BDA0001518238200000204
carrying out coupling reaction to obtain a compound I;
wherein m is an integer of 1 to 4 (in accordance with the definition in the organic electroluminescent material described above).
The above 2 steps can be realized by the ordinary means known to those skilled in the art, such as selecting suitable catalyst, solvent, determining suitable reaction temperature, time and the like.
Preferably, the preparation method comprises the following steps:
(a) taking a compound I-1 as a starting material, taking tetrahydrofuran as a solvent, reacting with n-butyl lithium at a temperature of between 90 ℃ below zero and 80 ℃ below zero, then controlling the temperature of between 90 ℃ below zero and 80 ℃ below zero, adding unsaturated cyclic diketone, stirring for 30 +/-2 hours, acidifying with hydrochloric acid, taking acetic acid as a solvent after conventional treatment, and carrying out reflux reaction with sodium hypophosphite and potassium iodide for 30 +/-2 hours to obtain a compound I-2;
(b) starting from the compound I-2, with
Figure BDA0001518238200000211
The compound I is obtained through the coupling reaction of piperidine formic acid and cuprous iodide.
Wherein m is an integer of 1 to 4 (in accordance with the definition in the organic electroluminescent material described above).
As a second alternative, when Ar is:
Figure BDA0001518238200000212
the reaction sequence is as follows:
Figure BDA0001518238200000213
the method comprises the following steps:
(e) taking the compound I-1 as a starting material, and firstly reacting with
Figure BDA0001518238200000214
Coupling reaction to obtain a compound I-3;
(f) the compound I-3 is subjected to lithiation reaction with n-butyl lithium, then is subjected to reaction with trimethyl borate, and is acidified to obtain a compound I-4;
(g) carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon to obtain a compound I;
wherein m is an integer of 1 to 4.
More preferably, the method comprises the steps of:
(e) starting from the compound I-1, with
Figure BDA0001518238200000221
Performing coupling reaction on piperidine formic acid and cuprous iodide to obtain a compound I-3;
(f) taking a compound I-3 as an initial raw material and tetrahydrofuran as a solvent, firstly carrying out lithiation reaction with n-butyllithium at a temperature of-80 +/-2 ℃, then carrying out reaction with trimethyl borate, and acidifying with hydrochloric acid to obtain a compound I-4;
(g) taking toluene, ethanol and water as solvents, palladium tetratriphenylphosphine as a catalyst, sodium carbonate as alkali, and under the protection of nitrogen, carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon under reflux to obtain a compound I;
wherein m is an integer of 1 to 4.
As described above
Figure BDA0001518238200000222
Trimethyl borate, piperidinecarboxylic acid, n-butyllithium and the like can be synthesized by publicly available commercial methods or methods known per se in the literature.
The invention further provides application of the organic electroluminescent material in an organic electroluminescent device.
Preferably, the organic electroluminescent material of the present invention is used as an electron transport layer in an organic electroluminescent device.
The invention also provides an organic electroluminescent device, wherein the organic functional layer of the organic electroluminescent device comprises the compound with the general formula, and the compound is used as an electron transport material in the organic functional layer.
Preferably, the organic electroluminescent device comprises a transparent substrate, an anode layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top in sequence.
The material for forming the transparent substrate is a glass substrate or a flexible substrate;
the substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. In the device manufacturing process, a glass substrate and ITO are selected as anode materials.
The anode layer is made of inorganic materials; wherein the inorganic material is at least one of Indium Tin Oxide (ITO), zinc oxide, zinc tin oxide, gold, silver or copper, preferably Indium Tin Oxide (ITO);
the material constituting the hole transport layer is selected from various triarylamine-based materials. The hole transport material selected for use in the fabrication of the devices of the present invention is at least one of the compounds represented by NPB and TPD:
Figure BDA0001518238200000231
the material constituting the organic light emitting layer is composed of a host material;
wherein the host material is any one of the following compounds:
Figure BDA0001518238200000232
the material for forming the electron transport layer is a compound shown in a formula I;
the material constituting the electron injection layer is selected from LiF, Li2O，MgO，Al2O3Preferably LiF.
The cathode is made of a material selected from the group consisting of lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver, preferably aluminum.
In particular, the method comprises the following steps of,
the thickness of the hole transport layer is 4-10nm, preferably 7 nm;
the thickness of the organic light-emitting layer is 10-100nm, preferably 20 nm;
the thickness of the electron transport layer is 10-50nm, preferably 20 nm;
the thickness of the electron injection layer is 5-30nm, preferably 8 nm;
the thickness of the cathode, preferably the Al layer, is 50-110nm, preferably 70 nm.
The novel OLED material provided by the invention takes a fused aromatic compound as a center, methyl-containing benzimidazole as an end group, and a substituent (2-phenylimidazole) with electron transport performance is introduced into an active position of the fused aromatic compound, so that the novel OLED material with the electron transport performance is obtained. The material has high electron mobility, good film stability and proper molecular energy level, and can be applied to the field of organic electroluminescence and used as an electron transport material.
Detailed Description
The basic chemical raw materials of various phenylbenzimidazole boric acids, various bromo-anthracene, bromo-perylene, bromo-pyrene, anthraquinone, benzoanthraquinone and the like used in the invention can be conveniently purchased in domestic chemical product markets, and various phenylbenzimidazole boric acids can be synthesized by using a common organic method.
The synthesis of the compounds in the present invention can be carried out by referring to the methods of example 1, example 2 and example 3. The following describes the synthesis of some of the main compounds of the present invention.
Example 1
Figure BDA0001518238200000241
Synthesis of (Compound 1)
The synthetic route is as follows:
Figure BDA0001518238200000242
1) synthesis of Compound 1-1
A1000 ml three-mouth bottle is stirred by magnetic force, 26.49g (purity 99 percent, 0.094mol) of 1-bromo-4-iodobenzene and THF500ml are added according to the amount after argon replacement. 38ml of n-BuLi (concentration 2.5M, 0.095mol) was added dropwise at-80 ℃ followed by 8.4g of anthraquinone (purity 99%, 0.04 mol). After the addition, the temperature is naturally raised to the room temperature, and the solution is bright yellow. Adding 500m of water for hydrolysis, separating liquid, extracting an aqueous phase by using dichloromethane, combining organic layers, evaporating the solvent to dryness, adding 600ml of acetic acid, 36g of KI and 36g of sodium hypophosphite, refluxing, reacting for 3 hours, cooling, filtering, and leaching by using water to obtain 17.49g of a yellow product with the purity of 99.5 percent and the yield of 90 percent.
2) Synthesis of Compound 1
N2Under the protection of gas, 16.53g (purity 94.5%, 0.034mol) of 9, 10-bis- (4-bromophenyl) anthracene, 21.23g (purity 99% 0.102mol) of 5-methyl-2-phenylbenzimidazole, 2.6g (purity AR0.0136mol) of copper iodide, 5.4g (purity AR0.0136mol) of piperidinecarboxylic acid and 35g (purity AR0.254mol) of potassium carbonate were charged into a 500mL three-necked flask. Adding DMF 500ml, magnetically stirring, refluxing for 50 hr, cooling, filtering, and boiling the yellow solid with ethanol for several times to obtain17.62g of yellow solid, 99.3% purity, 70% yield.
Product MS (m/e): 742.31, respectively; elemental analysis (C)54H33N4): theoretical value C: 87.30%, H: 5.16%, N: 7.54 percent; found value C: 87.33%, H: 5.22%, N: 7.45 percent.
According to the technical scheme of the example 1, the following compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0001518238200000251
Figure BDA0001518238200000261
Figure BDA0001518238200000271
Figure BDA0001518238200000281
Figure BDA0001518238200000291
Figure BDA0001518238200000301
Figure BDA0001518238200000311
Figure BDA0001518238200000321
Figure BDA0001518238200000331
Figure BDA0001518238200000341
Example 2:
Figure BDA0001518238200000342
synthesis of (Compound 2)
The synthetic route is as follows:
Figure BDA0001518238200000343
1) synthesis of Compound 2-1
N2Under the protection of gas, 9.58g (0.034mol) of 4-bromoiodobenzene, 21.23g (0.102mol) of 2-phenyl-5-methylbenzimidazole, 2.6g (purity AR0.0136mol) of copper iodide, 5.4g (purity AR0.0136mol) of piperidinecarboxylic acid and 35g (purity AR0.254mol) of potassium carbonate were put into a 500mL three-necked flask. DMF (600 ml) is stirred magnetically, refluxed for 30 hours, cooled and filtered, and the crude yellow solid is boiled with ethanol for several times to obtain 9.36g of yellow solid with purity of 99.6% and yield of 76%.
2) Synthesis of Compound 2-2
72.41g of 4- (5-methyl-2-phenylbenzimidazole) bromobenzene (compound 1-1, 0.2mol), 1000ml of tetrahydrofuran are added into a 2L dry and clean three-necked bottle, nitrogen is used for protection, liquid nitrogen is cooled to minus 80 ℃, 80ml of butyllithium is added dropwise, temperature control reaction is carried out for 1h after dropping, 32g of trimethyl borate (0.30mol) is added dropwise, temperature control is carried out for 30 minutes after dropping, then temperature is naturally raised to minus 20 ℃, and 600ml of hydrochloric acid aqueous solution is added dropwise. Separating, extracting the water phase twice with 400ml × 2 ethyl acetate, combining the organic phases, and spin-drying to obtain a white solid with liquid phase purity (LC) of 99.1%, theoretical yield of 65.63g, actual yield of 59.72g, and yield of 91%;
3) synthesis of Compound 2
N2Under the protection of gas, 7.34g (purity 98%, 0.02mol) of 1, 6-di-bromopyrene, 16.4g (purity 98%, 0.050mol) of 4- (5-methyl-2-phenylbenzimidazolyl) phenylboronic acid, 0.46g (purity AR, 0.0004mol) of palladium tetrakistriphenylphosphine, 17.3g (purity AR, 0.125mol) of potassium carbonate, 200mL of toluene, ethanol, and the like were added to a 1000mL three-necked flask150ml of water and 100ml of water. Heating and refluxing the materials. After 10 hours the reaction was stopped, allowed to cool and filtered to give a yellow solid which was recrystallized twice from 10 times THF. 16.22g of a pale yellow product are obtained, with a purity of 99.80% and a yield of 90%. Product MS (m/e): 766.31; elemental analysis (C)56H38N4): theoretical value C: 87.70%, H: 4.99%, N: 7.31 percent; found value C: 87.71%, H: 5.04%, N: 7.25 percent.
EXAMPLE 3 Synthesis of Compound 3
Figure BDA0001518238200000351
N2Under the protection of gas, 23.04g (purity 98%, 0.06mol) of 6, 12-dibromochrysene, 49.22g (purity 98%, 0.15mol) of 4- (5-methyl-2-phenylbenzimidazolyl) phenylboronic acid, 1.38g (purity AR, 0.0012mol) of palladium tetratriphenylphosphine, 51.76g (purity AR, 0.376mol) of potassium carbonate, 1000mL of toluene, 400mL of ethanol and 400mL of water were charged into a 5000mL three-necked flask. Heating and refluxing the materials. The reaction was stopped after 16 hours, allowed to cool, filtered to give a yellow solid, which was recrystallized from THF and repeated three times. 38.03g of a pale yellow product are obtained, purity 99.80%, yield 80%.
Product MS (m/e): 792.33.; elemental analysis (C)58H40N4): theoretical value C: 87.85%, H: 5.08%, N: 7.07 percent; found value C: 87.89%, H: 5.10%, N: 7.01 percent
According to the technical schemes of the embodiment 2 and the embodiment 3, the following compounds can be synthesized only by simply replacing corresponding raw materials without changing any substantial operation.
Figure BDA0001518238200000361
Figure BDA0001518238200000371
Figure BDA0001518238200000381
Figure BDA0001518238200000391
Figure BDA0001518238200000401
Example 4 preparation of devices OLED-1 to OLED-4
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-4Pa, evaporating a compound NPB on the anode layer film to form a hole transport layer, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 7 nm;
Figure BDA0001518238200000411
3) continuously evaporating ADN on the hole transport layer to serve as a main material and an organic light-emitting layer of the device, wherein the evaporation rate is 0.2nm/s, and the thickness of the organic light-emitting layer obtained by evaporation is 20 nm;
Figure BDA0001518238200000412
4) continuously evaporating a layer of the compound 1 which is prepared in the embodiment 1 and belongs to the formula I on the organic light-emitting layer to be used as an electron transport layer of a device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 20 nm;
5) continuously evaporating a layer of LiF on the electron transport layer to be used as an electron injection layer of the device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 8 nm;
6) continuously evaporating a layer of Al on the electron injection layer to be used as a cathode of the device, wherein the evaporation rate is 0.2nm/s, and the evaporation film thickness is 70 nm; obtaining the OLED device provided by the invention, and marking as OLED-1;
replacing the compound 1 in the step 4) with the compound 2 prepared in the example 2 according to the same procedure as above to obtain the OLED-2 provided by the invention;
replacing the compound 1 in the step 4) with the compound 3 prepared in the example 3 according to the same procedure as above to obtain the OLED-3 provided by the present invention;
replacing compound 1 in step 4) with ET1 following the same procedure as above to give a comparative device OLED-4;
ET1 (comparative Compound 1)
The performance test results of the obtained devices OLED-1 to OLED-4 under the same test conditions are shown in Table 1.
TABLE 1 measurement results of OLED-1 to OLED-4
Figure BDA0001518238200000414
Figure BDA0001518238200000421
From the above, the devices OLED-1 to OLED-4 prepared by using the organic electroluminescent material shown in formula I provided by the present invention have lower lighting voltage, and under the same brightness condition, the current efficiency is significantly higher than that of the device OLED-4 using ET1 as the electron transport material, and the lifetime of the device is significantly prolonged.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.

Claims (8)

1. A benzimidazole organic electroluminescent material is characterized in that: the organic electroluminescent material is selected from one of the following compounds:
Figure FDA0002596496710000011
2. a method for producing an organic electroluminescent material as claimed in claim 1, characterized in that: when the organic electroluminescent material is:
Figure FDA0002596496710000012
the reaction sequence is as follows:
Figure FDA0002596496710000013
the method specifically comprises the following steps:
(a) taking a compound I-1 as an initial raw material, firstly reacting with n-butyllithium to obtain a lithiation reagent, then carrying out lithiation reaction with unsaturated cyclic diketone, acidifying, and obtaining a compound I-2 under the action of sodium hypophosphite and potassium iodide, wherein the unsaturated cyclic diketone is 9, 10-anthraquinone;
(b) compound I-2 and
Figure FDA0002596496710000021
the coupling reaction to obtain the compound
Figure FDA0002596496710000022
When the organic electroluminescent material is:
Figure FDA0002596496710000023
the reaction sequence is as follows:
Figure FDA0002596496710000024
the method comprises the following steps:
(e) taking the compound I-1 as a starting material, and firstly reacting with
Figure FDA0002596496710000025
Coupling reaction to obtain a compound I-3;
(f) the compound I-3 is subjected to lithiation reaction with n-butyl lithium, then is subjected to reaction with trimethyl borate, and is acidified to obtain a compound I-4;
(g) carrying out SUZUKI coupling reaction on the compound I-4 and dibromo polycyclic aromatic hydrocarbon to obtain a compound
Figure FDA0002596496710000031
Wherein the dibromo polycyclic aromatic hydrocarbon is
Figure FDA0002596496710000032
3. Use of the organic electroluminescent material according to claim 1 in an organic electroluminescent device.
4. Use according to claim 3, characterized in that: the organic electroluminescent material is used as an electron transport layer in the organic electroluminescent device.
5. An organic electroluminescent device, characterized in that: comprising an electron transport layer made of the organic electroluminescent material as claimed in claim 1.
6. The organic electroluminescent device according to claim 5, wherein: the organic electroluminescent device consists of a transparent substrate, an anode layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top in sequence.
7. The organic electroluminescent device according to claim 6, wherein: the transparent substrate is made of a glass substrate or a flexible substrate;
and/or; the anode layer is made of at least one material selected from indium tin oxide, zinc oxide, tin zinc oxide, gold, silver and copper;
and/or; the material constituting the hole transport layer is at least one of compounds represented by NPB and TPD:
Figure FDA0002596496710000033
Figure FDA0002596496710000041
and/or; the host material constituting the organic light-emitting layer is any one of the following compounds:
Figure FDA0002596496710000042
and/or; the material constituting the electron injection layer is selected from LiF, Li2O, MgO or Al2O3One of (1);
and/or; the cathode layer is made of a material selected from one of lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver.
8. The organic electroluminescent device according to claim 6 or 7, characterized in that: the thickness of the hole transport layer is 4-10 nm; the thickness of the organic light-emitting layer is 10-100 nm; the thickness of the electron transmission layer is 10-50 nm; the thickness of the electron injection layer is 5-30 nm; the thickness of the cathode layer is 50-110 nm.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875637A (en) * 2009-11-13 2010-11-03 昆山维信诺显示技术有限公司 Organic material and application thereof in organic electroluminescence devices
CN102082231A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Green organic electroluminescent device
CN102082232A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Blue light organic electroluminescence device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875637A (en) * 2009-11-13 2010-11-03 昆山维信诺显示技术有限公司 Organic material and application thereof in organic electroluminescence devices
CN102082231A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Green organic electroluminescent device
CN102082232A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Blue light organic electroluminescence device

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