CN109796960B - Organic electroluminescent compound, preparation method and application thereof - Google Patents
Organic electroluminescent compound, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of luminescent compounds, in particular to an organic electroluminescent compound, and a preparation method and application thereof. In order to solve the problems of the conventional hole transport materials and to obtain a desired material, the present invention proposes a solution of introducing arylamine and anthracene derivatives to the 9-position of fluorene. Hole injection capability/transmission capability, high power efficiency and long service life are obtained by introducing arylamine; the anthracene derivative is introduced to obtain a proper glass transition temperature, so that the organic electroluminescent compound with high quality is obtained. Devices prepared from the compounds provided by the present invention have excellent current and power efficiencies and long lifetimes. The preparation method of the organic electroluminescent compound provided by the invention is simple and feasible, has high yield and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of luminescent compounds, in particular to an organic electroluminescent compound, and a preparation method and application thereof.
Background
An electroluminescent device (EL device) is an automatic light emitting device, which is advantageous in that it provides a wide viewing angle, a large contrast ratio, and a fast response time.
The organic EL element is a self-luminous element utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has a structure of an anode, a cathode and an organic layer interposed therebetween. In order to improve efficiency and stability of the organic EL element, the organic layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
Wherein the hole transport layer can change hole transport efficiency, light emitting efficiency, lifetime, etc. of holes to the light emitting layer. Therefore, copper phthalocyanine (CuPc), 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1,1' -biphenyl) -4,4' -diamine (TPD), and the like are used as the hole transporting material. However, organic EL devices using these materials still have problems in terms of quantum efficiency and service life.
Disclosure of Invention
The present invention is to solve the technical problems of the prior art and provide an organic electroluminescent compound having excellent current efficiency and power efficiency and long lifetime, a method for preparing the same, and applications thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an organic electroluminescent compound having the following structural formula:
wherein Ar is1And Ar2Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or an arylamine group;
or are linked to an adjacent substituent(s) to form a mono-or polycyclic ring, in particular a C3-C30 alicyclic or aromatic ring, the carbon atom(s) of which may be replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur;
preferably said Ar is1And Ar2Each independently selected from: a substituted or unsubstituted C6-C25 aryl, a substituted or unsubstituted C5-C22 heteroaryl, or a triarylamino group; further preferably Ar is1And Ar2Each independently selected from: substituted or unsubstituted C10-C21 aryl, substituted or unsubstituted C12-C18 heteroaryl, or triphenylamine; wherein the substituent is methyl or phenyl;
X1、X2each independently represents-O-, -S-, -SO2-、-C(R5)(R6)-、-N(R7) -, -Si-, -Sn-or-Ge-;
R1to R4Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, a substituted or unsubstituted C1-C30 hydrocarbyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, -NR, cyano, carboxyl, nitro, hydroxyl, a substituted or unsubstituted C3-C30 hydrocarbyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C-C8632 heteroaryl group8R9、-SiR10R11R12、-SR13、-OR14、-COR15、-B(OR16)(OR17)；
Or R1And R2Are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, particularly C3-C30, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably naphthalene, anthracene or pyrene, or substituted naphthalene, anthracene or pyrene; wherein the substituents are methyl or phenyl;
R5to R17Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, specifically C3-C30, aliphatic or aromatic ring;
L1、L2each independently is a substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; l is2May or may not be present; l is1Preferably benzene or deuterated benzene; l is2Preferably benzene;
a. b and d each independently represent an integer of 1 to 4;
c represents an integer of 1 to 3;
preferably a, b, c and d are all 1;
in the technical scheme, the organic electroluminescent compound is selected from any one of chemical formulas 2-13:
in the above technical solution, Ar is1And Ar2Each independently a substituent of the following structure:
wherein ". x" represents any position on the substituent group that may be attached to the N atom in chemical formula 1.
In the above technical solution, the organic electroluminescent compound is selected from any one of the following structures:
a method for preparing an organic electroluminescent compound, comprising the steps of:
step 1, preparation of intermediate 1
After adding compound 2 and tetrahydrofuran to a reaction vessel, cooling the vessel under a nitrogen atmosphere, then adding n-butyllithium dropwise to the mixture, stirring the mixture at room temperature for reaction, and cooling; thereafter, compound 1 dissolved in tetrahydrofuran was added dropwise to the above mixture, the reaction temperature was allowed to warm to room temperature, the stirring reaction was continued, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1;
step 2, preparation of compound shown in chemical formula 1
After adding the intermediate 1, the compound 3 and dichloromethane to a reaction vessel, sufficiently replacing air with nitrogen three times, dropwise adding boron trifluoride ethyl ether dissolved in dichloromethane to the above mixture, stirring the reaction at room temperature, quenching with distilled water, and extracting the mixture with dichloromethane, followed by drying the extracted organic layer using sodium sulfate and removing the solvent using a rotary evaporator, purifying the remaining substance by column chromatography to obtain the compound represented by chemical formula 1;
the synthetic route is as follows:
wherein R is1To R4、X1、X2、Ar1、Ar2、L1、L2And a, b, c, d are as defined above in formula 1, and Hal represents halogen.
In the above technical solution, the step 1 specifically includes the following steps:
after compound 2 and 200mL of tetrahydrofuran were added to a reaction vessel, the vessel was cooled to-78 ℃ under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, after the mixture was stirred at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃, after which compound 1 dissolved in 200mL of tetrahydrofuran was added dropwise to the above mixture, after the addition, the reaction temperature was allowed to warm to room temperature, and the mixture was stirred for 16 hours, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1.
In the above technical solution, the step 2 specifically includes the following steps:
after adding intermediate 1, compound 3 and 500L of dichloromethane to the reaction vessel, sufficiently replacing air with nitrogen three times, boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was added dropwise to the above mixture, after stirring the mixture at room temperature for 2 hours, quenched with distilled water, and the mixture was extracted with dichloromethane, followed by drying the extracted organic layer with sodium sulfate and removing the solvent using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain the compound represented by chemical formula 1.
The present invention also provides an organic electroluminescent device comprising the compound of the structure represented by chemical formula 1 of the present invention.
The organic electroluminescent device includes:
the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer contains a compound with a structure shown in chemical formula 1; the compound of the structure of formula 1 may be present in the organic layer in a single form or mixed with other substances. That is, the above-mentioned compound may comprise the organic electroluminescent compound according to the present invention alone, or may further comprise conventional materials generally used for organic electroluminescent materials.
One of the first and second electrodes is an anode and the other is a cathode. The organic layer includes a light emitting layer, and further includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention may be contained in at least one of the light-emitting layer and the hole transport layer.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
The "organic layer" in the present invention refers to a term of all layers disposed between the first electrode and the second electrode of the organic electroluminescent device.
When the compound of the structure shown in chemical formula 1 is present in the light emitting layer in the organic layer, the compound of the structure shown in chemical formula 1 may serve as a light emitting host or be doped in other fluorescent hosts;
when the compound of the structure represented by chemical formula 1 is present in the hole transport layer or the hole injection layer in the organic layer, the compound of the structure represented by chemical formula 1 may serve as a hole transport layer, a hole injection layer, and a functional layer having both hole injection and hole transport.
The device prepared by the compound having the structure of formula 1 according to the present invention may be used in an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic Paper (e-Paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT).
The device can be used for forming an anode by evaporating metal, conductive oxides and alloys thereof on a substrate by using methods such as thin film evaporation, electron beam evaporation, physical vapor deposition and the like, and can also be used for evaporating a spin-coating (spin-coating) or a thin strip head; the layer number can also be reduced by molding (tape-casting), doctor-blading (sector-Printing), Screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging).
The invention has the beneficial effects that:
the present invention provides a hole transport material for use in an organic EL device that can solve the conventional technical problems. Conventional hole transport materials are based essentially on triaryl derivatives. Although it has a hole transporting ability and a low driving voltage, a large number of substituents have to be introduced into its structure to raise its molecular weight in order to obtain a suitable glass transition temperature. But this reduces the triplet energy or LUMO energy, resulting in degradation of the organic electroluminescent device. Ideal hole transporting materials require high glass transition temperatures, hole injection and transport capabilities, and suitable triplet and LUMO energies. Therefore, in order to solve the problems of the conventional hole transport materials and to obtain a desired material, the present invention proposes a solution of introducing arylamine and anthracene derivatives to the 9-position of fluorene. Hole injection capability/transmission capability, high power efficiency and long service life are obtained by introducing arylamine; the anthracene derivative is introduced to obtain a proper glass transition temperature, so that the organic electroluminescent compound with high quality is obtained.
Devices prepared from the compounds provided by the present invention have excellent current and power efficiencies and long lifetimes.
The preparation method of the organic electroluminescent compound provided by the invention is simple and feasible, has high yield and is suitable for industrial production.
Detailed Description
The invention provides an organic electroluminescent compound, which has the following structural formula:
wherein Ar is1And Ar2Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or an arylamine group; or are linked to an adjacent substituent(s) to form a mono-or polycyclic ring, in particular a C3-C30 alicyclic or aromatic ring, the carbon atom(s) of which may be replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur; preferably said Ar is1And Ar2Each independently selected from: a substituted or unsubstituted C6-C25 aryl, a substituted or unsubstituted C5-C22 heteroaryl, or a triarylamino group;further preferably Ar is1And Ar2Each independently selected from: substituted or unsubstituted C10-C21 aryl, substituted or unsubstituted C12-C18 heteroaryl, or triphenylamine; wherein the substituent is methyl or phenyl; x1、X2Each independently represents-O-, -S-, -SO2-、-C(R5)(R6)-、-N(R7) -, -Si-, -Sn-or-Ge-; r1To R4Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, a substituted or unsubstituted C1-C30 hydrocarbyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, -NR, cyano, carboxyl, nitro, hydroxyl, a substituted or unsubstituted C3-C30 hydrocarbyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C-C8632 heteroaryl group8R9、-SiR10R11R12、-SR13、-OR14、-COR15、-B(OR16)(OR17) (ii) a Or R1And R2Are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, particularly C3-C30, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; preferably naphthalene, anthracene or pyrene, or substituted naphthalene, anthracene or pyrene; wherein the substituents are methyl or phenyl; r5To R17Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, specifically C3-C30, aliphatic or aromatic ring; l is1、L2Each independently is a substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; l is2May or may not be present; l is a radical of an alcohol1Preferably benzene or deuterated benzene; l is a radical of an alcohol2Preferably benzene; a. b and d each independently represent an integer of 1 to 4; c represents an integer of 1 to 3; preferably a, b, c and d are all 1;
further preferably, the organic electroluminescent compound is selected from any one of chemical formulas 2 to 13:
further preferably, Ar is1And Ar2Each independently a substituent of the following structure:
wherein ". x" represents any position on the substituent group that may be attached to the N atom in chemical formula 1.
Most preferably, the organic electroluminescent compound is selected from any one of the following structures:
the invention also provides a preparation method of the organic electroluminescent compound, which comprises the following steps:
step 1, preparation of intermediate 1
After adding compound 2 and tetrahydrofuran to a reaction vessel, cooling the vessel under a nitrogen atmosphere, then adding n-butyllithium dropwise to the mixture, stirring the mixture at room temperature for reaction, and cooling; thereafter, compound 1 dissolved in tetrahydrofuran was added dropwise to the above mixture, the reaction temperature was allowed to warm to room temperature, the stirring reaction was continued, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1;
step 2, preparation of compound shown in chemical formula 1
After adding the intermediate 1, the compound 3 and dichloromethane to a reaction vessel, sufficiently replacing air with nitrogen three times, dropwise adding boron trifluoride ethyl ether dissolved in dichloromethane to the above mixture, stirring the reaction at room temperature, quenching with distilled water, and extracting the mixture with dichloromethane, followed by drying the extracted organic layer using sodium sulfate and removing the solvent using a rotary evaporator, purifying the remaining substance by column chromatography to obtain the compound represented by chemical formula 1;
the synthetic route is as follows:
wherein R is1To R4、X1、X2、Ar1、Ar2、L1、L2And a, b, c, d are as defined in the above chemical formula 1, and Hal represents halogen.
Preferably, the step 1 specifically comprises the following steps:
after compound 2 and 200mL of tetrahydrofuran were added to a reaction vessel, the vessel was cooled to-78 ℃ under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, after the mixture was stirred at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃, after which compound 1 dissolved in 200mL of tetrahydrofuran was added dropwise to the above mixture, after the addition, the reaction temperature was allowed to warm to room temperature, and the mixture was stirred for 16 hours, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1.
Preferably, the step 2 specifically comprises the following steps:
after adding intermediate 1, compound 3 and 500L of dichloromethane to the reaction vessel, sufficiently replacing air with nitrogen three times, boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was added dropwise to the above mixture, after stirring the mixture at room temperature for 2 hours, quenched with distilled water, and the mixture was extracted with dichloromethane, followed by drying the extracted organic layer with sodium sulfate and removing the solvent using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain the compound represented by chemical formula 1.
The present invention also provides an organic electroluminescent device comprising the compound of the structure represented by chemical formula 1 of the present invention.
The organic electroluminescent device includes:
the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer contains a compound with a structure shown in chemical formula 1; the compound of the structure of formula 1 may be present in the organic layer in a single form or mixed with other substances. That is, the above-mentioned compound may comprise the organic electroluminescent compound according to the present invention alone, or may further comprise conventional materials generally used for organic electroluminescent materials.
One of the first and second electrodes is an anode and the other is a cathode. The organic layer includes a light emitting layer, and further includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention may be contained in at least one of the light-emitting layer and the hole transport layer.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
The "organic layer" in the present invention refers to a term of all layers disposed between the first electrode and the second electrode of the organic electroluminescent device.
When the compound of the structure shown in chemical formula 1 is present in the light emitting layer in the organic layer, the compound of the structure shown in chemical formula 1 may serve as a light emitting host or be doped in other fluorescent hosts;
when the compound of the structure represented by chemical formula 1 is present in the hole transport layer or the hole injection layer in the organic layer, the compound of the structure represented by chemical formula 1 may serve as a hole transport layer, a hole injection layer, and a functional layer having both hole injection and hole transport.
The device prepared by the compound having the structure of formula 1 according to the present invention may be used in an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic Paper (e-Paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT).
The device can be used for forming an anode by evaporating metal, conductive oxides and alloys thereof on a substrate by using methods such as thin film evaporation, electron beam evaporation, physical vapor deposition and the like, and can also be used for evaporating a spin-coating (spin-coating) or a thin strip head; the layer number can also be reduced by molding (tape-casting), doctor-blading (sector-Printing), Screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging).
Example 1: preparation of Compound 1
After 2-bromo-9, 9,10, 10-tetramethyl-9, 10-dihydroanthracene (60mmol) and 200mL of tetrahydrofuran were added to the reaction vessel, the vessel was cooled to-78 ℃ under a nitrogen atmosphere. N-butyllithium (2.5M, 60mmol) was then slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours and cooled to-78 ℃. Thereafter, 9-fluorenone (60mmol) dissolved in 200mL tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly raised to room temperature, and the mixture was stirred for 16 hours. Then, an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give compound 1-1(20.0g, 80% MW:416.56 in yield).
After the compound 1-1(45mmol), triphenylamine (46mmol) and 500L of methylene chloride were charged in a reaction vessel, the air was sufficiently replaced with nitrogen three times. Boron trifluoride diethyl etherate (46mmol) dissolved in 100mL of dichloromethane was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, it was quenched with distilled water, and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give compound 1(25.76g, 89% MW:643.72 yield).
Example 2: preparation of Compound 6
Compound 6 was prepared according to the procedure of example 1 (81% yield, MW: 719.83). The difference from example 1 is that intermediates 1-6 were used instead of intermediate 1-1.
Example 3: preparation of Compound 19
Compound 19 was prepared according to the procedure of example 1, (yield 72%, MW: 900.11). The difference from example 1 is that intermediates 1-19 are used instead of intermediate 1-1 and intermediates 2-19 instead of intermediate 2-1.
Example 4: preparation of Compound 25
Compound 25 was prepared according to the procedure of example 1 (73% yield, MW: 857.22). The difference from example 1 is that intermediates 1-25 are used instead of intermediate 1-1 and intermediates 2-25 instead of intermediate 2-1.
Example 5: preparation of Compound 34
Compound 34 was prepared according to the procedure of example 1, (80% yield, MW: 947.33). The difference from example 1 is that intermediates 1-34 are used instead of intermediate 1-1 and intermediates 2-34 are used instead of intermediate 2-1.
Example 6: preparation of Compound 40
Compound 40 was prepared according to the procedure of example 1 (75% yield, MW: 849.11). The difference from example 1 is that intermediate 1-40 was used instead of intermediate 1-1 and intermediate 2-40 was used instead of intermediate 2-1.
Example 7: preparation of Compound 52
Compound 52 was prepared according to the procedure of example 1 (76% yield, MW: 799.24). The difference from example 1 is that intermediates 1-52 were used instead of intermediate 1-1 and intermediates 2-52 were used instead of intermediate 2-1.
Example 8: preparation of Compound 57
Compound 57 was prepared according to the procedure of example 1 (84% yield, MW: 741.57). The difference from example 1 is that intermediates 1-57 were used instead of intermediate 1-1.
The compounds of chemical formulas 1 to 75 other than the compounds of the above examples, which are not listed here, were prepared according to the above preparation methods.
Example 9: production of organic electroluminescent devices containing Compound 1
Coating with a thickness of
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. 4,4' -tri [ 2-naphthyl phenylamino ] with the thickness of 50nm is evaporated on the prepared ITO transparent electrode]Triphenylamine (2-TNATA) as a hole injection layer. Then, compound 1 was vacuum-evaporated on the formed hole injection layer to form a hole transport layer having a thickness of 30 nm. Then, 9, 10-bis (2-naphthyl) Anthracene (ADN), which is a blue host material, and bis (4, 6-difluorophenylpyridine-N, C2), which is a dopant material, iridium picolinate (FIrpic), which is a dopant material, were deposited on the hole transport layer to a thickness of 30 nm. The weight ratio of host material to dopant material was 95: 5. TPBi with a thickness of 40nm is vacuum-evaporated on the light-emitting layer to form a hole blocking layer and an electron transporting layer. Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 0.5nm as an electron injection layer. And finally, evaporating aluminum with the thickness of 150nm as a cathode, thereby completing the preparation of the organic electroluminescent device. And testing the performance luminescence characteristics of the obtained device, wherein a KEITHLEY2400 type source measuring unit and a CS-2000 spectral radiance luminance meter are adopted for measurement so as to evaluate the driving voltage, the luminescence brightness and the luminescence efficiency.
Example 10: production of organic electroluminescent device containing Compound 6
An organic electroluminescent device containing compound 6 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 6.
Example 11: production of organic electroluminescent device comprising Compound 19
An organic electroluminescent device containing compound 19 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 19.
Example 12: production of organic electroluminescent device comprising Compound 25
An organic electroluminescent device containing compound 25 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 25.
Example 13: production of organic electroluminescent device comprising Compound 34
An organic electroluminescent device containing compound 34 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 34.
Example 14: production of organic electroluminescent devices comprising Compound 40
An organic electroluminescent device containing compound 40 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 40.
Example 15: production of organic electroluminescent devices comprising Compound 52
An organic electroluminescent device containing compound 52 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 52.
Example 16: production of organic electroluminescent device comprising Compound 57
An organic electroluminescent device containing compound 57 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 57.
Example 17: production of organic electroluminescent devices comprising Compound 60
An organic electroluminescent device containing compound 60 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 60.
Example 18: production of organic electroluminescent device comprising Compound 61
An organic electroluminescent device containing compound 61 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 61.
Example 19: production of organic electroluminescent device comprising Compound 63
An organic electroluminescent device containing compound 63 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 63.
Example 20: production of organic electroluminescent device comprising Compound 65
An organic electroluminescent device containing compound 65 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 65.
Example 21: production of organic electroluminescent devices comprising Compound 66
An organic electroluminescent device containing compound 66 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 66.
Example 22: production of organic electroluminescent device comprising Compound 67
An organic electroluminescent device containing compound 67 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 67.
Example 23: production of organic electroluminescent devices containing Compound 68
An organic electroluminescent device containing compound 68 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 68.
Example 24: production of organic electroluminescent device comprising Compound 69
An organic electroluminescent device containing compound 69 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 69.
Example 25: production of organic electroluminescent device comprising Compound 70
An organic electroluminescent device containing compound 70 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 70.
Example 26: production of organic electroluminescent device containing Compound 71
An organic electroluminescent device containing compound 71 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 71.
Example 27: production of organic electroluminescent devices containing Compound 72
An organic electroluminescent device containing compound 72 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 72.
Example 28: production of organic electroluminescent device containing Compound 73
An organic electroluminescent device containing compound 73 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 73.
Example 29: fabrication of organic electroluminescent device containing Compound 74
An organic electroluminescent device containing compound 74 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 74.
Example 30: fabrication of organic electroluminescent device containing Compound 75
An organic electroluminescent device containing compound 75 was produced in the same manner as in example 9 except that compound 1 was replaced with compound 75.
Comparative example 1:
the material of the hole transport layer was replaced from compound 1 by N '-bis (1-naphthyl) -N, N' -diphenyl- (1,1 '-biphenyl) -4,4' -diamine (NPD) according to the method of example 9.
Table 1 shows the results of the test of the light emitting characteristics of the compounds prepared in the examples of the present invention and the light emitting devices prepared by a-NPD.
TABLE 1
From the above table, it can be seen that the compound provided by the present invention has a suitable glass transition temperature, and the light emitting efficiency and lifetime of the device prepared by using the compound of the present invention as a hole transport layer are significantly improved compared with the device prepared by using NPD as a hole transport layer.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. An organic electroluminescent compound, characterized by being selected from any one of chemical formulas 2 to 13:
wherein Ar is1And Ar2Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or an arylamine group;
or are linked to an adjacent substituent(s) to form a mono-or polycyclic ring, in particular a C3-C30 alicyclic or aromatic ring, the carbon atom(s) of which may be replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur;
R1to R4Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, a substituted or unsubstituted C1-C30 hydrocarbyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C3-C7 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3832 cycloalkyl group, or a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C7 cycloalkyl group, or a substituted or unsubstituted C6-C30 heteroaryl group, or a substituted or unsubstituted C3-C3-C3-C3-C-3-C-3Or unsubstituted C3-C30 heteroaryl, -NR8R9、-SiR10R11R12、-SR13、-OR14、-COR15、-B(OR16)(OR17)；
Or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, specifically C3-C30, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
R8to R17Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic, specifically C3-C30, aliphatic or aromatic ring;
L1、L2each independently is a substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; l is2May or may not be present;
a. b and d each independently represent an integer of 1 to 4;
c represents an integer of 1 to 3.
2. The organic electroluminescent compound according to claim 1, wherein Ar is Ar1And Ar2Each independently selected from: a substituted or unsubstituted C6-C25 aryl, a substituted or unsubstituted C5-C22 heteroaryl, or a triarylamino group.
3. The organic electroluminescent compound according to claim 1, wherein Ar is Ar1And Ar2Each independently selected from: a substituted or unsubstituted C10-C21 aryl, a substituted or unsubstituted C12-C18 heteroaryl, or a triphenylamine group.
4. The organic electroluminescent compound according to claim 3, wherein the substituent is a methyl group or a phenyl group.
5. The organic electroluminescent compound according to claim 1, wherein Ar is Ar1And Ar2Each independently selected from the group of substituents of the following structures:
wherein ". x" represents any position on the substituent group that may be attached to the N atom in chemical formula 1.
6. An organic electroluminescent compound, characterized by being selected from any one of the following structures:
7. a method for preparing an organic electroluminescent compound according to any one of claims 1 to 6, comprising the steps of:
step 1, preparation of intermediate 1
After adding compound 2 and tetrahydrofuran to a reaction vessel, cooling the vessel under a nitrogen atmosphere, then adding n-butyllithium dropwise to the mixture, stirring the mixture at room temperature for reaction, and cooling; thereafter, compound 1 dissolved in tetrahydrofuran was added dropwise to the above mixture, the reaction temperature was allowed to warm to room temperature, the stirring reaction was continued, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1;
step 2, preparation of compound shown in chemical formula 1
After adding the intermediate 1, the compound 3 and dichloromethane to a reaction vessel, sufficiently replacing air with nitrogen three times, dropwise adding boron trifluoride ethyl ether dissolved in dichloromethane to the above mixture, stirring the reaction at room temperature, quenching with distilled water, and extracting the mixture with dichloromethane, followed by drying the extracted organic layer using sodium sulfate and removing the solvent using a rotary evaporator, purifying the remaining substance by column chromatography to obtain the compound represented by chemical formula 1;
the synthetic route is as follows:
wherein Hal represents halogen and the other substituents are as defined in claims 1 to 6.
8. The method for producing an organic electroluminescent compound according to claim 7, wherein the step 1 specifically comprises the steps of:
after adding compound 2 and 200mL of tetrahydrofuran in a reaction vessel, the vessel was cooled to-78 ℃ under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, after stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃, after which compound 1 dissolved in 200mL of tetrahydrofuran was added dropwise to the above mixture, after addition, the reaction temperature was warmed to room temperature, and the mixture was stirred for 16 hours, then an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, then the extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain intermediate 1;
the step 2 specifically comprises the following steps:
after adding intermediate 1, compound 3 and 500L of dichloromethane to the reaction vessel, sufficiently replacing air with nitrogen three times, boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was added dropwise to the above mixture, after stirring the mixture at room temperature for 2 hours, quenched with distilled water, and the mixture was extracted with dichloromethane, followed by drying the extracted organic layer with sodium sulfate and removing the solvent using a rotary evaporator, and the remaining substance was purified by column chromatography to obtain the compound represented by chemical formula 1.
9. An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1 to 6.
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| KR102676758B1 (en) * | 2020-08-24 | 2024-06-19 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
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| KR102649337B1 (en) * | 2020-09-17 | 2024-03-19 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| CN112079731B (en) * | 2020-09-18 | 2023-04-28 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
| CN113801026B (en) * | 2021-09-27 | 2022-08-23 | 陕西莱特光电材料股份有限公司 | Nitrogen-containing compound, and electronic component and electronic device comprising same |
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