CN112341458B - Electron transport material, organic electroluminescent device and display device - Google Patents
Electron transport material, organic electroluminescent device and display device Download PDFInfo
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- CN112341458B CN112341458B CN202011052841.9A CN202011052841A CN112341458B CN 112341458 B CN112341458 B CN 112341458B CN 202011052841 A CN202011052841 A CN 202011052841A CN 112341458 B CN112341458 B CN 112341458B
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- electron transport
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- PKZHIIVZRPUZSU-UHFFFAOYSA-N (4-bromo-2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1F PKZHIIVZRPUZSU-UHFFFAOYSA-N 0.000 description 1
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- HHVGZHHLRBNWAD-UHFFFAOYSA-N 4,6-diphenyltriazine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=NN=N1 HHVGZHHLRBNWAD-UHFFFAOYSA-N 0.000 description 1
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GOXNHPQCCUVWRO-UHFFFAOYSA-N dibenzothiophen-4-ylboronic acid Chemical compound C12=CC=CC=C2SC2=C1C=CC=C2B(O)O GOXNHPQCCUVWRO-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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Abstract
The invention discloses an electron transport material with a general formula I, which can be used as an electron transport layer of an organic electroluminescent device in a display device. The electron transport material has a parent structure of diversified fused heterocycles, high bond energy among atoms, good thermal stability, strong transition capability of electrons, and can be used as an electron transport layer material to effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device, and is beneficial to solid-state accumulation among molecules.
Description
Technical Field
The invention relates to the technical field of light-emitting display, in particular to an electron transport material, an organic electroluminescent device and a display device.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on 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 device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical properties, electrical properties, stability, etc. of the materials can be adjusted by changing the structure of the molecules, the choice of the materials has a large space, and in the most common OLED device structure, the following organic materials are generally included: a hole injection material, a hole transport material, an electron transport material, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. At present, as an important functional material, an electron transport material has a direct influence on the mobility of electrons, and ultimately influences the luminous efficiency of an OLED. However, the electron transport materials currently used in OLEDs have low electron transfer rates and poor energy level matching with adjacent layers, which severely limits the light emitting efficiency of OLEDs and the display function of OLED display devices.
Disclosure of Invention
The invention provides an electron transport material, an organic electroluminescent device and a display device, in order to improve the luminous efficiency and prolong the service life of the organic electroluminescent device.
The electron transport material has a structure shown as a formula I:
in formula I, A, B and C are three segments selected from the group consisting of the structures of formula II or III:
wherein,
when A is selected from II, at least one of B or C is selected from III, when A is selected from III, at least one of B or C is selected from II, when A is not II or III, A is selected from hydrogen, C unsubstituted or substituted by Ra 6 -C 30 Aryl, C unsubstituted or substituted by Ra 3 -C 30 Heteroaryl, B and C are independently selected from II or III, A, B and C may be the same or different;
X 1 -X 4 selected from N or CR, at least one of which is N, R is selected from hydrogen and C 1 -C 10 Alkyl radical, C 1 -C 6 Cycloalkyl, C unsubstituted or substituted by Ra 6 -C 30 Aryl, C unsubstituted or substituted by Ra 3 -C 30 Heteroaryl, and adjacent R can be connected to form a ring;
Y 1 -Y 8 selected from N or CR ', R' is selected from hydrogen, deuterium, C 1 -C 10 Alkyl radical, C 1 -C 6 Cycloalkyl, C unsubstituted or substituted by Ra 6 -C 30 Aryl, C unsubstituted or substituted by Ra 3 -C 30 A heteroaryl group;
z is O, S or CR 1 R 2 ，R 1 、R 2 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 6 Cycloalkyl, C unsubstituted or substituted by Ra 6 -C 30 Aryl, C unsubstituted or substituted by Ra 3 -C 30 Heteroaryl, and R 1 And R 2 Can be connected into a ring;
the substituents Ra of the individual radicals may be identical or different and are each, independently of one another, selected from hydrogen, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably, R is selected from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, or carbazolyl; r' is selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, or carbazolyl; r1 and R2 are independently from each other selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, or carbazolyl; a is selected from the following unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, or carbazolyl.
The invention also discloses a specific structure of the electron transport material shown in the formulas A1-A25:
the electron transport material has a parent structure of diversified fused heterocycles, high bond energy among atoms, good thermal stability, strong transition capability of electrons, and can be used as an electron transport layer material to effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device; the electron transport material is applied in an electron transport layer, has a proper energy level with the adjacent layers, is beneficial to the injection and the migration of electrons, can effectively reduce the take-off and landing voltage, has higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device; the electron transport material has a larger conjugate plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.
The present invention also provides an organic electroluminescent device comprising at least an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode electrode, wherein the electron transport layer is at least one selected from the above-mentioned compounds, and in the present invention, there is no particular limitation in the kind and structure of the organic electroluminescent device as long as the electron transport material provided by the present invention can be used. The organic electroluminescent device of the present invention may be a light-emitting device having a top emission structure, and examples thereof include a light-emitting device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode in this order on a substrate. The organic electroluminescent device of the present invention may also be a light-emitting device of a bottom emission structure, an example of the structure includes a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode in this order on a substrate. The organic electroluminescent element of the present invention may be a light-emitting element having a double-sided light-emitting structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode are sequentially provided on a substrate.
Drawings
Fig. 1 is a schematic structural diagram of a typical organic electroluminescent device of the organic electroluminescent device according to the present invention, which is shown from bottom to top: a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not intended to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present invention are within the scope of the present invention.
In the present invention, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, such as glass, polymer materials, glass with TFT elements, polymer materials, and the like, may be used.
In the present invention, the reflective anode electrode 2 is not particularly limited and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art 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 (poly 3,4-ethylenedioxythiophene), multilayer structures of the above materials, and the like can be used.
In the present invention, the hole injection layer 3 and the hole transport layer 4 are not particularly limited, and at least one of Hole Transport Materials (HTM) well known in the art may be selected, for example, the material for the hole injection layer host and the material for the hole transport layer may be selected from at least one of the following HT-1 to HT-32 compounds:
in the present invention, the light emitting material in the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art may be used, for example, the light emitting material may include a host material and a light emitting dye. The host material may be selected from at least one of the following GPH-1 to GPH-80 compounds:
the light-emitting layer 5 preferably contains a phosphorescent dopant, and the dopant may be at least one selected from the following compounds RPD-1 to RPD-28, and the amount of the dopant is not particularly limited and may be an amount known to those skilled in the art.
In the present invention, the electron transport layer 6 comprises at least one of the electron transport materials of the present invention, and the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of the present invention with at least one of the following known electron transport materials ET-1 to ET-57:
the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of BaO, na, li, ca and the like.
The cathode electrode 8 is not particularly limited and may be selected from, but not limited to, a magnesium silver mixture, liF/Al, ITO, al, and other metals, metal mixtures, oxides, and the like.
The method of preparing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art may be employed, for example:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) A hole injection layer 3 is vacuum evaporated on the reflecting anode electrode 2, the main material of the hole injection layer is HTM, and the hole injection layer contains P-type dopant (P-dopant) and has the thickness of 10-50nm;
(3) Vacuum evaporating a Hole Transport Material (HTM) as a hole transport layer 4 on the hole injection layer 3, wherein the thickness of the hole transport layer 4 is 80-150nm;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer contains a host material (GPH) and a guest material (RPD) and has a thickness of 20-50nm;
(5) Vacuum evaporation of an Electron Transport Material (ETM) as an electron transport layer 6 on the light emitting layer 5;
(6) Vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;
(7) A cathode material was vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The third aspect of the present invention provides a display device comprising the above organic electroluminescent device, and the display device of the present invention includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, and the like.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
1. Synthesis of electron transport materials
Example 1, synthesis of A1
Into a reaction flask were charged 100mmol of 2-bromo-4-chlorofluorobenzene, 100mmol of 2-boronic acid benzaldehyde, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (A) is 1mol% of 2-bromo-4-chlorofluorobenzene;
adding M1 (100mmol, 1.0eq), 4-bromo-1,2-diphenylamine (100mmol, 1.0eq) and 500ml of toluene into a single-port bottle, adding p-toluenesulfonic acid (10 mmol), heating to 100 ℃, reacting for 6 hours, monitoring by TLC (thin layer chromatography) for disappearance of raw materials, adding water into a reaction solution, filtering, leaching a filter cake by using water and ethanol, and washing until the filtrate is colorless clear liquid to obtain a brown solid M2;
adding M2 (100mmol, 1eq), 41.4g of potassium carbonate (300 mmol) and 800ml of DMF into a single-mouth bottle, heating to 120 ℃, reacting for 6h, monitoring the disappearance of raw materials by TLC, adding water into reaction liquid, filtering, leaching a filter cake by using water and ethanol, and washing until filtrate is colorless clear liquid to obtain brown solid M3;
100mmol of M3, 105mmol of 2- (3-phenylboronate) 4,6-diphenyltriazine, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) are introduced into a reaction flask 3 ) 4 At 120 ℃ to reactCooling the reaction product to room temperature after the reaction is finished, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The addition amount of (b) is 1mol% of M3;
into a reaction flask were charged 100mmol of M4, 105mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A1, wherein Pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M4.
The hydrogen spectrum of A1 is characterized as follows:
1 H NMR(400MHz,Chloroform)δ8.87(s,1H),8.39(dd,J＝12.4,8.0Hz, 4H),8.30(d,J＝9.6Hz,3H),8.19(s,1H),8.14–7.76(m,6H),7.75(s,1H),7.69(d,J＝8.0Hz,4H),7.62(dd,J＝10.0,6.4Hz,2H),7.52(d,J＝10.0Hz,3H), 7.48–7.43(m,5H),7.31(s,1H).
M/Z: experimental 740.9, theoretical 741.2.
The reaction scheme is as follows:
example 2, synthesis of A4
Into a reaction flask were charged 100mmol of 2-bromo-4-chlorofluorobenzene, 100mmol of 2-boronic acid benzaldehyde, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (A) is 1mol% of 2-bromo-4-chlorofluorobenzene;
adding M1 (100mmol, 1.0eq), 4-bromo-1,2-diphenylamine (100mmol, 1.0eq) and 500ml of toluene into a single-port bottle, adding p-toluenesulfonic acid (10 mmol), heating to 100 ℃, reacting for 6 hours, monitoring by TLC (thin layer chromatography) for disappearance of raw materials, adding water into a reaction solution, filtering, leaching a filter cake by using water and ethanol, and washing until the filtrate is colorless clear liquid to obtain a brown solid M2;
adding M2 (100mmol, 1eq), 41.4g of potassium carbonate (300 mmol) and 800ml of DMF into a single-mouth bottle, heating to 120 ℃, reacting for 6h, monitoring the disappearance of raw materials by TLC, adding water into reaction liquid, filtering, leaching a filter cake by using water and ethanol, and washing until filtrate is colorless clear liquid to obtain a brown solid M3;
100mmol of M3, 105mmol of 2-phenyl- (3-phenylboronate) -quinoxaline, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) are introduced into a reaction vessel 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The addition amount of (b) is 1mol% of M3;
100mmol of M4, 105mmol of 2-boronic acid-9,9-dimethylfluorene, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) were added to a reaction flask 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A4, wherein Pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M4.
The hydrogen spectrum of A4 is characterized as follows:
1 H NMR(400MHz,Chloroform)δ8.97(s,1H),8.59–8.40(m,3H),8.26 (s,1H),8.20(d,J＝8.4Hz,1H),8.08(d,J＝10.0Hz,4H),8.05–7.82(m,8H),7.90(s,1H),7.79(d,J＝10.0Hz,2H),7.72(d,J＝12.0Hz,4H),7.61(dt,J＝ 10.0,7.6Hz,2H),7.33(d,J＝8.4Hz,3H)1.69(s,6H).
M/Z: experimental 806.7, theoretical 807.3.
The reaction scheme is as follows:
synthesis of examples 3, A7
100mmol of 2-bromo-4-chlorobenzaldehyde, 100mmol of 2-fluorobenzeneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) are charged in a reaction flask 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The adding amount of the (D) is 1mol percent of that of the 2-bromo-4-chlorofluorobenzene;
adding M1 (100mmol, 1.0eq), 3-bromo-1,2-diphenylamine (100mmol, 1.0eq) and 500ml of toluene into a single-port bottle, adding p-toluenesulfonic acid (10 mmol), heating to 100 ℃, reacting for 6 hours, monitoring by TLC (thin layer chromatography) for disappearance of raw materials, adding water into a reaction solution, filtering, leaching a filter cake by using water and ethanol, and washing until the filtrate is colorless clear liquid to obtain a brown solid M2;
adding M2 (100mmol, 1eq), 41.4g of potassium carbonate (300 mmol) and 800ml of DMF into a single-mouth bottle, heating to 120 ℃, reacting for 6h, monitoring the disappearance of raw materials by TLC, adding water into reaction liquid, filtering, leaching a filter cake by using water and ethanol, and washing until filtrate is colorless clear liquid to obtain brown solid M3;
100mmol of M3, 105mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) are introduced into a reaction vessel 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The addition amount of (b) is 1mol% of M3;
a reaction flask was charged with 100mmol of M4, 105mmol of 4-dibenzothiopheneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A7, wherein Pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M4.
The hydrogen spectrum characterization of A7 resulted in:
1 H NMR(400MHz,Chloroform)δ9.24(s,1H),8.71(d,J＝10.0Hz,2H), 8.66(s,1H),8.59(d,J＝8.0Hz,2H),8.45(s,1H),8.32(d,J＝8.0Hz,2H),8.19-7.86(m,3H),7.82(s,1H),7.55(dd,J＝12.0,8.0Hz,4H),7.47-7.31(m, 4H).
M/Z: experimental 527.1, theoretical 527.1.
The reaction scheme is as follows:
example 4, synthesis of A15
100mmol of 2-iodo-5-chlorobenzaldehyde, 100mmol of 2-fluoro-4-bromo-phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) were added to a reaction flask 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M1, wherein Pd (PPh) 3 ) 4 The addition amount of (A) is 1mol% of 2-bromo-4-chlorofluorobenzene;
adding M1 (100mmol, 1.0eq), 1,2-diphenylamine (100mmol, 1.0eq) and 500ml of toluene into a single-opening bottle, adding p-toluenesulfonic acid (10 mmol), heating to 100 ℃, reacting for 6h, monitoring the disappearance of raw materials by TLC, adding water into a reaction liquid, filtering, leaching a filter cake with water and ethanol, and washing until a filtrate is a colorless clear liquid to obtain a brown solid M2;
adding M2 (100mmol, 1eq), 41.4g of potassium carbonate (300 mmol) and 800ml of DMF into a single-mouth bottle, heating to 120 ℃, reacting for 6h, monitoring the disappearance of raw materials by TLC, adding water into reaction liquid, filtering, leaching a filter cake by using water and ethanol, and washing until filtrate is colorless clear liquid to obtain a brown solid M3;
into a reaction flask were charged 100mmol of M3, 105mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder M4, wherein Pd (PPh) 3 ) 4 The addition amount of (b) is 1mol% of M3;
100mmol of M4, 105mmol of 2-phenyl-1- (4-phenylboronic acid) -1H-benzimidazole, 41.4g of potassium carbonate (300 mmol), 800ml of DMF, 200ml of water and Pd (PPh) are introduced into a reaction flask 3 ) 4 Reacting at 120 deg.C for 12h, cooling the reaction product to room temperature, adding water, filtering, washing with water, recrystallizing the obtained solid with toluene, and purifying to obtain white powder A15, wherein Pd (PPh) 3 ) 4 Is added in an amount of 1mol% based on M4.
The hydrogen spectrum of a15 is characterized as follows:
1 H NMR(400MHz,Chloroform)δ8.89(s,1H),8.66(s,1H),8.47(d,J＝ 10.0Hz,3H),8.29(d,J＝10.4Hz,3H),8.25–7.78(m,3H),7.81(d,J＝8.0Hz,2H),7.81(d,J＝8.0Hz,2H),7.74(t,J＝10.0Hz,4H),7.63(d,J＝8.0Hz,2H), 7.57–7.48(m,6H),7.39(s,1H),7.30(d,J＝12.0Hz,2H).
M/Z: experimental 701.8, theoretical 702.2.
The reaction scheme is as follows:
2. preparation of organic electroluminescent device
Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-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 solar beams;
placing the glass substrate with anode in a vacuum chamber, and vacuumizing to less than 10% -5 And (3) depositing HT-4 and a p-type dopant (p-dopant) in a mass ratio of 3% by vacuum on the anode layer film at a deposition rate of 0.1nm/s as a hole injection layer, wherein the deposition film has a thickness of 10nm, and the material of the hole injection layer and the p-type dopant are:
vacuum evaporating an HT-5 material on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness is 80nm;
a light-emitting layer of the device is vacuum evaporated on the hole transport layer, the light-emitting layer comprises a main material GHP-16 and a dye material RPD-1, evaporation is carried out by using a multi-source co-evaporation method, the evaporation rate of the main material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the main material, and the total thickness of the evaporation film is 30nm;
vacuum evaporation is carried out on the electron transport materials obtained in examples 1-4 on the luminescent layer to form an electron transport layer, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
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 aluminum layer with the thickness of 150nm is used as a cathode of the device.
Comparative example 1
The electron transport material obtained in any of examples 1 to 4 in the above organic electroluminescent device was replaced with ET-21, and the remainder was unchanged.
The organic electroluminescent devices of examples 1 to 4 and comparative example 1 were subjected to the following performance measurements:
measuring the driving voltage and current efficiency of the organic electroluminescent device and the lifetime of the device at the same brightness by using a digital source meter and a luminance meter, specifically, increasing the voltage at a rate of 0.1V per second, and measuring that the brightness of the organic electroluminescent device reaches 5000cd/m 2 The 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; life test of LT95 is as follows: using a luminance meter at 5000cd/m 2 The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance 2 Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Properties
| Required luminance (cd/m) 2 ) | Driving voltage/V | Current efficiency (cd/A) | Lifetime (LT 95)/h | |
| Example 1 | 5000.00 | 4.2 | 39.3 | 196 |
| Example 2 | 5000.00 | 4.1 | 40.8 | 204 |
| Example 3 | 5000.00 | 4.1 | 38.7 | 210 |
| Example 4 | 5000.00 | 4.0 | 39.6 | 190 |
| Comparative example 1 | 5000.00 | 4.4 | 36.8 | 165 |
As can be seen from Table 1, the compounds A1, A4, A7 and A15 prepared by the method are used for the electron transport material of the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency and prolong the service life of the device, and are electron transport materials with good performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. An electron transport material having a structure represented by formulas A1, A4, A7 and a 15:
2. an organic electroluminescent device comprising an anode electrode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode electrode, wherein the electron transport layer comprises at least one of the electron transport materials of claim 1.
3. The organic electroluminescent device of claim 2, wherein the electron transport layer further comprises at least one transport material of the formula ET-1 to ET-57, wherein the structures of the formulae ET-1 to ET-57 are as follows,
4. a display device comprising the organic electroluminescent element according to claim 2 or 3.
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