Organic compound and application thereof
阅读说明：本技术 一种有机化合物及其应用 (Organic compound and application thereof ) 是由 张磊 高威 代文朋 冉佺 翟露 刘营 过宇阳 于 2021-09-24 设计创作，主要内容包括：本发明提供一种有机化合物及其应用,所述有机化合物具有较深的LUMO能级,可以降低电子传输的势垒,提高电子的注入能力,有效降低OLED的器件电压；化合物均具有较深的HOMO能级,这可以有效地阻挡空穴,使更多的空穴-电子在发光区进行复合,可以实现较高的发光效率。适用于OLED器件的电子传输层材料,能够降低器件的电压和功耗,提高发光效率,延长工作寿命,使OLED器件具有更好的综合性能。(The invention provides an organic compound and application thereof, wherein the organic compound has a deeper LUMO energy level, can reduce the potential barrier of electron transmission, improves the injection capability of electrons, and effectively reduces the voltage of an OLED device; the compounds have deeper HOMO energy levels, which can effectively block holes, so that more holes-electrons are combined in a light emitting region, and higher light emitting efficiency can be realized. The material is suitable for the electron transport layer material of an OLED device, can reduce the voltage and power consumption of the device, improves the luminous efficiency, prolongs the service life and enables the OLED device to have better comprehensive performance.)
1. An organic compound having a structure represented by formula I:
wherein X is respectively and independently selected from O or S or N-Ar2，LlAnd L2The same or different from each other, and each independently is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group;
a. b is respectively and independently an integer from 0 to 3, c is an integer from 1 to 3;
Ar2selected from phenyl, biphenyl or naphthyl;
Ar1is any one selected from the following structural formulas;
Y1to Y3Two of them are N, the other is CH; or Y1To Y3Are all N;
z is N-Ar6S or O;
Z1-Z13is an N or C atom, wherein Z6-Z8At least one is N;
X1-X5is an N or C atom;
U1-U4is N or C atom, and at least one is N atom;
Ar3to Ar6Selected from phenyl, biphenyl or naphthyl; ar (Ar)7Selected from hydrogen, phenyl, biphenyl or naphthyl.
2. An organic compound according to claim 1, wherein X is O, L1 is an arylene group having C6-C60, a heteroarylene group having C3-C60, L2 is an arylene group having C6-C60 or a heteroarylene group having C3-C60.
3. An organic compound according to claim 2, wherein L1 is phenylene and L2 is phenylene, naphthylene or phenanthrylene.
4. An organic compound according to claim 1, wherein X is S, L1 is an arylene group of C6-C60, a heteroarylene group of C3-C60, L2 is an arylene group of C6-C60 or a heteroarylene group of C3-C60.
5. An organic compound according to claim 1, wherein X is N-Ar2L1 is an arylene group of C6-C60, a heteroarylene group of C3-C60, L2 is an arylene group of C6-C60 or a heteroarylene group of C3-C60; ar (Ar)2Selected from phenyl, biphenyl or naphthyl.
6. The organic compound of claim 1, wherein Ar is Ar1Is composed of
7. The organic compound according to claim 1, wherein the substituent in the substituted arylene or substituted heteroarylene is any one of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, cyano, C1-C20 linear or branched alkyl, C1-C20 alkoxy, or C1-C20 alkylthio.
8. The organic compound according to claim 1, wherein the organic compound is any one of the following compounds:
9. an electron transport material comprising the organic compound according to any one of claims 1 to 8.
10. An OLED device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode, wherein the material of the organic thin film layer comprises the organic compound according to any one of claims 1 to 8.
11. The OLED device of claim 10, wherein the organic thin film layer comprises an electron transport layer comprising the organic compound according to any one of claims 1 to 9 as a host material.
12. A display panel characterized in that it comprises an OLED device according to claim 10 or 11.
13. An electronic device characterized in that it comprises a display panel as claimed in claim 12.
Technical Field
The invention belongs to the technical field of organic electroluminescence, and relates to an organic compound and application thereof.
Background
The electron transport material used in conventional electroluminescent devices is Alq3, but the electron mobility ratio of Alq3 is relatively low (approximately at l 0)-6cm2Vs) such that electron transport and hole transport of the device are not balanced. With the commercialization and practicability of electroluminescent devices, it is desirable to obtain ETL materials with higher transmission efficiency and better usability, and researchers have done a great deal of exploratory work in this field.
W02007/011170 Al and CN 101003508A in LG chemistry disclose a series of naphthoimidazole and pyrene derivatives, respectively, for use as electron transporting and injecting materials in electroluminescent devices to improve the luminous efficiency of the devices. Kodak publication nos. US 2006/0204784 and US 2007/0048545 disclose hybrid electron transport layers formed by doping one material with a low LUMO level with another electron transport material with a low ignition voltage and other materials such as metallic materials. The efficiency, lifetime, etc. of devices based on such hybrid electron transport layers are improved. However, the electron transport material has a planar molecular structure and a large intermolecular attraction, which is not favorable for vapor deposition and application; in addition, the electron transport material also has the defects of low mobility, poor energy level matching, poor thermal stability, short service life, doping property and the like, and further development of the OLED display device is limited.
Most of the electron transport materials currently used in the market, such as batho-phenanthroline (BPhen), Bathocuproine (BCP) and TmPyPB, can substantially meet the market demand of organic electroluminescent panels, but their glass transition temperature is low, generally less than 85 ℃, and the generated joule heat during device operation can cause molecular degradation and change of molecular structure, resulting in low panel efficiency and poor thermal stability. Meanwhile, the molecular structure is symmetrical regularly, and the crystal is easy to crystallize after a long time. Once the electron transport material is crystallized, the intermolecular charge jump mechanism is different from the normal amorphous thin film mechanism, resulting in the decrease of electron transport performance, the imbalance of electron and hole mobility of the whole device, the great decrease of exciton formation efficiency, and the concentration of exciton formation at the interface of the electron transport layer and the light emitting layer, resulting in the serious decrease of device efficiency and lifetime.
Therefore, the electron transport material and/or the electron injection material which are stably and efficiently designed and developed, have high electron mobility and high glass transition temperature, are effectively doped with metal, reduce threshold voltage, improve device efficiency, prolong device service life and have important practical application value.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide an organic compound and its application.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide an organic compound having a structure represented by the following formula I:
wherein X is respectively and independently selected from O or S or N-Ar2，LlAnd L2Are the same or different from each other and are each independentlyIs a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group;
a. b is independently an integer selected from 0 to 3 (e.g., 0, 1, 2, 3), c is selected from an integer from 1 to 3 (e.g., 1, 2, 3);
Ar2selected from phenyl, biphenyl or naphthyl;
Ar1is any one selected from the following structural formulas;
Y1to Y3Two of them are N, the other is CH; or Y1To Y3Are all N;
z is N-Ar6S or O;
Z1-Z13is an N or C atom, wherein Z6-Z8At least one is N;
X1-X5is an N or C atom;
U1-U4is N or C atom, and at least one is N atom;
Ar3to Ar6Selected from phenyl, biphenyl or naphthyl; ar (Ar)7Selected from hydrogen, phenyl, biphenyl or naphthyl.
The organic compound has the characteristics of good Electron Transport (ET) materials, has a deeper LUMO energy level, can reduce the potential barrier of electron transport, improves the injection capability of electrons, and effectively reduces the voltage of OLED devices; the compounds have deeper HOMO energy levels, so that holes can be effectively blocked, more holes-electrons are compounded in a light emitting region, and higher light emitting efficiency can be realized; the compound of the invention has reversible electrochemical reducibility, has sufficiently high reduction potential and is beneficial to electron transmission; the compound has high electron mobility, can ensure that electrons can be compounded in a light-emitting layer, so that the generation rate of excitons is improved, the glass transition temperature Tg and the thermal decomposition stability are high, and further the influence of joule heat generated by the device during operation on the service life and the efficiency of the device is avoided; the material has good film forming uniformity, and can avoid degradation or attenuation caused by light scattering or crystallization induction.
It is a second object of the present invention to provide an electron transport material comprising an organic compound according to the first object.
It is a further object of the present invention to provide an OLED device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode, the material of the organic thin film layer comprising an organic compound according to one of the objects.
It is a fourth object of the present invention to provide a display panel including the OLED device of the third object.
The fifth object of the present invention is to provide an electronic device, which includes the display panel according to the fourth object.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound has the characteristics of good Electron Transport (ET) materials, has a deeper LUMO energy level, can reduce the potential barrier of electron transport, improves the injection capability of electrons, and effectively reduces the voltage of OLED devices; the compounds have deeper HOMO energy levels, which can effectively block holes, so that more holes-electrons are combined in a light emitting region, and higher light emitting efficiency can be realized.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device of the present invention;
wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is a cathode, and the arrow represents a light emitting direction of the device.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
One of the objects of the present invention is to provide an organic compound having a structure represented by the following formula I:
wherein X is respectively and independently selected from O or S or N-Ar2，LlAnd L2The same or different from each other, and each independently is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group;
a. b is independently an integer selected from 0 to 3 (e.g., 0, 1, 2, 3), c is selected from an integer from 1 to 3 (e.g., 1, 2, 3);
Ar2selected from phenyl, biphenyl or naphthyl;
Ar1is any one selected from the following structural formulas;
Y1to Y3Two of them are N, the other is CH; or Y1To Y3Are all N;
z is N-Ar6S or O;
Z1-Z13is an N or C atom, wherein Z6-Z8At least one is N;
X1-X5is an N or C atom;
U1-U4is N or C atom, and at least one is N atom;
Ar3to Ar6Selected from phenyl, biphenyl or naphthyl; ar (Ar)7Selected from hydrogen, phenyl, biphenyl or naphthyl.
The organic compound has the characteristics of good Electron Transport (ET) materials, has a deeper LUMO energy level, can reduce the potential barrier of electron transport, improves the injection capability of electrons, and effectively reduces the voltage of OLED devices; the compounds have deeper HOMO energy levels, so that holes can be effectively blocked, more holes-electrons are compounded in a light emitting region, and higher light emitting efficiency can be realized; the compound of the invention has reversible electrochemical reducibility, has sufficiently high reduction potential and is beneficial to electron transmission; the compound has high electron mobility, can ensure that electrons can be compounded in a light-emitting layer, so that the generation rate of excitons is improved, the glass transition temperature Tg and the thermal decomposition stability are high, and further the influence of joule heat generated by the device during operation on the service life and the efficiency of the device is avoided; the material has good film forming uniformity, and can avoid degradation or attenuation caused by light scattering or crystallization induction.
In one embodiment, X is O, L1 is an arylene group of C6-C60, a heteroarylene group of C3-C60, L2 is an arylene group of C6-C60 or a heteroarylene group of C3-C60.
In one embodiment, L1 is phenylene and L2 is phenylene, naphthylene, or phenanthrylene.
In one embodiment, X is S, L1 is an arylene group of C6-C60, a heteroarylene group of C3-C60, L2 is an arylene group of C6-C60 or a heteroarylene group of C3-C60.
In one embodiment, X is N-Ar2L1 is an arylene group of C6-C60, a heteroarylene group of C3-C60, L2 is an arylene group of C6-C60 or a heteroarylene group of C3-C60; ar (Ar)2Selected from phenyl, biphenyl or naphthyl.
In the present invention, each of C6 to C60 may be, independently, C7, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C33, C35, C38, C40, C45, C48, C50, C53, C55, C58, or the like.
Each of C3 to C60 may be, independently, C4, C6, C7, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C33, C35, C38, C40, C45, C48, C50, C53, C55, C58, or the like.
In one embodiment, Ar1Is composed of
In one embodiment, the substituted arylene or substituted heteroarylene group has a substituent selected from phenyl, biphenyl, naphthyl, anthryl, phenanthryl, cyano, C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight or branched alkyl, C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) alkoxy, or C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) alkylthio.
In one embodiment, the organic compound is any one of the following compounds:
it is a second object of the present invention to provide an electron transport material comprising an organic compound according to the first object.
It is a further object of the present invention to provide an OLED device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode, the material of the organic thin film layer comprising an organic compound according to one of the objects.
In one embodiment, the organic thin film layer includes an electron transport layer including an organic compound as one of the objects as a host material.
In the OLED device provided by the invention, the anode material can be metal, metal oxide or conductive polymer; wherein the metal includes copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof, the metal oxide includes Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide, Indium Gallium Zinc Oxide (IGZO), etc., and the conductive polymer includes polyaniline, polypyrrole, poly (3-methylthiophene), etc. In addition to the above materials and combinations thereof that facilitate hole injection, known materials suitable for use as anodes are also included.
In the OLED device, the cathode material can be metal or a multi-layer metal material; wherein the metal comprises aluminum, magnesium, silver, indium, tin, titanium and the like and alloys thereof, and the multilayer metal material comprises LiF/Al, LiO2/Al, BaF2/Al and the like. In addition to the above materials and combinations thereof that facilitate electron injection, known materials suitable for use as cathodes are also included.
In the OLED device, the organic thin film layer comprises at least one light emitting layer (EML) and any one or a combination of at least two of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL) or an Electron Injection Layer (EIL) which are arranged on two sides of the light emitting layer. The hole/electron injecting and transporting layer may be a carbazole-based compound, an arylamine-based compound, a benzimidazole-based compound, a metal compound, or the like, in addition to the organic compound described as one of the objects of the present invention. A cap layer (CPL) may optionally be provided on the cathode (the side remote from the anode) of the OLED device.
The OLED device can be prepared by the following method: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. Among them, known film forming methods such as evaporation, sputtering, spin coating, dipping, ion plating, and the like can be used to form the organic thin layer.
It is a fourth object of the present invention to provide a display panel including the OLED device of the third object.
The fifth object of the present invention is to provide an electronic device, which includes the display panel according to the fourth object.
Several preparation examples of the organic compounds according to the invention are listed below by way of example:
preparation examples:
synthesis of compound E1, the structure of which is as follows:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 1-bromo-4- (4-chlorophenyl) -naphthalene (12mmol), Compound M1(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H2O (75/25/50, mL) solvent, respectively, to form a mixed solution, and then Pd (PPh) was added3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate E1-1.
In a 250ml round-bottom flask, intermediate E1-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E1.
Elemental analysis structure (molecular formula C41H24BNO2) for compound E1: theoretical value: c, 85.87; h, 4.22; b, 1.89; n, 2.44; and O, 5.58. Test values are: c, 85.82; h, 4.25; b, 1.89; n, 2.44; and O, 5.59. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 573.19 and the test value is 573.45.
Synthesis of compound E2, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 1-bromo-4- (4-chlorophenyl) -naphthalene (12mmol), Compound M3(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate E2-1.
In a 250ml round-bottom flask, intermediate E2-1(12mmol), Compound M4(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E2.
Elemental analysis structure (molecular formula C49H30BN3O2) for compound E2: theoretical value: c, 83.65; h, 4.30; b, 1.54; n, 5.97; and O, 4.55. Test values are: c, 83.61; h, 4.32; b, 1.54; n, 5.97; and O, 4.56. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 703.24 and the test value is 703.59.
Synthesis of compound E3, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 1-bromo-4- (4-chlorophenyl) -naphthalene (12mmol), Compound M5(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate E3-1.
In a 250ml round-bottom flask, intermediate E3-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E3.
Elemental analysis structure (molecular formula C49H30BN3O2) for compound E3: theoretical value: c, 83.65; h, 4.30; b, 1.54; n, 5.97; and O, 4.55. Test values are: c, 83.61; h, 4.32; b, 1.54; n, 5.97; and O, 4.56. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 703.24 and the test value is 703.59.
Synthesis of compound E4, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 1-bromo-4- (4-chlorophenyl) -naphthalene (12mmol), Compound M6(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate E4-1.
In a 250ml round-bottom flask, intermediate E4-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E4.
Elemental analysis structure (molecular formula C49H30BN3O2) for compound E4: theoretical value: c, 85.21; h, 4.32; b, 1.60; n, 4.14; and O, 4.73. Test values are: c, 85.19; h, 4.34; b, 1.60; n, 4.14; and O, 4.74. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 676.23 and the test value is 676.57.
Synthesis of compound E5, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 4' -bromo-4-chlorobiphenyl (12mmol), compound M5(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate E5-1.
In a 250ml round-bottom flask, intermediate E5-1(12mmol), Compound M7(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E5.
Elemental analysis structure (molecular formula C45H28BN3S2) for compound E5: theoretical value: c, 78.83; h, 4.12; b, 1.58; n, 6.13; and S, 9.35. Test values are: c, 78.81; h, 4.14; b, 1.58; n, 6.13; s, 9.34. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 685.18 and the test value is 685.66.
Synthesis of compound E6, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 4' -bromo-4-chlorobiphenyl (12mmol), compound M5(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then Pd (PPh3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain an intermediate E6-1.
In a 250ml round-bottom flask, intermediate E6-1(12mmol), Compound M8(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E6.
Elemental analysis structure (molecular formula C50H33BN6) for compound E6: theoretical value: c, 82.42; h, 4.56; b, 1.48; n, 11.53. Test values are: c, 82.40; h, 4.58; b, 1.48; n, 11.53. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 728.29 and the test value is 728.65.
Synthesis of compound E7, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 9-bromo-10- (4-chlorophenyl) -anthracene (12mmol), compound M9(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then Pd (PPh3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain an intermediate E7-1.
In a 250ml round-bottom flask, intermediate E7-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E7.
Elemental analysis structure (molecular formula C45H26BNO2) for compound E7: theoretical value: c, 86.68; h, 4.20; b, 1.73; n, 2.25; and O, 5.13. Test values are: c, 86.66; h, 4.22; b, 1.73; n, 2.25; and O, 5.14. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 623.21 and the test value is 623.50.
Synthesis of compound E8, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 4' -bromo-3-chlorobiphenyl (12mmol), compound M3(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then Pd (PPh3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain an intermediate E8-1.
In a 250ml round-bottom flask, intermediate E8-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E8.
Elemental analysis structure (molecular formula C57H38BN5) for compound E8: theoretical value: c, 85.18; h, 4.77; b, 1.35; n, 8.71. Test values are: c, 85.16; h, 4.79; b, 1.35; n, 8.71. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 803.32 and the test value is 803.76.
Synthesis of compound E8, which has the structure:
the preparation method comprises the following specific steps:
in a 250ml round-bottom flask, 9-bromo-10- (3-chlorophenyl) -anthracene (12mmol), compound M6(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then Pd (PPh3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while extracting with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, and after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain an intermediate E9-1.
In a 250ml round-bottom flask, intermediate E9-1(12mmol), Compound M2(12mmol) and Na2CO3(80mmol) were added to toluene/EtOH (absolute ethanol)/H, respectively2O (75/25/50, mL) solvent to form a mixed solution, and then adding Pd (PPh)3)4(0.48mmol) was added to the above mixed solution, and the intermediate obtained by the reflux reaction under a nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, and then filtered through a celite pad while being extracted with dichloromethane, followed by washing with water, and drying with anhydrous magnesium sulfate, after filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain product E9.
Elemental analysis structure (molecular formula C52H31BN2O2) for compound E9: theoretical value: c, 85.95; h, 4.30; b, 1.49; n, 3.86; and O, 4.40. Test values are: c, 85.93; h, 4.32; b, 1.49; n, 3.86; o, 4.41. ESI-MS (M/z) (M +) by liquid mass spectrometry: the theoretical value is 726.25 and the test value is 726.63.
Simulated calculation of compound energy levels:
by using Density Functional Theory (DFT), the distribution of the molecular front linear orbitals HOMO and LUMO is optimized and calculated by the Guassian 09 package (Guassian Inc.) at the calculation level of B3LYP/6-31G (d) for the organic compounds provided by the embodiments of the present invention, and the lowest singlet energy level S1 and the lowest triplet energy level T1 of the compound molecules are calculated based on time-dependent density functional theory (TD-DFT) simulation, and the results are shown in the following table 1.
TABLE 1
As can be seen from Table 1, the compounds provided by the invention have deeper LUMO energy levels, can reduce the potential barrier of electron transmission, improve the injection capability of electrons, and effectively reduce the voltage of OLED devices; the compounds have deeper HOMO energy levels, which can effectively block holes, so that more holes-electrons are combined in a light emitting region, and higher light emitting efficiency can be realized.
The following are some examples of applications of the organic compounds of the present invention in OLED devices:
the present application example provides an OLED device, which has a structure as shown in fig. 1, and includes a substrate 1, an anode 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, and a cathode 9, which are sequentially stacked.
The specific preparation steps of the OLED device are as follows:
1) cutting a glass substrate with an Indium Tin Oxide (ITO) anode (thickness 15nm) into a size of 50mm × 50mm × 0.7mm, performing ultrasonic treatment in isopropanol and deionized water, respectively, for 30 minutes, and then exposing to ozone for about 10 minutes for cleaning, and mounting the cleaned glass substrate on a vacuum deposition apparatus;
2) on the ITO anode 2, a hole injection layer material compound b and a P-doping material compound a are evaporated together in a vacuum evaporation mode, and the doping proportion is 3 percent (mass ratio); a thickness of 5nm, this layer serving as a hole injection layer 3;
3) a hole transport material compound b is vacuum-evaporated on the hole injection layer 3 to a thickness of 100nm to form a first hole transport layer 4;
4) a hole transport material compound d is vacuum-evaporated on the first hole transport layer 4, and the thickness of the hole transport material compound d is 5nm to form a second hole transport layer 5;
5) a luminescent main body material compound e and a doping material compound f are evaporated on the second hole transport layer 5 in vacuum together, the doping proportion is 3 percent (mass ratio), the thickness is 30nm, and the luminescent main body material compound e and the doping material compound f are used as a luminescent layer 6;
6) a compound g is vacuum-evaporated on the light-emitting layer 6 to a thickness of 30nm as a hole blocking layer 7;
7) a compound E1 and an N-doping material compound h are evaporated on the hole blocking layer 7 in a vacuum co-evaporation mode, and the doping mass ratio is 1: 1; the thickness is 5nm, and the electron transport layer 8 is formed;
8) and (3) performing vacuum evaporation on the electron transport layer 8 to form a magnesium-silver electrode, wherein the mass ratio of Mg to Ag is 1:9, the thickness is 10nm, and the magnesium-silver electrode is used as a cathode 9.
Application example 2
This application example provides an OLED device, which differs from application example 1 only in that compound E1 in step 7) is replaced by compound E2, and the other preparation steps are the same.
Application example 3
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E3, and the other preparation steps were the same.
Application example 4
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E4, and the other preparation steps were the same.
Application example 5
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E5, and the other preparation steps were the same.
Application example 6
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E6, and the other preparation steps were the same.
Application example 7
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E7, and the other preparation steps were the same.
Application example 8
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E8, and the other preparation steps were the same.
Application example 9
This application example provides an OLED device, which differs from application example 1 only in that compound E1 was replaced with compound E9, and the other preparation steps were the same.
Comparative example 1
This comparative example provides an OLED device, differing from application example 1 only in that compound E1 was replaced by comparative compound 1 as follows:
comparative example 2
This comparative example provides an OLED device, differing from application example 1 only in that compound E1 was replaced with comparative compound 2 as follows:
comparative example 3
This comparative example provides an OLED device, differing from application example 1 only in that compound E1 was replaced with comparative compound 3 as follows:
performance evaluation of OLED devices:
obtaining a working voltage V and a current efficiency CE (cd/A) under a certain current density (10mA/cm2) according to the current density and the brightness of the OLED device under different voltages; lifetime LT95 (under 50mA/cm2 test conditions) was obtained by measuring the time when the luminance of the OLED device reached 95% of the initial luminance; the test data are shown in table 2.
TABLE 2
OLED device
Electron transport layer material
Vvop(V)
E/CIEy
Life LT95
Application example 1
Compound E1
3.80
150.8
110％
Application example 2
Compound E2
3.82
153.2
109％
Application example 3
Compound E3
3.78
151.3
112％
Application example 4
Compound E4
3.81
153.0
110％
Application example 5
Compound E5
3.80
152.8
107％
Application example 6
Compound E6
3.81
151.7
115％
Application example 7
Compound E7
3.82
150.9
116％
Applications ofExample 8
Compound E8
3.80
151.1
111％
Application example 9
Compound E9
3.83
150.5
118％
Comparative example 1
Comparative Compound 1
3.99
143.6
100％
Comparative example 2
Comparative Compound 2
4.08
141.6
98％
Comparative example 3
Comparative Compound 3
4.02
138.2
97％
As can be seen from table 2, application examples 1 to 6 have lower operating voltage, higher b.i. luminous efficiency, longer device life, compared to comparative example 1; the parameters are respectively improved by more than 5.0 percent, 6.0 percent and 7 percent. The compound has deeper LUMO energy level, and the difference of band gap between the compound and the LUMO energy level of the adjacent layer material is smaller, so that the compound is beneficial to the effective injection and transmission of electrons; at the same time, the increase of the device lifetime is also based on the fact that the compounds of the invention can be better complexed with N-dopants.
The applicant states that the present invention is illustrated by the above examples of the organic compounds of the present invention and their applications, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must rely on the above examples to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
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