CN111138393A - Arylamine compound and organic electroluminescent device using the same - Google Patents

Arylamine compound and organic electroluminescent device using the same Download PDF

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CN111138393A
CN111138393A CN201811430521.5A CN201811430521A CN111138393A CN 111138393 A CN111138393 A CN 111138393A CN 201811430521 A CN201811430521 A CN 201811430521A CN 111138393 A CN111138393 A CN 111138393A
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林晋声
谢雨佑
陈唯圣
温涵芳
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E Ray Optoelectronics Technology Co Ltd
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Abstract

The invention provides an arylamine compound and an organic electroluminescent device thereof, wherein the arylamine compound is represented by the following formula (I):
Figure DDA0001882590550000011
wherein X is O, S, or C (R)1)(R2)；R1And R2Each independently is a hydrogen atom, an alkyl or aryl group, or R1And R2A ring formed together; n1, n2 and n3 are all integers; l is1、L2And L3Each independently is an arylene or heteroarylene group; a is aryl, heteroaryl, or-N (Ar)3)(Ar4) A group; and Ar1To Ar4Each independently is an aryl or heteroaryl group.

Description

Arylamine compound and organic electroluminescent device using the same
Technical Field
The present invention relates to an arylamine compound and an organic electroluminescent device using the same, and more particularly, to an arylamine compound as a material for a hole transport layer or a capping layer and an organic electroluminescent device using the same.
Background
With the progress of technology, Organic Light Emitting Devices (OLEDs) are receiving attention due to their advantages of high response rate, light weight, thinness, wide viewing angle, bright color, high contrast, no need of backlight, low energy consumption, and the like, but OLEDs still have the problems of low efficiency and short lifetime.
In order to improve efficiency and stability of the OLED, a plurality of organic thin films are generally connected in series between a cathode and an anode of the OLED, for example, the OLED may be sequentially provided with a substrate, an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Emission Layer (EL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode. When a voltage is applied to the anode and the cathode, holes conducted from the anode are transmitted to the light-emitting layer through the hole injection layer and the hole transport layer, electrons emitted from the cathode are transmitted to the light-emitting layer through the electron injection layer and the electron transport layer, and the holes and the electrons are recombined in the light-emitting layer to form electron-hole pairs, namely excitons, light is emitted when the excitons decline from an excited state to a ground state.
The hole transport layer is formed by vacuum deposition, so that the stability of the hole transport layer is not sufficient, the hole transport layer may be partially crystallized due to heat generated during driving of the device, the hole transport material may be deteriorated, and the current efficiency and the light emitting efficiency of the OLED may be reduced. In order to improve the performance of OLEDs, several novel compounds have been developed as hole transport materials.
As disclosed in U.S. patent publication No. 2007/0262703, a2, 2 '-disubstituted 9,9' -spirobifluorenyltriaryldiamine is proposed as a hole transporting material for a hole transporting layer. However, even though the aforementioned hole transport material is used, the current efficiency and the light emitting efficiency of the OLED still remain to be improved.
In addition, as in international patent publication No. 2017196081, a fused heterocyclic compound having an amino group and linking two benzene rings is proposed as a hole transport material for a hole transport layer. However, even with the use of the aforementioned hole transport materials, the lifetime of OLEDs is still not satisfactory. Accordingly, the present invention provides a novel arylamine compound in order to overcome the problems of the prior art.
Disclosure of Invention
The object of the present invention is to provide a novel arylamine compound which can be used for an organic electroluminescent device.
The present invention also provides an organic electroluminescent device using the arylamine compound, thereby having a lower driving voltage.
The present invention also provides an organic electroluminescent device using the arylamine compound, thereby having good luminous efficiency.
The invention also provides an organic electroluminescent device using the arylamine compound, thereby prolonging the service life of the organic electroluminescent device.
To achieve the above object, the arylamine compound of the present invention may be represented by the following formula (I):
Figure BDA0001882590530000021
in the formula (I), X is O, S or C (R)1)(R2)；R1And R2Each independently is hydrogen, C1-12 alkyl, or C6-30 aryl, or R1And R2Together form a ring having 6 to 15 carbon atoms;
n1, n2 and n3 are each independently an integer of 0 to 2, and n1, n2 and n3 are the same as or different from each other;
L1、L2and L3Each independently an arylene group having 6 to 30 carbon atoms in the ring or a heteroarylene group having 3 to 30 carbon atoms in the ring, and L1、L2And L3Are the same or different from each other;
a is an aryl group having 6 to 30 carbon atoms in the ring, a heteroaryl group having 3 to 30 carbon atoms in the ring, or-N (Ar)3)(Ar4) A group; and
Ar1to Ar4Each independently is an aryl group having 6 to 30 carbon atoms in the ring or a heteroaryl group having 3 to 30 carbon atoms in the ring, Ar1、Ar2、Ar3And Ar4The same or different from each other.
Preferably, in formula (I), X is O, S, or C (CH)3)2。
When n1 is the integer 2,2 consecutive L1Each independently is an arylene group having 6 to 30 carbon atoms in the ring or a heteroarylene group having 3 to 30 carbon atoms in the ring, 2L1May be the same or different from each other; for example 1L1Is arylene with 6 to 30 carbon atoms on the ring, and another 1L1An arylene group having an upper carbon number of 3 to 30; similarly, 2 consecutive L2Identical or different from each other, 2 linked L3May be the same or different from each other.
Specifically, when n1, n2 or n3 is 1 or 2, L1、L2And L3The arylene group having 6 to 30 carbon atoms in the ring represented by (a) may be any one of the following groups:
Figure BDA0001882590530000031
wherein m is1Is an integer of 1 to 4, m2Is an integer of 1 to 2, m3Is an integer from 1 to 3; and
R3to R6Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12;
when m is1、m2Or m3When it is an integer of more than 1, each R3May be the same or different from each other, each R4May be the same or different from each other, each R5May be the same or different from each other, each R6May be the same or different from each other.
Specifically, when n1, n2 or n3 is 1 or 2, L1、L2And L3The heteroarylene group having 3 to 30 carbon atoms in the ring represented by (a) may be any one of:
Figure BDA0001882590530000032
wherein m is1Is an integer of 1 to 4, m3Is an integer from 1 to 3; and
R3and R4Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12;
when m is1Or m3When it is an integer of more than 1, each R3May be the same or different from each other, each R4May be the same or different from each other.
Preferably, in formula (I), n1 and n2 are each independently 0 or 1.
Specifically, A, Ar1To Ar4Any one of the aryl groups having 6 to 30 carbon atoms in the ring is selected from the group consisting of: phenyl, biphenyl, terphenyl, naphthyl, fluorenyl), 9-dimethylfluorenyl, 9' -spirobifluorenyl, naphthylphenyl, and isomers thereof.
Specifically, A, Ar1To Ar4The heteroaryl group having 3 to 30 carbon atoms in the ring represented by any one of the above groups is selected from the group consisting of: furyl, pyrrolyl, thienyl, imidazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, benzofuryl, isobenzofuran, dibenzofuran, benzothienyl, isobenzothiophene, dibenzothiophene, quinolinyl, isoquinoline, benzimidazole, carbazole, dicarbazolyl, and acridinyl.
Preferably A, Ar1To Ar4Any one of the aryl groups having 6 to 30 carbon atoms in the ring is selected from the group consisting of:
Figure BDA0001882590530000041
wherein m is1Is an integer of 1 to 4, m3Is an integer of 1 to 3, m4Is an integer from 1 to 5; and
R3to R6Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12;
when m is1、m3Or m3When it is an integer of more than 1, each R3May be the same or different from each other, each R4May be the same or different from each other, each R5May be the same or different from each other, each R6May be the same or different from each other.
Preferably A, Ar1To Ar4Any one of the heteroaryl groups having 3 to 30 carbon atoms in the ring is selected from the group consisting of:
Figure BDA0001882590530000042
wherein m is1Is an integer of 1 to 4, m3Is an integer from 1 to 3; and
R3and R4Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12;
when m is1Or m3When it is an integer of more than 1, each R3May be the same or different from each other, each R4May be the same or different from each other.
In some embodiments of the invention, n1 and n2 are the same integer, L1And L2Are selected the same, and Ar1And Ar2The same applies to the selection of (1). For example,n1 and n2 are both 1, L1And L2Are phenylene, biphenylene, or 9, 9-dimethylfluorenylene, but are not limited thereto.
In some embodiments of the invention, when n3 is the integer 1, L3Is an arylene group having 6 to 30 carbon atoms in the ring, and A is-N (Ar)3)(Ar4) When radical, the amine polycyclic moiety (i.e.
Figure BDA0001882590530000043
Is and L3In the position of contact) with A at L3The upper positions are not in meta-position. For example, when L is3When it is phenylene, the group-N (Ar)3)(Ar4) The group and the amino polycyclic moiety can be in para-position and have the structure
Figure BDA0001882590530000051
When L is3When it is naphthylene, the group-N (Ar)3)(Ar4) The group is not meta to the amino polycyclic moiety and may have the structure
Figure BDA0001882590530000052
Figure BDA0001882590530000053
Figure BDA0001882590530000054
But is not limited thereto.
In the specification, X is C (R)1)(R2) So called "R1And R2A ring having 6 to 15 carbon atoms in the ring, which may be an unsubstituted ring having 6 to 15 carbon atoms in the ring, or a ring having 6 to 15 carbon atoms in the ring and substituted with at least one substituent; the substituent on the ring may be the aforementioned R3To R6Any of them.
In the specification, L1、L2Or L3The "arylene group having 6 to 30 carbon atoms in the ring" may be an unsubstituted arylene group having 6 to 30 carbon atoms in the ring or an arylene group having 6 to 30 carbon atoms in the ring and substituted with at least one substituent(ii) a The substituent on the arylene group may be the aforementioned R3To R6Any of the above; likewise, L1、L2Or L3The term "heteroarylene group having 3 to 30 carbon atoms in the ring" may be an unsubstituted heteroarylene group having 3 to 30 carbon atoms in the ring, or a heteroarylene group having 3 to 30 carbon atoms in the ring and substituted with at least one substituent; the substituent on the heteroarylene group may be the aforementioned R3To R6Any of them.
In the specification, the "aryl" may be an unsubstituted aryl or an aryl substituted with at least one substituent; the "heteroaryl" may be unsubstituted heteroaryl or heteroaryl substituted with at least one substituent. The substituent on the aromatic group may be the aforementioned R3To R6Any of the above; the substituents on the heteroaryl group may be as defined above for R3To R6Any of them.
In the specification, the "alkyl group" may be an unsubstituted alkyl group or an alkyl group substituted with at least one substituent; the substituents on the alkyl group may be, but are not limited to, deuterium atoms; the alkyl group may be linear or have a branched structure.
For example, the arylamine compound may be selected from the group consisting of:
Figure BDA0001882590530000061
Figure BDA0001882590530000071
Figure BDA0001882590530000081
Figure BDA0001882590530000091
the present invention further provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the arylamine compound.
Specifically, the organic electroluminescent device comprises a hole auxiliary layer formed on the anode, a light-emitting layer formed on the hole auxiliary layer, an electron transport layer formed on the light-emitting layer, and an electron injection layer between the electron transport layer and the cathode; the hole assist layer includes the organic layer.
In some embodiments, the hole assist layer may be a single layer structure or a multi-layer structure disposed between the anode and the light emitting layer; for example, when the hole assist layer has a multi-layer structure, the hole assist layer includes a hole injection layer and a hole transport layer; wherein the hole injection layer is formed on the anode, and the hole transport layer is formed between the hole injection layer and the light emitting layer; the arylamine compound of the present invention is used as a hole transport material in a hole transport layer.
In some embodiments, the hole injection layer may be a single layer structure or a multi-layer structure disposed between the anode and the hole transport layer; when the hole injection layer is a multi-layer structure, for example, the hole injection layer includes a first hole injection layer and a second hole injection layer.
Specifically, the hole injection layer may include an HTM, a p-type dopant, and the like, but is not limited thereto.
In some embodiments, the hole transport layer may be a single layer structure or a multi-layer structure disposed between a two-layer hole injection layer and a light emitting layer; when the hole transporting layer has a multi-layer structure, for example, the hole transporting layer includes a first hole transporting layer and a second hole transporting layer, the hole transporting material in the first hole transporting layer may include the aforementioned arylamine compound of the present invention or a conventional hole transporting material, and the hole transporting material in the second hole transporting layer may include another arylamine compound of the present invention.
Preferably, the luminescent layer is made of guest luminophor and host luminophor materials. The host material may be BH, EPH, etc., but is not limited thereto.
For the blue light emitting OLED, the guest light emitter in the light emitting layer material can be BD, etc., but is not limited thereto.
For the green light emitting organic electroluminescent device, the guest light emitter in the light emitting layer material can be GD, etc., but is not limited thereto.
For the red-emitting organic electroluminescent device, the guest light-emitting body in the light-emitting layer material may be RD, etc., but is not limited thereto.
Preferably, the electron transport layer may include ET, lithium 8-hydroxyquinoline, and the like, but is not limited thereto.
Preferably, the electron injection layer may include lithium fluoride (LiF), etc., but is not limited thereto.
Preferably, the anode may be an indium tin oxide electrode, but is not limited thereto.
Preferably, the cathode may be an aluminum electrode.
The present invention also provides an organic electroluminescent device, which comprises an anode, a cathode and a cover layer disposed on the cathode, wherein the cathode is disposed between the anode and the cover layer, and the cover layer comprises the arylamine compound.
Because the arylamine compound has a higher refractive index, when the arylamine compound is used as a material of the covering layer, the arylamine compound can increase the reflection of the frame surface between the covering layer and the outside. By increasing the reflection, the cover layer can collect light to enhance the brightness of the top-emitting OLED or generate the micro-cavity effect at a specific wavelength.
Other objects, effects and technical features of the present invention will be described in more detail with reference to the drawings, examples and comparative examples.
Drawings
FIG. 1 is a side sectional view of an organic electroluminescent device.
FIGS. 2 and 3 are the hydrogen nuclear magnetic resonance spectra (H) of Compound 31-NMR)。
FIGS. 4 and 5 are H for Compound 51-NMR。
FIGS. 6 and 7 are H for Compound 61-NMR。
FIGS. 8 and 9 are H of Compound 91-NMR。
FIGS. 10 and 11 are H for Compound 131-NMR。
FIGS. 12 and 13 are H for Compound 181-NMR。
Detailed Description
Several examples are listed below as examples to illustrate embodiments of the compounds of the present invention and their organic electronic devices, to highlight the differences of the present invention compared to the prior art; those skilled in the art can readily appreciate from the disclosure of the present invention that the advantages and utilities of the present invention may be realized and attained without departing from the spirit and scope of the present invention as defined by the appended claims.
Synthesis of intermediate An
The intermediate An is used for preparing An arylamine compound, and can be synthesized by the following steps.
Figure BDA0001882590530000111
Synthesis mechanism A1
Wherein X is O, S or C (R)1)(R2)；R1And R2Each independently is a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 30 carbon atoms in the ring, or R1And R2Together form a ring having 6 to 15 carbon atoms; n1 and n2 are each independently an integer of 0 to 2, and n1 and n2 are the same as or different from each other; l is1And L2Each independently an arylene group having 6 to 30 carbon atoms in the ring or a heteroarylene group having 3 to 30 carbon atoms in the ring, and L1And L2Are the same or different from each other; and Ar1And Ar2Each independently is an aryl group having 6 to 30 carbon atoms in the ring or a heteroaryl group having 3 to 30 carbon atoms in the ring.
Synthesis of intermediate A1
Intermediate A1 was synthesized by the following synthetic mechanism A1-1.
Figure BDA0001882590530000121
Synthesis scheme A1-1
Step 1: synthesis of intermediate A1-1
4-Bromobenzofuran (10g (g), 40.47 mmol (mmole)), bis (4-biphenylyl) amine (12.36g, 38.45mmole) and sodium tert-butoxide (11.67g, 121.41mmole) were placed in a 500mL (mL) reaction flask, followed by 100mL of toluene. Next, tris (dibenzylideneacetone) dipalladium (Pd (dba) was added to a 50mL scintillation vial2) (1.16g, 2.02mmole) and 20mL of toluene, and then tri-tert-butylphosphine (P (t-Bu)3) (0.98g, 4.86mmole) to form a first mixed solution, heating the scintillation vial to change the color of the first mixed solution from dark red to dark green; finally, slowly adding the first mixed solution into the reaction bottle, and heating to 110 ℃ for reacting for 18 hours to form a second mixed solution. Cooling the second mixed solution to room temperature after confirming the reaction completion by TLC plate, adding 300mL deionized water, stirring for 30 min, standing for layering, extracting with 200mL ethyl acetate each time, repeating the extraction three times, adding magnesium sulfate (MgSO)4) Carrying out dewatering, filtering separation, concentration and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (10: 1 by volume) to give 14.8g of the product (i.e., intermediate A1-1) in 75% yield.
Step 2: synthesis of intermediate A1
Intermediate A1-1(10g, 20.51mmole) was mixed with 200mL of dichloromethane in a 500mL reaction flask to form a third mixed solution, which was then transferred to an ice bath at 0 ℃ and an addition funnel was added to the flask. N-bromosuccinimide (4.02g, 22.56mmole) was then dissolved in 40mL of acetonitrile, and then added dropwise from an addition funnel at a rate of 2 drops/sec into the reaction flask, and the reaction was continued at 0 ℃ for 1 hour. After confirming the completion of the reaction by TLC plate, 200mL of saturated aqueous sodium bicarbonate solution was added, the mixture was stirred for 30 minutes and then allowed to stand to separate into layers, each with 200mL of dichloromethane, and extraction was repeated three times, and magnesium sulfate (MgSO) was added to the organic layer collected by three-time extraction4) Removing water, filtering, separating and concentratingCondensing and drying to obtain a crude product; the crude product was purified by column chromatography using a wash solution mixed with n-hexane and ethyl acetate (20: 1 by volume) to give 9.3g of the product (i.e. intermediate a1) in 80% yield.
Synthesis of intermediate A2
Intermediate a2 can be synthesized by a synthetic mechanism similar to intermediate a1, a1-1, the main difference being the difference in reactant An. Intermediate A2 was synthesized by the following synthetic mechanism A1-2.
Figure BDA0001882590530000131
Synthesis scheme A1-2
In step 1, the difference was that in which 12.36g of bis (4-biphenylyl) amine was substituted with 15.44 g (38.45mmole) of bis (9, 9-dimethylfluorene) amine, 17g of intermediate A2-1 was obtained, with a yield of intermediate A2-1 of 74%.
Step 2: synthesis of intermediate A2
Intermediate A2-1(10g, 17.61mmole) was mixed with 176mL of methylene chloride in a 500mL reaction flask to form a mixed solution, the mixed solution was transferred to an ice bath at 0 deg.C, and an addition funnel was added to the reaction flask. NBS (3.45g, 19.38mmole) was then dissolved in 35mL acetonitrile and added dropwise from the addition funnel at a rate of 2 drops/sec to the flask and the reaction was continued at 0 ℃ for 1 hour. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 176mL of saturated sodium bicarbonate aqueous solution, stirring for 30 minutes, standing for layering, extracting with 200mL of dichloromethane each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a wash solution mixed with n-hexane and ethyl acetate (20: 1 by volume) to give 8.7g of product (i.e. intermediate a2) in 76% yield.
Synthesis of intermediate A3
Intermediate A3 can be synthesized by a synthetic mechanism similar to intermediate a1, a1-1, the main difference being the difference in the reactant Sn. Intermediate A3 was synthesized by the following synthetic mechanism A1-3.
Figure BDA0001882590530000132
Synthesis mechanism A1-3
Step 1: synthesis of intermediate A3-1
4-bromodibenzothiophene (10g, 38.0mmole), bis (4-biphenylyl) amine (11.6g, 36.10mmole) and sodium tert-butoxide (10.96g, 114mmole) were placed in a 500mL reaction flask, followed by 120mL of toluene. Next, a 50mL scintillation vial was charged with Pd (dba)2(1.09g, 1.90mmole) and 20mL of toluene, and then P (t-Bu) was added3(0.92g, 4.56mmole) to form a first mixed solution, heating the scintillation vial to change the color of the first mixed solution from dark red to dark green; finally, slowly adding the first mixed solution into the reaction bottle, and heating to 110 ℃ for reacting for 16 hours to form a second mixed solution. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, cooling the second mixed solution to room temperature, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of toluene each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (10: 1 by volume) to give 14.3g of the product (i.e., intermediate A3-1) in 75% yield.
Step 2: synthesis of intermediate A3
Intermediate A3-1(10g, 19.85mmole) was mixed with 200mL of dichloromethane in a 500mL reaction flask to form a third mixed solution, which was then transferred to an ice bath at 0 ℃ and an addition funnel was added to the flask. Next, NBS (3.53g, 19.85mmole) was dissolved in 40mL of acetonitrile, added dropwise from an addition funnel at a rate of 2 drops/sec, and the reaction was continued at 0 ℃ for 2 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of saturated sodium bicarbonate aqueous solution, stirring for 30 minutes, standing for layering, extracting with 100mL of dichloromethane each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three-time extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a wash solution mixed with n-hexane and ethyl acetate (20: 1 by volume) to give 10.4g of the product (i.e. intermediate a3) in 90% yield.
Synthesis of arylamine compounds
The intermediate An can be used for synthesizing arylamine compounds by a synthesis mode I or a synthesis mode II; in the synthesis mode I, the reactant An is An amine compound having a diaryl and/or heteroaryl substitution, such as bis (4-biphenylyl) amine, bis (9, 9-dimethylfluorene) amine, or the like; in synthesis mode II, the reactant Bn is an aromatic compound having a boronic acid group or a boronic acid pinacol ester group, such as phenylboronic acid, 3-boronic acid pinacol ester-N-biphenylcarbazole, and the like.
Synthesis mode I:
Figure BDA0001882590530000141
synthesis scheme II:
Figure BDA0001882590530000142
synthesis mode I:
synthesis of Compound 1
Figure BDA0001882590530000143
In Synthesis mode I, intermediate A1(10g, 17.65mmole), bis (4-biphenylyl) amine (5.2g, 16.18mmole) (i.e., reactant A1) and sodium tert-butoxide (4.66g, 48.54mmole) were placed in a 500mL reaction flask and 100mL of toluene was added. Next, a 50mL scintillation vial was charged with Pd (dba)2(0.47g, 0.81mmole) and 20mL of toluene, and then P (t-Bu) was added3(0.39g, 1.94mmole) to form a first mixed solution, heating the scintillation vial to change the color of the first mixed solution from dark red to dark green; finally, slowly adding the first mixed solution into the reaction bottle, and heating to 110 ℃ for reacting for 18 hours to form a second mixed solution. To be treatedConfirming the reaction completion by using a TLC (thin layer chromatography) plate, cooling the second mixed solution to room temperature, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 200mL of ethyl acetate every time, repeating the extraction for three times, adding magnesium sulfate into organic layers collected by the three-time extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (volume ratio 10: 1) to obtain 10g of compound 1, with a yield of compound 1 of 76%.
Synthesis of Compound 2
Figure BDA0001882590530000151
Compound 2 was synthesized as in compound 1 using synthesis mode I, the main difference being that when compound 2 was synthesized, 6.5g (16.19mmole) of bis (9, 9-dimethylfluorene) amine (i.e., reactant A2) was used in place of 5.2g of bis (4-biphenylyl) amine (i.e., reactant A1) to provide 11.5g of compound 2, with a yield of compound 2 of 80%.
Synthesis scheme II:
synthesis of Compound 3
Figure BDA0001882590530000152
In synthesis mode II, intermediate a1(10g, 17.65mmole), 3- (4-dibenzofuranyl) phenylboronic acid (5.59g, 19.42mmole) (i.e., reactant B1) were placed in a 500mL reaction flask, followed by 120mL of toluene; followed by addition of potassium carbonate (K)2CO3) (6.10g, 44.13mmole) was dissolved in 65mL of deionized water and added to the reaction flask; next, tetrakis (triphenylphosphine) palladium (Pd (PPh) was added under a nitrogen system3)4) (1.02g, 0.88mmole) and 22mL of ethanol were added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After confirming the reaction completion by TLC plate, adding 300mL deionized water, stirring for 30 min, standing for layering, extracting with 200mL ethyl acetate each time, repeating the extraction for three times, adding magnesium sulfate into the organic layer collected by the three-time extraction for removing water, and filteringSeparating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (volume ratio 10: 1) to obtain 10.0g of compound 3, compound 3 in 78% yield. The chemical structure of the compound 3 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 2, and signals with chemical shifts of 7ppm to 8.4ppm are amplified particularly and are shown in figure 3; the characteristic peak signals are as follows:1H-NMR(CDCl3): 8.24(s,1H),8.07(t,1H),7.99(d,1H),7.96(d,1H),7.80(d,1H),7.73(d,2H),7.69(d,1H),7.60(d,4H),7.53(d,4H),7.51(d,1H),7.46 to 7.24(m,17H),7.16(t, 1H).
Synthesis of Compound 4
Figure BDA0001882590530000161
Compound 4 was synthesized in the same manner as Compound 3, except that Compound 4 was synthesized in such a manner that 4.12g (19.42 mmoles) of 4-dibenzofuranboronic acid (reactant B2) was used in place of 5.59g of reactant B1, to give 9.1g of Compound 4, giving a 79% yield of Compound 4.
Synthesis of Compound 5
Figure BDA0001882590530000162
Compound 5 was synthesized in the same manner as Compound 3, except that Compound 5 was synthesized in a manner such that 4.82g (19.42 mmoles) of 4- (1-naphthyl) phenylboronic acid (i.e., reactant B3) was used in place of 5.59g of reactant B1 to provide 8.9g of Compound 5, with a 73% yield of Compound 5. The chemical structure of the compound 5 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 4, and signals with chemical shifts of 7ppm to 8.3ppm are amplified particularly and are shown in figure 5; the characteristic peak signals are as follows:1H-NMR(CDCl3): 8.09(d,1H),7.96(d,1H),7.92(dd,1H),7.81(d,2H),7.74(d,1H),7.68(d,2H),7.62-7.50(m,12H),7.45 to 7.26(m,14H),7.18(t, 1H).
Synthesis of Compound 6
Figure BDA0001882590530000163
Compound 6 was synthesized in the same manner as Compound 3, except that Compound 6 was synthesized in a 75% yield of compound 6 using 2.37g (19.42mmole) of phenylboronic acid (i.e., reactant B4) in place of 5.59g of reactant B1 to provide 7.5g of Compound 6. The chemical structure of the compound 6 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 6, and signals with chemical shifts of 6.9ppm to 7.9ppm are amplified particularly and are shown in figure 7; the characteristic peak signals are as follows:1H-NMR(CDCl3): 7.66(d,2H),7.59(dd,4H),7.56 to 7.46(m,8H),7.41(t,4H),7.39(d,1H),7.34(dd,2H),7.30(t,2H),7.26 to 7.21(m,5H),7.10(td, 1H).
Synthesis of Compound 7
Figure BDA0001882590530000171
Compound 7 was synthesized in the same manner as Compound 3, except that Compound 7 was synthesized in a 75% yield of compound 7 using 3.34g (19.42mmole) of 1-naphthalene boronic acid (i.e., reactant B5) in place of 5.59g of reactant B1 to provide 8.0g of Compound 7.
Synthesis of Compound 8
Figure BDA0001882590530000172
Compound 8 was synthesized in the same manner as Compound 3, except that Compound 8 was synthesized in a manner such that 3.34g (19.42 mmoles) of 2-naphthalene boronic acid (i.e., reactant B6) was used in place of 5.59g of reactant B1 to provide 8.4g of Compound 8, with a 78% yield of Compound 8.
Synthesis of Compound 9
Figure BDA0001882590530000173
Compound 9 is synthesized in a synthesis mode II as compound 3; will be inPlacing the intermediate A1(10g, 17.65mmole) and 3-boronic acid pinacol ester-N-biphenylcarbazole (namely the reactant B7) (9.17g, 20.60mmole) into a 500mL reaction bottle, and then adding 120mL of toluene; then K is put2CO3(5.93g, 42.91mmole) was dissolved in 70mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(0.99g, 0.86mmole) and 30mL of ethanol were added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of ethyl acetate each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (volume ratio 10: 1) to obtain 10.5g of compound 9, with a yield of 79% of compound 9. The chemical structure of the compound 9 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 8, and signals with chemical shifts of 6.9ppm to 8.6ppm are amplified particularly and are shown in figure 9; the characteristic peak signals are as follows:1H-NMR(CDCl3): 8.24(s,1H),8.46(s,1H),8.17(d,1H),7.88(d,1H),7.54(dd,4H),7.53(s,1H),7.65(d,1H),7.60(d,4H),7.56 to 7.26(m,25H),7.06(t, 1H).
Synthesis of Compound 10
Figure BDA0001882590530000181
Compound 10 was synthesized in the same manner as Compound 3, except that in the synthesis of Compound 10, 6.99g (19.42 mmoles) of B-9,9 '-spirobifluoren-2' -ylboronic acid (i.e., reactant B8) was used in place of 5.59g of reactant B1 to provide 10.5g of Compound 10, with a 74% yield of Compound 10.
Synthesis of Compound 11
Figure BDA0001882590530000182
Compound 11 was synthesized in synthesis mode II as compound 3, the main difference being that compound 11 was synthesized using 5.58g (19.42mmole) of N-phenyl-3-carbazolboronic acid (i.e., reactant B9) in place of 5.59g of reactant B1 to provide 10g of compound 11, with a 78% yield of compound 11.
Synthesis of Compound 12
Figure BDA0001882590530000191
Compound 12 is synthesized in the same manner as compound 3 in the synthesis mode II; putting the intermediate A1(10g, 17.65mmole), 4- (2-naphthyl) phenylboronic acid (reactant B10) (4.82g, 19.42mmole) into a 500mL reaction flask, and adding 150mL of toluene; then K is put2CO3(6.10g, 44.13mmole) was dissolved in 65mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(1.53g, 1.32mmole) and 22mL of ethanol were added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ to continue the reaction for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of toluene each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a washing solution in which n-hexane and ethyl acetate were mixed (volume ratio: 10: 1), whereby 8.56g of compound 12 was obtained, with a yield of compound 12 of 70%.
Synthesis of Compound 13
Figure BDA0001882590530000192
Compound 13 is synthesized in the same manner as compound 3 in the synthesis mode II; putting the intermediate A1(10g, 17.65mmole) and 3-biphenylboronic acid (reactant B11) (4.19g, 21.18mmole) into a 500mL reaction bottle, and then adding 120mL of toluene; then K is put2CO3(6.09g, 44.13mmole) was dissolved in 50mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(1.02g, 0.88mmole) and ethanol20mL of the solution was added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After TLC (thin layer chromatography) plates are used for confirming that the reaction is finished, 100mL of deionized water is added, the mixture is stirred for 30 minutes and then stands for layering, 100mL of ethyl acetate is used for extraction every time, extraction is carried out for three times, magnesium sulfate is added into organic layers collected by the three-time extraction for dewatering, filtering separation, concentrating and drying, and a crude product is obtained; the crude product was purified by column chromatography using a washing solution in which n-hexane and ethyl acetate were mixed (volume ratio: 10: 1), whereby 12g of compound 13 was obtained, with a yield of compound 13 of 67%. The chemical structure of the compound 13 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 10, and signals with chemical shifts of 6.8ppm to 8.4ppm are amplified particularly and are shown in figure 11; the characteristic peak signals are as follows:1H-NMR(CDCl3): 7.92(s,1H),7.72(d,1H),7.68(d,1H),7.64(d,1H),7.62(d,2H),7.59(d,4H),7.52(d,4H),7.46 to 7.26(m,17H),7.11(t, 2H).
Synthesis of Compound 14
Figure BDA0001882590530000201
In synthesis mode II, intermediate A2(10g, 15.47mmole) and reactant B1(4.9g, 17.01mmole) were placed in a 500mL reaction flask, followed by addition of 120mL of toluene; then K is put2CO3(5.34g, 38.66mmole) was dissolved in 65mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(0.89g, 0.77mmole) and 22mL of ethanol were added to the flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 200mL of ethyl acetate every time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a washing solution in which n-hexane and ethyl acetate were mixed (volume ratio: 10: 1), whereby 9.0g of compound 14 was obtained, with a yield of compound 14 of 72%.
Synthesis of Compound 15
Figure BDA0001882590530000202
In synthesis mode II, intermediate A2(10g, 15.47mmole) and reactant B4(2.27g, 18.56mmole) were placed in a 500mL reaction flask, followed by addition of 120mL toluene; then K is put2CO3(5.34g, 38.66mmole) was dissolved in 70mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(0.89g, 0.77mmole) and 30mL of ethanol were added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ to continue the reaction for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of ethyl acetate each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a washing solution in which n-hexane and ethyl acetate were mixed (volume ratio: 20: 1), whereby 8.1g of compound 15 was obtained, with a yield of compound 15 of 82%.
Synthesis of Compound 16
Figure BDA0001882590530000211
Compound 16 was synthesized in the same manner as Compound 15, except that compound 16 was synthesized in a yield of 85% using 3.68g (18.56mmole) of reactant B11 instead of 2.27g of reactant B4, yielding 9.46g of compound 16.
Synthesis of Compound 17
Figure BDA0001882590530000212
Compound 17 was synthesized as in compound 15 using synthesis mode II, the main difference being that compound 17 was synthesized using 4.42g (18.56mmole) of 9, 9-dimethyl-2-boronic acid fluorene (i.e., reactant B12) in place of 2.27g of reactant B4 to provide 10.34g of compound 17, with a 88% yield of compound 17.
Synthesis of Compound 18
Figure BDA0001882590530000213
In synthesis mode II, intermediate A3(10g, 17.17mmole) and reactant B4(2.30g, 18.88mmole) were placed in a 500mL reaction flask, and 150mL of toluene was added; then K is put2CO3(5.93g, 42.91mmole) was dissolved in 65mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(1.49g, 1.29mmole) and 22mL of ethanol were added to the flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of toluene each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent mixture of n-hexane and ethyl acetate (volume ratio 10: 1) to obtain 7.66g of compound 18, which was found to be 77% of compound 18. The chemical structure of the compound 18 is identified by a nuclear magnetic resonance spectrometer with 400MHz, the NMR spectrum of the compound is shown in figure 12, and signals with chemical shifts of 6.6ppm to 7.9ppm are amplified particularly and are shown in figure 13; the characteristic peak signals are as follows:1H-NMR(CDCl3): 7.68(d,1H),7.58(d,4H),7.54 to 7.49(m,9H),7.43-7.36(m,5H),7.29(t,2H),7.28(d,2H),7.21(d,4H),7.17(d,1H),7.05(t, 1H).
Synthesis of Compound 19
Figure BDA0001882590530000221
Compound 19 was synthesized as in compound 18 using synthesis mode II, the main difference being that compound 19 was synthesized using 3.74g (18.88mmole) of reactant B11 instead of 2.30g of reactant B4 to provide 8.44g of compound 19, with a 75% yield of compound 19.
Synthesis of Compound 20
Figure BDA0001882590530000222
Compound 20 was synthesized in the same manner as Compound 18, except that compound 20 was synthesized in a 70% yield of compound 20 using 4.5g (18.88mmole) of reactant B12 instead of 2.30g of reactant B4, to give 8.36g of compound 20.
Synthesis of Compound 21
Figure BDA0001882590530000223
Compound 21 is synthesized in the same manner as compound 3 in synthesis mode II; putting the intermediate A1(10g, 17.65mmole) and the reactant B12(4.62g, 19.42mmole) into a 500mL reaction bottle, and then adding 120mL of toluene; then K is put2CO3(6.10g, 44.13mmole) was dissolved in 65mL of deionized water and added to the reaction flask; next, Pd (PPh) was added under a nitrogen system3)4(1.02g, 0.88mmole) and 22mL of ethanol were added to a reaction flask to form a mixed solution, and the mixed solution was heated to 76 ℃ for 16 hours. After confirming that the reaction is finished by a TLC (thin layer chromatography) plate, adding 300mL of deionized water, stirring for 30 minutes, standing for layering, extracting with 100mL of ethyl acetate each time, extracting for three times repeatedly, adding magnesium sulfate into organic layers collected by three times of extraction for dewatering, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a washing solution in which n-hexane and ethyl acetate were mixed (volume ratio: 10: 1), whereby 9g of compound 21 was obtained, with a yield of compound 21 of 75%.
Physical Property analysis of arylamine Compound
1. Measurement of glass transition temperature (T)g): compounds 1 to 20 and NPB were measured using a differential scanning thermal analyzer (DSC) (instrument model PerkinElmer, DSC8000) at a programmed temperature rate of 20 ℃/min.
2. Measurement of thermal cracking temperature (T)d): using a thermogravimetric analyzer (instrument typePerkin Elmer, TGA8000), the thermal cracking properties of compounds 1 to 20 and NPB were measured at a temperature programmed rate of 20 ℃/min under normal pressure and in a nitrogen atmosphere, and the temperature at which the weight was reduced to 95% of the starting weight was defined as the thermal cracking temperature.
3. The energy level value of the highest filled molecular orbital (HOMO) of the molecule was measured: the compounds 1 to 20 and NPB were prepared in a thin film state, and the ionization potential values thereof were measured using a photoelectron spectrophotometer (instrument model: Riken Keiki, Surface Analyzer) under the atmosphere, and the values were further converted to obtain HOMO level values.
4. Measuring the energy level of the Lowest Unfilled Molecular Orbital (LUMO) of the molecule: the boundary value (onset) of the absorption wavelength of the thin films of the above compounds 1 to 20 and NPB was measured with an ultraviolet-visible spectrophotometer (model Perkin Elmer, Lambda20), the boundary value was converted into a band gap value, and the band gap value was subtracted from the HOMO level value to obtain the LUMO level value.
5. Refractive index: the refractive index was measured using a full spectrum ellipsometer (instrument model SE-RD), and Spectroscopic Ellipsometry (SE) using infrared, visible or ultraviolet spectral regions, thereby measuring complex refractive index, and films of compounds 1 to 20 and NPB were fixedly measured at a thickness of 500 angstroms, and the refractive index of the films at 555nm was observed.
TABLE 1T of Compounds 1 to 13, Compounds 15 to 20, NPBgMeasurement results of HOMO energy level and LUMO energy level
Figure BDA0001882590530000241
Preparation of blue light organic electroluminescent device
Before the substrate 10 is loaded into the evaporation system, the substrate is cleaned by a solvent (acetone and isopropyl alcohol) and ultraviolet ozone for degreasing, and then the cleaned substrate 10 is transferred to the evaporation equipment. Referring to FIG. 1, the evaporation boat is heated at about 10 deg.C-6The layers are sequentially deposited on the substrate 10 under a vacuum of torr (torr). After each layer is formed in the evaporation equipment, each layer is platedThe layered substrate 10 is transferred from the evaporation apparatus to a drying oven, and then encapsulated with an ultraviolet curable epoxy resin and a glass cover plate (not shown) containing a moisture absorbent, thereby obtaining a blue organic electroluminescent device (B-OLED). The B-OLED emits blue light and has a light emitting area of 9 square millimeters. The sequence of the individual layers, the layer names and their symbols, the thicknesses, and the materials used for the preparation of the B-OLED are listed in Table 2; the chemical structural formulae of the materials used, except for the chemical structural formula of the arylamine compound of the present invention, are shown in Table 5.
TABLE 2B OLED the sequence of the individual layers, the layer names and their designations, the thicknesses, and the materials used
Figure BDA0001882590530000251
Preparation of green light organic electroluminescent device
Before the substrate 10 is loaded into the evaporation system, the substrate is cleaned by a solvent (acetone and isopropyl alcohol) and ultraviolet ozone for degreasing, and then the cleaned substrate 10 is transferred to the evaporation equipment. Referring to FIG. 1, the evaporation boat is heated at about 10 deg.C- 6Layers are sequentially deposited on the substrate 10 under a vacuum of torr. After the layers are formed in the evaporation apparatus, the substrate 10 coated with the layers is transferred from the evaporation apparatus to a drying oven, and then encapsulated with an ultraviolet curable epoxy resin and a glass cover plate (not shown) containing a moisture absorbent, thereby obtaining a green organic electroluminescent device (G-OLED). The G-OLED emits green light and has a light emitting area of 9 square millimeters. The sequence of the layers, the layer names and their symbols, the thicknesses, and the materials used to prepare the G-OLED are listed in table 3; the chemical structural formulae of the materials used, except for the chemical structural formula of the arylamine compound of the present invention, are shown in Table 5.
TABLE 3G-OLED in which the order of the individual layers, the layer names and their designations, the thicknesses, and the materials used
Figure BDA0001882590530000252
Preparation of red light organic electroluminescent device
Before the substrate 10 is loaded into the evaporation system, the substrate is cleaned by a solvent (acetone and isopropyl alcohol) and ultraviolet ozone for degreasing, and then the cleaned substrate 10 is transferred to the evaporation equipment. Referring to FIG. 1, the evaporation boat is heated at about 10 deg.C- 6Layers are sequentially deposited on the substrate 10 under a vacuum of torr. After the layers are formed in the evaporation apparatus, the substrate 10 coated with the layers is transferred from the evaporation apparatus to a drying oven, and then encapsulated with an ultraviolet curable epoxy resin and a glass cover plate (not shown) containing a moisture absorbent, thereby obtaining a red organic electroluminescent device (R-OLED). The R-OLED emits red light and has a light emitting area of 9 square millimeters. The sequence of the layers for the preparation of the R-OLED, their layer names and their symbols, thicknesses, and materials used are listed in table 4; the chemical structural formulae of the materials used, except for the chemical structural formula of the arylamine compound of the present invention, are shown in Table 5.
TABLE 4R-OLED in which the order of the layers, the layer names and their designations, the thicknesses, and the materials used
Figure BDA0001882590530000261
Table 5: chemical structure of material for organic electroluminescent device
Figure BDA0001882590530000262
Figure BDA0001882590530000271
Effect of B-OLED/G-OLED/R-OLED device
The performance of the B-OLED/G-OLED/R-OLED was measured at room temperature using a constant current source (KEITHLEY 2400) and a photometer (PHOTO RESEARCH SpectraScan PR 650). At a current density of 10 milliamperes per square centimeter (mA/cm)2) The efficiency of each example and each comparative example was measured under the conditions of (1): drive voltage, luminance (L, unit: candlepower/square meter), current efficiency (yield, unit): candlepower/ampere), luminous efficiency (efficacy, unit: lumens/watt), external quantum efficiency, and lifetime (LT95 value), and the measurement results of B-OLED/G-OLED/R-OLED are listed in tables 6 to 8, respectively. The service life test of the B-OLED is that the fixed initial brightness is 1000 nits (nit), the service life test of the G-OLED is that the fixed initial brightness is 10000nits, and the service life test of the R-OLED is that the fixed initial brightness is 6000 nits.
B-OLED/G-OLED/R-OLED efficacy testing
1. The organic electroluminescent devices were measured for their luminescent properties such as driving voltage, luminance, current efficiency, and luminous efficiency at room temperature using a constant current Source (model: KEITHLEY2400Source Meter, manufactured by KEITHLEY instruments, U.S.) and a photometer (model: PHOTO RESEARCH PR650, manufactured by pho RESEARCH);
LT95 value test: the brightness level was measured from the initial brightness (initial brightness of B-OLED 1000 cd/m)2G-OLED initial luminance is 10000cd/m2And the initial brightness of the R-OLED is 6000cd/m2) The time taken to fall to a level of 95% relative to the initial brightness serves as a measure of the lifetime or stability of the OLED.
Table 6: measurement results of Compound No. used for B-OLED, drive Voltage, luminance, Current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value
Figure BDA0001882590530000281
Table 7: measurement results of Compound No. used for G-OLED, Driving Voltage, luminance, Current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value
Figure BDA0001882590530000282
Figure BDA0001882590530000291
Table 8: measurement results of Compound No. used for R-OLED, Driving Voltage, luminance, Current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value
Figure BDA0001882590530000292
From the experimental results of tables 6 to 8, it can be confirmed that the arylamine compound of the present invention can be suitably used as a hole auxiliary material for a blue, green or red organic electroluminescent device, and can be advantageous in that an OLED using the same has characteristics of a low driving voltage, preferably, a light emitting efficiency, an external quantum efficiency, a long service life, and the like. Especially the OLEDs of embodiments 1 to 11, 13 to 17, which also have a preferred brightness and current efficiency.
The above-described embodiments are merely examples illustrating the present invention and do not limit the scope of the claims of the present invention in any way, and those skilled in the art can adjust the number, position or arrangement of the substituents according to the spirit of the present invention. The scope of the invention is not to be limited to the specific embodiments described above, but only by the claims.

Claims (12)

1. An arylamine compound represented by the following formula (I):
Figure FDA0001882590520000011
wherein X is O, S or C (R)1)(R2)；R1And R2Each independently is hydrogen, C1-12 alkyl, or C6-30 aryl, or R1And R2Together form a ring having 6 to 15 carbon atoms;
n1, n2 and n3 are each independently an integer of 0 to 2, and n1, n2 and n3 are the same as or different from each other;
L1、L2and L3Each independently an arylene group having 6 to 30 carbon atoms in the ring or a heteroarylene group having 3 to 30 carbon atoms in the ring, and L1、L2And L3Are the same or different from each other;
a is an aryl group having 6 to 30 carbon atoms in the ring, a heteroaryl group having 3 to 30 carbon atoms in the ring, or-N (Ar)3)(Ar4) A group; and
Ar1to Ar4Each independently is an aryl group having 6 to 30 carbon atoms in the ring or a heteroaryl group having 3 to 30 carbon atoms in the ring, and Ar1、Ar2、Ar3And Ar4The same or different from each other.
2. The arylamine compound according to claim 1, wherein X in the formula (I) is O, S or C (CH)3)2。
3. The arylamine compound according to claim 1, wherein when n1, n2 or n3 is 1 or 2, L is1、L2And L3The arylene group having 6 to 30 carbon atoms in the ring represented by (A) is any one of the following groups:
Figure FDA0001882590520000012
wherein m1 is an integer from 1 to 4, m2 is an integer from 1 to 2, m3 is an integer from 1 to 3; and
R3to R6Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12.
4. The arylamine compound according to claim 1, wherein when n1, n2 or n3 is 1 or 2, L is1、L2And L3The arylene group having 6 to 30 carbon atoms in the ring represented by (A) is any one of the following groups:
Figure FDA0001882590520000021
wherein m is1Is an integer of 1 to 4, m3Is an integer from 1 to 3; and
R3and R4Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12.
5. The arylamine compound according to claim 1, wherein A, Ar1To Ar4Any one of the aryl groups having 6 to 30 carbon atoms in the ring is selected from the group consisting of: phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, 9' -spirobifluorenyl, naphthylphenyl and isomers thereof.
6. The arylamine compound according to claim 1, wherein A, Ar1To Ar4The heteroaryl group having 3 to 30 carbon atoms in the ring represented by any one of the above groups is selected from the group consisting of: furyl, pyrrolyl, thienyl, imidazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, benzofuryl, isobenzofuryl, dibenzofuryl, benzothienyl, isobenzothienyl, dibenzothienyl, quinolyl, isoquinolyl, benzimidazole, carbazolyl, dicarbazolyl, and acridinyl.
7. The arylamine compound according to any one of claims 1 to 4, wherein A, Ar1To Ar4Any one of the aryl groups having 6 to 30 carbon atoms in the ring is selected from the group consisting of:
Figure FDA0001882590520000022
wherein m is1Is an integer of 1 to 4, m3Is an integer of 1 to 3, m4Is an integer from 1 to 5; and
R3to R6Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silane group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12.
8. The arylamine compound according to any one of claims 1 to 4, wherein A, Ar1To Ar4The heteroaryl group having 3 to 30 carbon atoms in the ring represented by any one of the above groups is selected from the group consisting of:
Figure FDA0001882590520000031
wherein m is1Is an integer of 1 to 4, m3Is an integer from 1 to 3; and
R3and R4Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having a carbon number of 1 to 12, and an alkoxy group having a carbon number of 1 to 12.
9. The arylamine compound according to claim 1, wherein the arylamine compound is selected from the group consisting of:
Figure FDA0001882590520000032
Figure FDA0001882590520000041
10. an organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the anode and the cathode, the organic layer comprising the arylamine compound according to any one of claims 1 to 9.
11. The organic electroluminescent device of claim 10, further comprising a hole-assist layer, a light-emitting layer, an electron-transport layer, and an electron-injection layer; the hole auxiliary layer is formed on the anode; the light-emitting layer is formed on the hole auxiliary layer; the electron transport layer is formed on the light-emitting layer; the electron injection layer is formed between the electron transport layer and the cathode; the hole assist layer includes the organic layer.
12. An organic electroluminescent device comprising an anode, a cathode and a capping layer disposed on the cathode, the cathode being disposed between the anode and the capping layer, the capping layer comprising the arylamine compound according to any one of claims 1 to 9.
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