CN111138393B - Arylamine compound and organic electroluminescent device using the same - Google Patents
Arylamine compound and organic electroluminescent device using the same Download PDFInfo
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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):
wherein X is O, S, or C (R) 1 )(R 2 )；R 1 And R 2 Each independently is a hydrogen atom, an alkyl or aryl group, or R 1 And R 2 A ring formed together; n1, n2 and n3 are integers; l is 1 、L 2 And L 3 Each independently an arylene or heteroarylene group; a is aryl, heteroaryl, or-N (Ar) 3 )(Ar 4 ) A group; and Ar 1 To Ar 4 Each independently is an aryl or heteroaryl group.
Description
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 a hole transport material of a hole transport layer, a fused heterocyclic compound having an amine group and linking two benzene rings is proposed as in international patent publication No. 2017196081. 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):
in the formula (I), X is O, S, or C (R) 1 )(R 2 )；R 1 And R 2 Each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 30 carbon atoms in the ring, or R 1 And R 2 Together 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;
L 1 、L 2 and L 3 Each 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 L 1 、L 2 And L 3 Are 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 )(Ar 4 ) A group; and
Ar 1 to Ar 4 Each 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, ar 1 、Ar 2 、Ar 3 And Ar 4 The same or different from each other.
Preferably, in formula (I), X is O, S, or C (CH) 3 ) 2 。
When n1 is an integer of 2,2 linked L 1 Each independently of the other being the number of carbons in the ringArylene of 6 to 30 or heteroarylene having 3 to 30 carbon atoms in the ring, 2L 1 May be the same or different from each other; for example 1L 1 Is arylene with 6 to 30 carbon atoms on the ring, and another 1L 1 Is an arylene group having 3 to 30 carbon atoms; similarly, 2 connected L 2 Identical or different from each other, 2 consecutive L 3 May be the same or different from each other.
Specifically, when n1, n2 or n3 is 1 or 2, L 1 、L 2 And L 3 The arylene group having 6 to 30 carbon atoms in the ring represented by (a) may be any one of the following groups:
wherein m is 1 Is an integer of 1 to 4, m 2 Is an integer of 1 to 2, m 3 Is an integer from 1 to 3; and
R 3 to R 6 Each 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 is 1 、m 2 Or m 3 When it is an integer of more than 1, each R 3 May be the same or different from each other, each R 4 May be the same or different from each other, each R 5 May be the same or different from each other, each R 6 May be the same or different from each other.
Specifically, when n1, n2 or n3 is 1 or 2, L 1 、L 2 And L 3 The heteroarylene group having 3 to 30 carbon atoms in the ring represented by (a) may be any one of:
wherein m is 1 Is an integer of 1 to 4, m 3 Is an integer from 1 to 3; and
R 3 and R 4 Each independently selected from the group consisting of: hydrogen atom, cyano, nitroA group, a silane group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms;
when m is 1 Or m 3 When is an integer greater than 1, each R 3 May be the same or different from each other, each R 4 May be the same or different from each other.
Preferably, in formula (I), n1 and n2 are each independently 0 or 1.
Specifically, A and Ar 1 To Ar 4 Any 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 and Ar 1 To Ar 4 Wherein the 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, ar 1 To Ar 4 Any one of the aryl groups having 6 to 30 carbon atoms in the ring is selected from the group consisting of:
wherein m is 1 Is an integer of 1 to 4, m 3 Is an integer of 1 to 3, m 4 Is an integer from 1 to 5; and
R 3 to R 6 Each independently selected from the group consisting of: a hydrogen atom, a cyano group, a nitro group, a silyl group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms;
when m is 1 、m 3 Or m 3 When it is an integer of more than 1, each R 3 May be the same or different from each otherEach R 4 May be the same or different from each other, each R 5 May be the same or different from each other, each R 6 May be the same or different from each other.
Preferably, A, ar 1 To Ar 4 Any one of the heteroaryl groups having 3 to 30 carbon atoms in the ring is selected from the group consisting of:
wherein m is 1 Is an integer of 1 to 4, m 3 Is an integer from 1 to 3; and
R 3 and R 4 Each 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 is 1 Or m 3 When it is an integer of more than 1, each R 3 May be the same or different from each other, each R 4 May be the same or different from each other.
In some embodiments of the invention, n1 and n2 are the same integer, L 1 And L 2 Are selected the same, and Ar 1 And Ar 2 The same applies to the selection of (1). For example, n1 and n2 are both 1,L 1 And L 2 Are phenylene, biphenylene, or 9, 9-dimethylfluorenylene, but are not limited thereto.
In some embodiments of the invention, when n3 is an integer of 1,L 3 Is an arylene group having 6 to 30 carbon atoms in the ring, and A is-N (Ar) 3 )(Ar 4 ) When radical, the amine polycyclic moiety (i.e.
* Is equal to L 3 In the position of contact) with A at L 3 The upper positions are not meta. For example, when L is 3 When it is phenylene, the group-N (Ar) 3 )(Ar 4 ) The radical may be para to the amino polycyclic moiety and has the structure->
When L is 3 When it is an naphthylene group, -N (Ar) 3 )(Ar 4 ) The group is not meta to the polycyclic part of the amino group and can be constructed in such a way that it is->
/>
But is not limited thereto.
In the specification, X is C (R) 1 )(R 2 ) So called "R 1 And R 2 A 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 R 3 To R 6 Any of them.
In the specification, L 1 、L 2 Or L 3 The term "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; the substituent on the arylene group may be the aforementioned R 3 To R 6 Any of the above; likewise, L 1 、L 2 Or L 3 The "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 R 3 To R 6 Any 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 R 3 To R 6 Any of the above; the mixture isSubstituents on the aryl radical may be as defined above for R 3 To R 6 Any 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:
the present invention also 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 3 1 -NMR)。
FIGS. 4 and 5 are H for Compound 5 1 -NMR。
FIGS. 6 and 7 are H for Compound 6 1 -NMR。
FIGS. 8 and 9 are H of Compound 9 1 -NMR。
FIGS. 10 and 11 are H for Compound 13 1 -NMR。
FIGS. 12 and 13 are H for Compound 18 1 -NMR。
Detailed Description
Several examples are listed below 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.
Synthetic mechanism A1
Wherein X is O, S, or C (R) 1 )(R 2 )；R 1 And R 2 Each 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 R 1 And R 2 Together 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 is 1 And L 2 Each 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 L 1 And L 2 Are the same or different from each other; and Ar 1 And Ar 2 Each independently 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
The intermediate A1 can be synthesized by the following synthesis mechanism A1-1.
Synthetic mechanism A1-1
Step 1: synthesis of intermediate A1-1
4-Bromobenzofuran (10 g (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, and 100mL of toluene was added. Next, tris (dibenzylideneacetone) dipalladium (Pd (dba) was added to a 50mL scintillation vial 2 ) (1.16g, 2.02mmole) and 20mL of toluene, 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, the first step is performedThe mixed solution is slowly added into the reaction bottle, and the temperature is increased to 110 ℃ for reaction 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 ) 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 (10% by volume) to obtain 14.8g of the product (i.e., intermediate A1-1) in 75% yield.
And 2, step: synthesis of intermediate A1
Intermediate A1-1 (10 g, 20.51mmole) was mixed with 200mL of dichloromethane in a 500mL reaction flask to form a third mixed solution, which was then brought to an ice bath at 0 ℃ and an addition funnel was added to the reaction flask. N-bromosuccinimide (4.02g, 22.56mmole) was then dissolved in 40mL of acetonitrile, and added dropwise from an addition funnel to the flask at a rate of 2 drops/sec, 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 of which was performed with 200mL of dichloromethane, and extraction was repeated three times, and magnesium sulfate (MgSO. Sub.MgSO) was added to the organic layer collected by the three-time extraction 4 ) Carrying out dewatering, filtering separation, concentration 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% by volume) to obtain 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, with the main difference being the difference in reactant An. The intermediate A2 can be synthesized by the following synthesis mechanism A1-2.
Synthetic mechanism A1-2
In step 1, the difference was that in which 12.36g of bis (4-biphenylyl) amine was substituted with 15.44 g (38.45 mmole) of bis (9, 9-dimethylfluorene) amine, 17g of intermediate A2-1 was obtained, the yield of intermediate A2-1 was 74%.
Step 2: synthesis of intermediate A2
Intermediate A2-1 (10g, 17.61mmole) was mixed with 176mL of dichloromethane in a 500mL reaction flask to form a mixed solution, the mixed solution was transferred to an ice bath at 0 ℃ and an addition funnel was added to the reaction flask. NBS (3.45g, 19.38mmole) was then dissolved in 35mL of acetonitrile, added dropwise from the addition funnel at a rate of 2 drops/sec, and the reaction was continued for 1 hour while maintaining 0 ℃. 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% by volume) to obtain 8.7g of the product (i.e., intermediate A2) in 76% yield.
Synthesis of intermediate A3
Intermediate A3 can be synthesized by a synthetic mechanism A1-1 similar to intermediate A1, the main difference being the difference in the reactant Sn. The intermediate A3 can be synthesized by the following synthesis mechanism A1-3.
Synthetic mechanism A1-3
Step 1: synthesis of intermediate A3-1
4-bromodibenzothiophene (10 g,38.0 mmole), bis (4-biphenyl) amine (11.6 g,36.10 mmole) and sodium tert-butoxide (10.96g, 114mmole) were placed in a 500mL reaction flask, followed by 120mL of toluene. Next, pd (dba) was added to a 50mL scintillation vial 2 (1.09g，1.90mmole) 20mL of toluene, then P (t-Bu) was added 3 (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, 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 wash solution mixed with n-hexane and ethyl acetate (10% by volume) to obtain 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 methylene chloride in a 500mL reaction flask to form a third mixed solution, the third mixed solution was transferred to an ice bath at 0 ℃ and an addition funnel was added to the reaction flask. NBS (3.53g, 19.85mmole) was then 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% by volume) to obtain 10.4g of the product (i.e., intermediate A3) in 90% yield.
Synthesis of arylamine compounds
The arylamine compound can be synthesized from the intermediate An 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:
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synthesis scheme II:
synthesis scheme I:
synthesis of Compound 1
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, pd (dba) was added to a 50mL scintillation vial 2 (0.47g, 0.81mmole) and 20mL of toluene, then P (t-Bu) was added 3 (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. 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 200mL of ethyl acetate each 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 wash solution mixed with 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
Synthesis scheme II:
synthesis of Compound 3
In Synthesis mode II, intermediate A1 (10g, 17.65mmole) and 3- (4-dibenzofuranyl) phenylboronic acid (5.59g, 19.42mmole) (i.e., reactant B1) were placed in a 500mL reaction flask, and then 120mL of toluene was added; followed by addition of potassium carbonate (K) 2 CO 3 ) (6.10g, 44.13mmole) was dissolved in 65mL of deionized water and then added into the reaction flask; next, tetrakis (triphenylphosphine) palladium (Pd (PPh) was reacted under a nitrogen system 3 ) 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 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 wash solution in which n-hexane and ethyl acetate (volume ratio 10: 1) were mixed, and 10.0g of compound 3 was obtained, with a yield of compound 3 of 78%. 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: 1 H-NMR(CDCl 3 )：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
Compound 4 was synthesized in the same manner as Compound 3 in Synthesis mode II, except that Compound 4 was synthesized in such a manner that 4.12g (19.42 mmole) of 4-dibenzofuranboronic acid (i.e., reactant B2) was used in place of 5.59g of reactant B1, to give 9.1g of Compound 4, with a 79% yield of Compound 4.
Synthesis of Compound 5
Synthesis of Compound 6
Synthesis of Compound 7
Synthesis of Compound 8
Synthesis of Compound 9
Synthesis of Compound 10
Synthesis of Compound 11
Synthesis of Compound 12
Compound 12 is synthesized in the same manner as compound 3 in the synthesis mode II; placing intermediate A1 (10g, 17.65mmole) and 4- (2-naphthyl) phenylboronic acid (namely reactant B10) (4.82g, 19.42mmole) in a 500mL reaction bottle, and then adding 150mL of toluene; then K is put 2 CO 3 (6.10g, 44.13mmole) was dissolved in 65mL of deionized water and then added into the reaction flask; next, pd (PPh) was added under a nitrogen system 3 ) 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 wash solution in which n-hexane and ethyl acetate (volume ratio 10: 1) were mixed, and 8.56g of compound 12 was obtained, with a yield of compound 12 of 70%.
Synthesis of Compound 13
Synthesis of Compound 14
In Synthesis mode II, intermediate A2 (10g, 15.47mmole) and reactant B1 (4.9g, 17.01mmole) were placed in a 500mL reaction flask, and then 120mL of toluene was added; then K is put in 2 CO 3 (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 system 3 ) 4 (0.89g, 0.77mmole) 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 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 wash solution mixed with n-hexane and ethyl acetate (10% by volume) to obtain 9.0g of compound 14 with a yield of 72% of compound 14.
Synthesis of Compound 15
In combinationIn the method II, the intermediate A2 (10g, 15.47mmole) and the reactant B4 (2.27g, 18.56mmole) are placed in a 500mL reaction bottle, and then 120mL of toluene is added; then K is put in 2 CO 3 (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 system 3 ) 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, adding magnesium sulfate into organic layers collected by extraction for three times, removing water, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a wash solution in which n-hexane and ethyl acetate (volume ratio 20: 1) were mixed, and 8.1g of compound 15 was obtained, with a yield of compound 15 of 82%.
Synthesis of Compound 16
Synthesis of Compound 17
Compound 17 was synthesized as in compound 15 using synthesis II, the main difference being that compound 17 was synthesized using 4.42g (18.56 mmole) 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
In synthesis mode II, intermediate A3 (10 g, 17.17mmole) and reactant B4 (2.30g, 18.88mmole) were placed in a 500mL reaction flask, followed by addition of 150mL of toluene; then K is put 2 CO 3 (5.93g, 42.91mmole) was dissolved in 65mL of deionized water and then added into a reaction flask; next, pd (PPh) was added under a nitrogen system 3 ) 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 ℃ 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, adding magnesium sulfate into organic layers collected by extraction for three times, removing water, filtering, separating, concentrating and drying to obtain a crude product; the crude product was purified by column chromatography using a eluent containing n-hexane and ethyl acetate (volume ratio: 10: 1) to obtain 7.66g of compound 18, which was a 77% yield 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: 1 H-NMR(CDCl 3 ): 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
Compound 19 was synthesized in the same manner as Compound 18, except that compound 19 was synthesized using 3.74g (18.88 mmole) of reactant B11 instead of 2.30g of reactant B4, yielding 8.44g of Compound 19, with a 75% yield of Compound 19.
Synthesis of Compound 20
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 (18.88 mmole) of reactant B12 instead of 2.30g of reactant B4, to give 8.36g of compound 20.
Synthesis of Compound 21
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 put 2 CO 3 (6.10g, 44.13mmole) was dissolved in 65mL of deionized water and then added into the reaction flask; next, pd (PPh) was added under a nitrogen system 3 ) 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 eluent containing n-hexane and ethyl acetate (volume ratio 10: 1) to obtain 9g of compound 21 with a yield of 75% of compound 21.
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 Perkin Elmer, DSC 8000) at a programmed temperature rate of 20 ℃/min.
2. Measurement of thermal cracking temperature (T) d ): measured using a thermogravimetric analyzer (instrument model Perkin Elmer, TGA 8000), the chemical conversion is carried out at a programmed temperature rate of 20 ℃/min under normal pressure and in a nitrogen atmosphereThe thermal cracking properties of compounds 1 to 20 and NPB were measured, 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 by an ultraviolet-visible spectrophotometer (model Perkin Elmer, lambda 20), 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, NPB g Measurement results of HOMO energy level and LUMO energy level
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 -6 The layers are sequentially deposited on the substrate 10 under a vacuum of torr (torr). After the layers are formed in the evaporation equipment, the substrate 10 coated with the layers is transferred from the evaporation equipment to a drying oven, and then ultraviolet light curable epoxy resin is appliedAnd a glass cover plate (not shown) containing a moisture absorbent is encapsulated to obtain 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
Preparation of green light organic electroluminescent device
Before the substrate 10 is loaded into the deposition system, the substrate is cleaned by a solvent (acetone and isopropyl alcohol) and ultraviolet ozone to be degreased, and then the cleaned substrate 10 is transferred to the deposition apparatus. Referring to FIG. 1, the evaporation boat is heated at about 10 deg.C - 6 Layers 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
Preparation of red light organic electroluminescent device
Before the substrate 10 is loaded into the deposition system, the substrate is cleaned by a solvent (acetone and isopropyl alcohol) and ultraviolet ozone to be degreased, and then the cleaned substrate 10 is transferred to the deposition apparatus. Referring to FIG. 1, the evaporation boat is heated at about 10 deg.C - 6 Layers are sequentially deposited on the substrate 10 under a vacuum of torr. After the formation of each layer in the evaporation apparatus, the substrate 10 coated with each layer 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 structures of the materials used, except for the chemical structure 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
Table 5: chemical structure of material for organic electroluminescent device
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): driving voltage, luminance (L, unit: candlepower/square meter), electricityFlow efficiency (yield in candelas per ampere), luminous efficiency (efficacy in lumens per watt), external quantum efficiency, and lifetime (LT 95 value), and the measurement results of B-OLED/G-OLED/R-OLED are listed in tables 6 to 8, respectively. Wherein, the lifetime test of the B-OLED is to fix the initial brightness of 1000 nits (nit), the lifetime test of the G-OLED is to fix the initial brightness of 10000nits, and the lifetime test of the R-OLED is to fix the initial brightness of 6000nits.
Efficiency test of B-OLED/G-OLED/R-OLED
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 PR 650, manufactured by pho RESEARCH);
LT95 value test: the brightness level was measured from the initial brightness (initial brightness of B-OLED 1000 cd/m) 2 And the initial brightness of the G-OLED is 10000cd/m 2 And the initial brightness of the R-OLED is 6000cd/m 2 ) The time taken to fall to a level of 95% relative to the initial brightness is a measure of the lifetime or stability of the OLED.
Table 6: measurement results of Compound number, driving Voltage, luminance, current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value used for B-OLED
Table 7: measurement results of Compound number, driving Voltage, luminance, current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value used for G-OLED
Table 8: measurement results of Compound number, driving Voltage, luminance, current efficiency, light-emitting efficiency, external Quantum efficiency, and LT95 value used for R-OLED
From the experimental results of tables 6 to 8, it can be confirmed that the arylamine compounds of the present invention can be suitably used as a hole assist material for blue, green or red organic electroluminescent devices, and can be advantageous in that OLEDs using the same have low driving voltages, preferably, light-emitting efficiency, external quantum efficiency, and long lifetime. 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 (4)
1. An arylamine compound selected from the group consisting of:
2. 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 claim 1.
3. The organic electroluminescent device of claim 2, 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.
4. 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 claim 1.
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| CN108623545A (en) * | 2017-03-21 | 2018-10-09 | 北京绿人科技有限责任公司 | A kind of organic compound and its application and a kind of organic electroluminescence device |
| CN109053698A (en) * | 2018-09-19 | 2018-12-21 | 上海道亦化工科技有限公司 | A kind of aromatic amine compound and luminescent device containing dibenzofurans |
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| Publication number | Publication date |
|---|---|
| CN111138393A (en) | 2020-05-12 |
| TW202017911A (en) | 2020-05-16 |
| TWI702207B (en) | 2020-08-21 |
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