CN110526926B - Nitrogen-doped material and application thereof - Google Patents
Nitrogen-doped material and application thereof Download PDFInfo
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Abstract
The present invention discloses compounds of the general formula (1):
Description
Technical Field
The invention relates to a novel organic compound, in particular to a compound for an organic electroluminescent device and application of the compound in the organic electroluminescent device.
Background
The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage direct current drive, full curing, wide viewing angle, light weight, simple composition and process and the like, and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle, low power, 1000 times of response speed of the liquid crystal display, and lower manufacturing cost than the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.
With the continuous advance of the OLED technology in the two fields of illumination and display, people pay more attention to the research of efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of the device structure and various organic materials. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. The phosphorescent host materials used at present have single carrier transport capability, such as hole-based transport hosts and electron-based transport hosts. The single carrier transport ability causes mismatching of electrons and holes in the light emitting layer, resulting in severe roll-off of efficiency and shortened lifetime. At present, in the use process of a phosphorescent host, a bipolar material or a double-host material matching mode is adopted to solve the problem of unbalanced carriers of a single-host material. The bipolar material realizes the common transmission of electrons and holes in one compound, and the molecular structure is more complex; the double-main-body material is used for realizing the transmission and combination of electrons and holes in the luminous layer by matching two materials, wherein one material is used as an electron type material, the other material is used as a hole type material, the electrons and the holes are combined at an interface after being conducted by the two materials, the two materials have wider sources, and the better device performance can be realized by adopting a combination mode of different materials.
Disclosure of Invention
In order to overcome the above disadvantages of the conventional host materials in the prior art, the present invention provides a novel class of compounds for organic electroluminescent devices.
The compound of the general formula of the present invention is represented by the following general formula (1):
in formula (1): x1-X8At least one is N, and the others are selected from CR ', and when a plurality of R ' exist, adjacent R ' can be connected to form a ring;
a is selected from one of NR', O or S;
r 'and R' are independently selected from hydrogen atom, alkyl of C1-C10, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;
ar is selected from substituted or unsubstituted C6-C50 aryl or substituted or unsubstituted C3-C50 heteroaryl.
When the substituent group exists on the aryl or heteroaryl, the substituent group is independently selected from halogen and C1～C10Alkyl of (C)3～C10Cycloalkyl of, C2～C10Alkenyl radical, C1～C6Alkoxy group of (C)1～C6Thioalkoxy of, C6～C30Aryl and C3～C30The heteroaryl group of (a).
Further, R 'and R' are each independently preferably selected from a hydrogen atom, a C1-C5 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 heteroaryl group.
Further, Ar is preferably selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl.
In particular, when the substituent groups are present on the above-mentioned aryl or heteroaryl groups, the substituent groups are each independently preferably selected from C1～C5Alkyl of (C)3～C5Cycloalkyl of, C1～C6Alkoxy group of (C)1～C6Thioalkoxy of, C6～C10Aryl and C3～C10The heteroaryl group of (a);
when a plurality of R's are present, adjacent R's may be linked to form a fused ring structure, and the fused ring structure is preferably selected from a phenyl group, a naphthyl group or an anthracenyl group.
Still further, R' and R "are each independently preferably selected from the group consisting of: hydrogen, methyl, ethyl, butyl, pentyl, phenyl, biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl, indenyl, pyrenyl, perylenyl, perylene,
A phenyl group, a tetracenyl group, a benzofluorenyl group, a spirofluorenyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a pyrrolyl group, a phenylpyridyl group, a pyrazinyl group, a quinolyl group, a triazinyl group, a benzotriazinyl group, a benzopyrazinyl group, a benzoquinolyl group, a dibenzopyrrolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-naphthylcarbazolocarbazolyl group or a dibenzocarbazolyl group;
still further, Ar is preferably selected from the following groups: phenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, phenanthryl, indenyl, benzofluorenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9 '-dialkylfluorene, 9' -spirobifluorenyl, indenofluorenyl, fluoranthenyl, triphenylenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, perylenyl,
Phenyl, 1-tetracenyl, 9-tetracenyl, furyl, dibenzofuran, thienyl, dibenzothiophene, pyrrolyl, pyridyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and derivatives thereof, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and mixtures thereof,
Phenyl, tetracenyl, 9-dimethylfluorenyl, distyrylphenyl, benzofluorenyl, indenofluorenyl, or indenyl.
Further, in the general formula (1) of the present invention, the following specific structural compounds P1 to P57 can be preferably selected, and these compounds are merely representative.
On the other hand, the invention simultaneously protects the application scheme that the compound with the general formula can be used as a luminescent main material in an organic electroluminescent device, and particularly can be used as a phosphorescent main material.
In still another aspect, the present invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer comprises at least one compound represented by formula (1) above.
In the general formula compound design, the LUMO energy level of molecules of the compound is deepened through nitrogen hybridization of aromatic rings, so that the passing of electrons can be more effectively blocked, and holes and electrons are effectively compounded in a light emitting layer to form excitons. Further ensures that the voltage and the efficiency of the compound are obviously improved when the compound is applied to an organic electroluminescent device.
On one hand, the general formula compound takes benzocarbazole benzofuran or thiophene with polycyclic conjugated characteristics as a parent structure, and is favorable for intermolecular solid-state accumulation due to high bond energy among atoms, has good thermal stability and is favorable for prolonging the service life of materials. On the other hand, the compounds of the invention are hybridized on the structure due to the aza-form. For an electronic host, the LUMO becomes deep, which is beneficial to the transmission of electrons, and the HOMO value becomes correspondingly deep, so that the electronic host has the capacity of blocking holes and the luminous efficiency is increased; for a hole-type host, intermolecular interaction force exists on molecular stacking of the aza-molecules, so that the molecules are arranged in a layered manner, which is favorable for charge transport.
The preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
When the compound with the general formula is used as a main material of a light-emitting layer in an organic electroluminescent device, the light-emitting efficiency of the device can be effectively improved, the stability of the device is improved, and the organic electroluminescent device with long service life is obtained.
Detailed Description
Specific methods for producing the above-described novel compounds of the present invention will be described in detail below by way of examples of synthesis, but the production method of the present invention is not limited to these examples of synthesis, and those skilled in the art can make modifications, equivalents, improvements, etc. without departing from the principles of the present invention and extend the methods to the scope of the claims of the present invention.
Synthetic examples
Different intermediate compounds can be obtained by substituting X at different positions from nitrogen. It should be noted that the buchwald hartwig coupling reaction or other ring closure reaction may be used in the above synthesis method, but the method is not limited to this method, and those skilled in the art may select other methods, which may be selected according to the needs.
More specifically, the following gives synthetic methods of representative compounds of the present invention.
Synthesis example 1: synthesis of Compound M1
33g (100mmol) of 1-bromo-5-iodonaphthalene, 18.4g (110mmol) of o-nitrobenzeneboronic acid and Pd are added into a reaction bottle2(PPh3)40.9g, toluene 500mL, potassium carbonate 43.3g (314mmol), water 100Ml, reaction at 100 ℃ for 3.5 h. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered and the resulting solid purified by recrystallization from toluene to give M1-1 as a white powder.
To a reaction flask, M1-116.3g (100mmol), triphenylphosphine 26.2g (100mmol) and o-dichlorobenzene (500 ml) were added and the reaction was carried out at 140 ℃ for 10 hours. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered and the resulting solid purified by recrystallization from toluene to give M1-2 as a white powder.
In a reaction flask, M1-229.5 g (100mmol), CuI-ZMS 52 g, S10 g, KOH 12g, DMF300mL were added and reacted for 24 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, adding cold water, filtering, and purifying the obtained solid by column chromatography to obtain intermediate M1-3.
To a reaction flask, M1-336 g (100mmol), palladium acetate 1.2g (5mmol), tricyclohexylphosphine 2.8g (10mmol), sodium tert-butoxide 19g, DMAC500ml were added and reacted for 5 hours. And stopping the reaction after the reaction is finished. Cooled to room temperature, filtered in cold water and the resulting solid recrystallized from toluene to give intermediate M1.
Synthesis example 2: synthesis of Compound M2
Similarly by substituting chloropyridine boronic acids in different positions we can obtain the following
Synthesis example 3: synthesis of Compound M3
Similarly, the method is obtained by replacing o-nitrobenzeneboronic acid in the reaction route with o-nitropyridineboronic acid and replacing chloropyridineboronic acid in the reaction formula with chloropyridineboronic acid
Synthesis example 4: synthesis of Compound M4
The method is the same as the synthesis of the intermediate M1, and is different from the following reaction
Adding M1-250 mmol, 4-chloropyridine-3-boric acid 100mmol, copper acetate 50mmol, triethylamine 500mmol, 4A molecular sieve 10g and dichloromethane 500mL into a reaction bottle, reacting at 0 deg.C for 6h in air atmosphere, filtering after complete reaction, concentrating, and separating by column chromatography to obtain intermediate M4
Synthesis example 5: synthesis of Compound M5
The procedure was as in Synthesis example 4, except that 4-chloropyridine-3-boronic acid was replaced with 5-chloropyridine-4-boronic acid to give intermediate M5
Synthesis example 6: synthesis of Compound M6
The method is the same as synthesis example 3, except that:
wherein Step1 method is synthesized with M1-2, Step2 method is synthesized with M1 to obtain intermediate M6
Synthesis example 7: synthesis of Compound P1
Mixing M250 mmol, S152 mmol and Pd2(dba)3Adding 0.5mmol of tri-tert-butylphosphine, 1mmol of sodium tert-butoxide, 100mmol of sodium tert-butoxide and 300mL of xylene into a reaction bottle, heating and refluxing for 6h, cooling to room temperature after the reaction is finished, filtering, dissolving filter cake dichloromethane, passing through a silica gel column, and concentrating to obtain a product P11H NMR(500MHz,Chloroform)δ9.51(s,1H),9.03–8.91(m,1H),8.66–8.49(m,2H),8.43–8.31(m,2H),8.24(d,J＝15.0Hz,1H),8.06–7.90(m,2H),7.89–7.73(m,3H),7.58–7.29(m,8H),7.22–7.05(m,3H)；MS＝606。
Synthesis example 8: synthesis of Compound P5
The procedure is as in synthesis example 7, except that S1 is replaced with an equivalent amount of 2-chloro-4-phenylquinazoline to give product P5.1H NMR(500MHz,Chloroform)δ9.51(s,1H),8.61(d,J＝7.5Hz,1H),8.55(dd,J＝7.3,1.6Hz,1H),8.23(d,J＝7.5Hz,1H),8.13(dd,J＝7.4,1.5Hz,1H),8.00(dd,J＝7.5,1.6Hz,1H),7.79(ddd,J＝7.5,5.4,1.6Hz,4H),7.65(t,J＝7.5Hz,2H),7.58–7.45(m,3H),7.40(d,J＝7.5Hz,1H),7.33(d,J＝7.5Hz,1H),7.21–7.06(m,3H)；MS＝529。
Synthesis example 9: synthesis of Compound P39
The procedure is as in Synthesis example 7, except that M2 is replaced by equivalent M4 and S1 is replaced by equivalent 2-chloro-4, 6-diphenylpyrimidineProduct P39.1H NMR(500MHz,Chloroform)δ8.86(s,1H),8.66–8.49(m,3H),8.31(d,J＝14.9Hz,1H),7.98–7.88(m,4H),7.64–7.44(m,8H),7.40(d,J＝15.0Hz,1H),7.27–7.05(m,4H)；MS＝539
Synthesis example 10: synthesis of Compound P41
The procedure is as in Synthesis example 7, except that M2 is replaced by equivalent M3 and S1 is replaced by equivalent 2-chloro-4 (1-naphthyl) quinazoline to give product P41.1H NMR(500MHz,Chloroform)δ9.01–8.92(m,1H),8.48–8.35(m,3H),8.13(dd,J＝7.4,1.5Hz,1H),8.00(t,J＝7.5Hz,1H),7.97–7.88(m,2H),7.88–7.75(m,5H),7.61–7.43(m,6H),7.35–7.26(m,2H),7.07(t,J＝7.5Hz,1H)；MS＝579
Synthesis example 11: synthesis of Compound P50
The process is the same as that of synthetic example 7, except that M2 is replaced by equivalent M6 to obtain product P50.1H NMR(500MHz,Chloroform)δ9.02–8.91(m,1H),8.55(dd,J＝14.2,3.7Hz,1H),8.47–8.29(m,4H),8.05–7.90(m,2H),7.89–7.78(m,2H),7.69–7.40(m,14H),7.21–7.00(m,4H)；MS＝665
Device embodiments
Detailed description of the preferred embodiments
The organic light emitting diode comprises a first electrode and a second electrode which are arranged on a substrate, and an organic material arranged between the electrodes, wherein a hole transport layer, a light emitting layer and an electron transport layer are arranged between the first electrode and the second electrode.
As the substrate, a substrate for an organic light emitting display is used, for example: glass, polymer materials, glass with TFT components, polymer materials, and the like.
The anode material can be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin dioxide (SnO)2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of these materials.
The cathode includes but is not limited to magnesium silver mixture, metal such as LiF/Al, ITO, etc., metal mixture, oxide.
Hole transport layers include, but are not limited to, combinations of one or more of HT1-HT31 listed below.
The light-emitting layer of the organic electroluminescent device comprises a host material and a dye, wherein the host material comprises but is not limited to one or a combination of GPH1-GPH80
Dyes include, but are not limited to, combinations of one or more of RPD1-RPD29 listed below.
The electron transport layer includes, but is not limited to, one or more combinations of ET1-ET57 listed below.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10-5Vacuum evaporating HT-11 on the anode layer film to form a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-5 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
a luminescent layer of the device is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material P1 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-5 is set in a proportion of 3%, and the total film thickness of evaporation is 30nm by using a multi-source co-evaporation method;
vacuum evaporating an electron transport layer material ET42 of the device on the light-emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
Device examples 2-5 and comparative example 1 were prepared as in example 1 except that the host material was changed from P1 to P5, P39, P41, P50 and C1.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 5 and comparative example 1 and the lifetime of the devices were measured at the same luminance using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 10000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 10000cd/m2The luminance drop of the organic electroluminescent device was measured to be 9500cd/m by maintaining a constant current at luminance2Time in hours.
The organic electroluminescent device properties are given in the following table:
as can be seen from the performance test results of the devices prepared in examples 1-5 and comparative example 1, when the compound synthesized by the invention is applied to a host material in a light-emitting layer in a device, compared with a scheme of adopting a known OLED material C1 as a light-emitting host, the current efficiency and the service life of the device are greatly improved, particularly the service life is obviously improved, and the pull-off voltage of the device is effectively reduced. Therefore, when the novel organic material is applied to an organic electroluminescent device, the novel organic material can be used as a main body material with good performance.
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 compound of the formula (1):
in formula (1): a is selected from NR', O or S;
X1-X8each is independently selected from N or CR', and one of them is N;
when a plurality of R's are present, adjacent R's may be linked to form a fused ring structure selected from phenyl;
r 'and R' are independently selected from hydrogen atom, alkyl of C1-C5, substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl;
ar is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;
when a substituent group exists on the aryl or heteroaryl, the substituent group is independently selected from C1～C5Alkyl of (C)3～C5Cycloalkyl of, C1～C6Alkoxy group of (C)1～C6Thioalkoxy of, C6～C10Aryl and C3～C10The heteroaryl group of (a).
2. Compounds of the general formula according to claim 1, in which:
r 'and R' are each independently selected from the following groups: hydrogen, methyl, ethyl, butyl, pentyl, phenyl, biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl, indenyl, pyrenyl, perylenyl, perylene,
A phenyl group, a tetracenyl group, a benzofluorenyl group, a spirofluorenyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a pyrrolyl group, a phenylpyridyl group, a pyrazinyl group, a quinolyl group, a triazinyl group, a benzotriazinyl group, a benzopyrazinyl group, a benzoquinolyl group, a dibenzopyrrolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-naphthylcarbazolocarbazolyl group or a dibenzocarbazolyl group;
ar is selected from the following groups: phenyl, indenyl, perylene,
A phenyl group, a furyl group, a dibenzofuran group, a thienyl group, a dibenzothiophene group, a pyrrolyl group, a pyridyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an indenofluorenyl group, a fluoranthenyl group, a tetracenyl group, a distyrylphenyl group, a benzofluorenyl group, a pyrenyl group, a 9, 9-dimethylfluorenyl group, and a 9, 9' -spirobifluorenyl group.
3. A compound of formula (la) according to claim 2, wherein:
ar is selected from the following groups: 2-biphenyl, 3-biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-dimethylfluorenyl, 9' -spirobifluorenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 1-tetracenyl and 9-tetracenyl.
4. A compound of formula (la) according to claim 1, selected from the following specific compounds:
5. use of a compound of the general formula according to claim 1 or 2 as a light-emitting host material in the light-emitting layer of an organic electroluminescent device.
6. Use of a compound according to claim 4 as a light-emitting host material in the light-emitting layer of an organic electroluminescent device.
7. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, characterized in that the organic layers comprise at least one compound of the general formula (1) as defined in claim 1.
8. An organic electroluminescent device according to claim 7, wherein the compound of the general formula represented by the formula (1) according to claim 1 included in the organic layer is selected from the following specific compounds:
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