CN108383842B - Organic light-emitting compound, preparation method thereof and organic light-emitting device - Google Patents

Organic light-emitting compound, preparation method thereof and organic light-emitting device Download PDF

Info

Publication number
CN108383842B
CN108383842B CN201810141134.3A CN201810141134A CN108383842B CN 108383842 B CN108383842 B CN 108383842B CN 201810141134 A CN201810141134 A CN 201810141134A CN 108383842 B CN108383842 B CN 108383842B
Authority
CN
China
Prior art keywords
compound
organic light
formula
emitting
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810141134.3A
Other languages
Chinese (zh)
Other versions
CN108383842A (en
Inventor
尹恩心
林文晶
彭勃
王辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Sheng Xi Photoelectric Technology Co Ltd
Original Assignee
Shanghai Sheng Xi Photoelectric Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Sheng Xi Photoelectric Technology Co Ltd filed Critical Shanghai Sheng Xi Photoelectric Technology Co Ltd
Priority to CN201810141134.3A priority Critical patent/CN108383842B/en
Publication of CN108383842A publication Critical patent/CN108383842A/en
Application granted granted Critical
Publication of CN108383842B publication Critical patent/CN108383842B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of organic electroluminescent devices, in particular to an organic luminescent compound, a preparation method thereof and an organic luminescent device. The organic luminescent compound provided by the invention is prepared by selecting a specific parent nucleus structure and a substituent R1、R2And R3And Ar1、Ar2And Ar3The obtained compound with a novel structure is used as an electron transport layer material to be applied to an organic light-emitting device, so that the light-emitting efficiency of the device is improved, and the service life is long. The preparation method of the organic luminescent compound provided by the invention has the advantages of easily available raw materials and simple preparation method, and is suitable for large-scale production.

Description

Organic light-emitting compound, preparation method thereof and organic light-emitting device
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to an organic luminescent compound, a preparation method thereof and an organic luminescent device.
Background
An electroluminescent device (EL device) as a self-luminous display device has advantages of a wide viewing angle, a good contrast ratio, and a fast response speed. In 1987, Kodak (Eastman Kodak) corporation first developed an organic electroluminescent device using a low-molecular aromatic diamine and an aluminum complex as a material of a light emitting layer.
An organic electroluminescent device (OLED) is a device that converts electric energy into light energy by applying a voltage to an organic light emitting material, and generally has a structure including an anode (anode), a cathode (cathode), and an organic layer between the anode and the cathode. The organic layer in the organic electroluminescent device may be formed of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The electron transport material is a material that transports electrons from the cathode to the light-emitting layer smoothly and suppresses the movement of holes that are not combined in the light-emitting layer to increase the chance of recombination of holes and electrons in the light-emitting layer, and generally, a material having excellent electron affinity can be used as the electron transport material. An organometallic complex having a light-emitting function like Alq3 is excellent in an electron-transporting ability and is used as an electron-transporting material. However, Alq3 has problems in moving to other layers and degrading color purity when used in blue devices. Therefore, a new electron transport material is required to be available, which does not have the above-mentioned problems, has high electron affinity, and exhibits high luminous efficiency due to rapid electron mobility when used in an organic electroluminescent device.
Disclosure of Invention
The invention aims to provide an organic light-emitting compound, a preparation method thereof and an organic light-emitting device.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an organic light-emitting compound having the formula:
Figure GDA0002298542140000021
in the formula:
R1is aryl;
R2the structure of (A) is as follows:
Figure GDA0002298542140000022
wherein X is nitrogen, oxygen or sulfur; r2The position indicated by "-" and on the benzene ring to which it is attached;
R3is hydrogen;
Ar1is any one of the following structures:
Figure GDA0002298542140000023
Figure GDA0002298542140000031
wherein X is C or N, at least one is N,
Figure GDA0002298542140000032
is a connecting part with N;
Ar2and Ar3Each independently selected from hydrogen, substituted or unsubstituted phenyl, or substituted or unsubstituted aromatic heterocyclic group.
In the above technical scheme, R1Is phenyl, Ar2And Ar3Each independently selected from hydrogen, a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 12 carbon atoms.
In the above technical scheme, R1Is phenyl, Ar2And Ar3Each independently selected from hydrogen, phenyl, biphenyl or dibenzothienyl.
In the above technical solution, the organic light emitting compound is any one of the following structures:
Figure GDA0002298542140000033
Figure GDA0002298542140000041
a method for preparing an organic light-emitting compound, comprising the steps of:
mixing a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) for reaction to obtain an organic luminescent compound with a structure shown in a formula (I);
Figure GDA0002298542140000042
according to the invention, the compound with the structure of formula (II) and the compound with the structure of formula (III) are mixed and reacted to obtain the compound with the structure of formula (I), and in the invention, R in the compound with the structure of formula (II)1、R2And R3The selection ranges are as defined for the compounds described above; ar in the compound with the structure of the formula (III)1、Ar2And Ar3The substituents are also selected as defined in the above compounds, the conditions for the reaction are not particularly limited in the present invention, and those skilled in the art can select appropriate reaction conditions according to the existing reaction. In addition, the compound with the structure of formula (II) and the compound with the structure of formula (III) are not particularly limited in source, and can be prepared by the preparation method known in the field.
The invention also provides an organic light-emitting device, wherein the electron transport layer of the organic light-emitting device is the organic light-emitting compound.
The invention has the beneficial effects that:
the organic luminescent compound provided by the invention is prepared by selecting a specific parent nucleus structure and a substituent R1、R2And R3And Ar1、Ar2And Ar3The obtained compound with a novel structure is used as an electron transport layer material to be applied to an organic light-emitting device, so that the light-emitting efficiency of the device is improved, and the service life is long.
The preparation method of the organic luminescent compound provided by the invention has the advantages of easily available raw materials and simple preparation method, and is suitable for large-scale production.
Detailed Description
The invention provides an organic luminescent compound, which has the following structural formula:
Figure GDA0002298542140000051
in the formula: r1Is aryl;
R2the structure of (A) is as follows:
Figure GDA0002298542140000061
wherein X is nitrogen, oxygen or sulfur; r2The position indicated by "-" and on the benzene ring to which it is attached;
R3is hydrogen;
Ar1is any one of the following structures:
Figure GDA0002298542140000062
wherein X is C or N, at least one is N,
Figure GDA0002298542140000063
is a connecting part with N;
Ar2and Ar3Each independently selected from hydrogen, substituted or unsubstituted phenyl, or substituted or unsubstituted aromatic heterocyclic group.
Preferably, R is1Is phenyl, Ar2And Ar3Each independently selected from hydrogen, a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 12 carbon atoms.
Preferably, R is1Is phenyl, Ar2And Ar3Each independently selected from hydrogen, phenyl, biphenyl or dibenzothienyl.
Most preferably, the organic light-emitting compound is any one of the following structures:
Figure GDA0002298542140000071
Figure GDA0002298542140000082
the invention also provides a preparation method of the organic luminescent compound, which comprises the following steps:
mixing a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) for reaction to obtain an organic luminescent compound with a structure shown in a formula (I);
Figure GDA0002298542140000081
according to the invention, a compound of formula (II) and a compound of formula (II)I) Mixing the compounds with the structure for reaction to obtain the compound with the structure of formula (I), wherein R in the compound with the structure of formula (II) in the invention1、R2And R3The selection ranges are as defined for the compounds described above; ar in the compound with the structure of the formula (III)1、Ar2And Ar3The substituents are also selected as defined in the above compounds, the conditions for the reaction are not particularly limited in the present invention, and those skilled in the art can select appropriate reaction conditions according to the existing reaction. In addition, the compound with the structure of formula (II) and the compound with the structure of formula (III) are not particularly limited in source, and can be prepared by the preparation method known in the field.
The invention also provides an organic light-emitting device, wherein the electron transport layer of the organic light-emitting device is the organic light-emitting compound.
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The compound of formula (III) is preferably a substance of the following structure:
Figure GDA0002298542140000091
synthesis of intermediate 1:
to a 1L round bottom flask were added reactants 1-1(19.48g, 89mmol), pinacol diboron (27g, 106mmol), bis (triphenylphosphine) palladium dichloride (3.1g, 4.45mmol), potassium acetate (KOAc) (22g, 222mmol) and 1, 4-dioxane (445mL) in this order, heated and stirred to reflux, after 3 hours, the mixture was extracted with dichloromethane and deionized water, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered with suction, the resulting solid was dissolved with chloroform and isolated by column chromatography to give intermediate 1-1(13.08g, 60%).
TABLE 1
Figure GDA0002298542140000092
According to the above preparation method, intermediate 1-2 and intermediate 1-3 were prepared by replacing reactant 1-1 with the reactant of sequence number 2 or 3 in the same molar ratio.
Synthesis of intermediates 2 and 3:
0.10mol of intermediate 1-1, 0.10mol of diiodoaniline and 7.0g of palladium tetratriphenylphosphine were put into a reaction flask, 600mL of toluene and aqueous sodium carbonate solution (2N, 250mL) were added, and the mixture was subjected to an oil bath under nitrogen protection at 90 ℃ for reaction overnight. And (3) cooling, separating liquid and spin-drying the reacted system, fully dissolving the obtained residue with dichloromethane, adding an equal amount of petroleum ether, passing through a silica gel funnel, and reacting with dichloromethane: petroleum ether is 1: 2 (vol.%) until no product was decanted, the filtrate was collected and the solvent was spun off to afford intermediate 2-1(0.081mol, y 81%).
0.081mol of intermediate 2-1, hydrochloric acid (10mL) and acetic acid (350mL) were added to a 500mL two-necked flask under nitrogen, and the mixture was refluxed and stirred for 24 hours, and the reaction mixture was cooled at room temperature, and then the solid was filtered, washed with methanol several times, and separated with a hexane silica gel column to obtain intermediate 3-1(11.27g, y ═ 50%).
TABLE 2
Figure GDA0002298542140000101
Figure GDA0002298542140000111
According to the above preparation method, reaction product 2 and intermediate 1 were replaced with the corresponding substances shown in the table, and intermediate 2-2-intermediate 2-14 and intermediate 3-2-intermediate 3-14 were prepared using the same molar weight ratio.
Synthesis of intermediate 3':
to a 500mL round-bottom flask were added successively intermediate 3-1(8.4g, 20.6mmol), fluorobenzene (2.38g, 24.8mmol), palladium acetate (232mg, 1.0mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (850mg, 2.0mmol), sodium tert-butoxide (5g, 51.6mmol) and o-xylene (200 mL) and stirred at 180 ℃ for 2 hours, the reaction mixture was worked up with ethyl acetate/water, the residual water was removed with magnesium sulfate, and the reaction mixture was distilled under reduced pressure to give intermediate 3' -1(4.45g, 55%) which was isolated by column chromatography using dichloromethane/n-hexane.
TABLE 3
Figure GDA0002298542140000121
Intermediate 3 '-2-intermediate 3' -5 was prepared according to the above preparation method by replacing intermediate 3-1 with the corresponding substance shown in the table and using the same molar ratio.
Synthesis of intermediate 4:
Figure GDA0002298542140000131
acenaphthene-5 (2aH) -one (111mmol) was added to the flask, and after dissolving in tetrahydrofuran (554mL), phenylmagnesium bromide (36.9mL) was slowly added dropwise at 0 deg.C, and stirred at room temperature for 24 hours, after completion of the reaction, the organic layer was extracted with ethyl acetate, and the resulting organic layer was freed of residual water using anhydrous magnesium sulfate, and separated by column chromatography to give 1-phenyl-1H-benzonaphthalen-1-ol (21.5g, 75%).
1-phenyl-1H-benzonaphthalen-1-ol (17.5g, 67.7mmol) and bromobenzene (10.6, 67.7mmol) were dissolved in dichloromethane (450mL) in a flask, a solution of diphosphorus pentoxide in methanesulfonic acid (0.04mL, 1.35mmol) was added dropwise to the reaction mixture, the mixture was stirred for ten minutes, and after the reaction was completed, a sodium bicarbonate solution was added to extract the organic layer with dichloromethane. Residual water was removed with anhydrous magnesium sulfate and the residue was separated by column chromatography to give 1- (4-bromophenyl) -1-phenyl-1H-benzonaphthalene (24.2g, 90%).
To a 1-L round-bottom flask were added 1- (4-bromophenyl) -1-phenyl-1H-benzonaphthalene (35.4g, 89mmol), pinacol diboron (27g, 106mmol), bis (triphenylphosphine) palladium dichloride (3.1g, 4.45mmol), potassium acetate (KOAc) (22g, 222mmol) and 1, 4-dioxane (445mL) in this order, and the mixture was heated under stirring to reflux for 3 hours, then extracted with dichloromethane and deionized water, the dichloromethane layer was dried over anhydrous magnesium sulfate and then filtered under suction, and the resulting solid was dissolved with chloroform and then isolated by column chromatography to give intermediate 4(23.73g, 60%).
Intermediate 5 and intermediate 6 synthesis:
to a 2L round bottom flask was added 78mmol of intermediate 3-1, 93mmol of intermediate 4, 3.1mmol of tetrakis (triphenylphosphine) palladium, 195mmol of sodium carbonate, 400mL of toluene, 50mL of ethanol and 100mL of water in that order, and the mixture was stirred overnight at 130 deg.C, and the reaction mixture was dissolved with ethyl acetate/H2O treatment, drying over anhydrous magnesium sulfate, vacuum distillation, and column chromatography of the crude product using dichloromethane/n-hexane gave intermediate 5-1, (60.84mmol, 78%).
Adding 57.8mmol of intermediate 5-1, triethyl phosphite 200mL and o-dichlorobenzene 200mL into a 1L round-bottom flask in sequence, stirring at 150 ℃ for 2 hours, carrying out rotary evaporation on a reaction mixed solution to obtain a solid, and adding dichloromethane to a crude product: column chromatography of n-hexane afforded intermediate 6-1(45.66mmol, 79%).
TABLE 4
Figure GDA0002298542140000141
Figure GDA0002298542140000151
According to the above preparation method, intermediate 3 or 3' was replaced with the corresponding substance described in the table, and intermediate 5-2-intermediate 5-14 and intermediate 6-2-intermediate 6-14 were prepared using the same molar ratio.
Synthesizing target compounds 1-16:
20.6mmol of intermediate 6, 24.8mmol of the compound of formula (III), 1.0mmol of palladium acetate, 2.0mmol of 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, 51.6mmol of sodium tert-butoxide and 200mL of o-xylene are added in this order to a 500mL round-bottomed flask, the mixture is stirred at 180 ℃ for 2 hours, the reaction mixture is worked up with ethyl acetate/water, the residual water is removed with magnesium sulfate, the distillation is carried out under reduced pressure, and the crude product is separated by column chromatography with dichloromethane: n-hexane to give the desired compound 1(11.54mmol, 56%).
TABLE 5
Figure GDA0002298542140000161
Figure GDA0002298542140000171
Figure GDA0002298542140000181
According to the above preparation method, the intermediate 6 and the compound represented by the formula (III) are replaced by the corresponding substances shown in the table, and the target compounds 2 to 16 are prepared by using the same molar weight ratio.
The target compounds 1-16 were labeled as P1-P16, and FD-MS measurements were made, the results of which are shown in Table 6.
TABLE 6
Serial number FD-MS Serial number FD-MS
P1 m/z＝879.34(C54H41N5＝880.94) P2 m/z＝803.30(C56H37N5＝803.95)
P3 m/z＝802.31(C59H38N4＝802.96) P4 m/z＝801.31(C60H39N3＝801.97)
P5 m/z＝803.30(C58H57N5＝803.95) P6 m/z＝878.34(C65H42N4＝879.06)
P7 m/z＝820.27(C58H36N4S＝821.00) P8 m/z＝925.26(C65H39N3S2＝926.16)
P9 m/z＝896.30(C64H40N4S＝897.09) P10 m/z＝743.24(C53H33N3S＝743.91)
P11 m/z＝773.20(C63H31N3S2＝773.96) P12 m/z＝803.29(C59H37N3O＝803.29)
P13 m/z＝833.25(C59H35N3OS＝833.99) P14 m/z＝804.29(C58H36N4O＝804.93)
P15 m/z＝727.26(C53H33N3O＝727.85) P16 m/z＝757.22(C53H31N3OS＝757.90)
Preparation and evaluation of organic light-emitting device
Experimental example Green light organic light emitting device (Electron transport layer)
First, 4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (hereinafter, abbreviated as 2-TNATA) having a thickness of 60nm was vacuum-deposited on the indium tin oxide layer (anode) formed on the glass substrate to form a hole injection layer, and N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (hereinafter, abbreviated as NPD) having a thickness of 60nm was vacuum-deposited on the formed hole injection layer to form a hole transport layer. Then, a mixture containing 4,4' -bis (9-carbazole) biphenyl as a host (hereinafter abbreviated as "CBP") and tris (2-phenylpyridine) iridium as a dopant was vacuum-deposited on the hole transport layer to a thickness of 30nm, and the weight ratio of the host material to the dopant was 95: 5. Subsequently, a hole-blocking layer was formed on the light-emitting layer by vacuum deposition of bis (2-methyl-8-quinolinolato-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (hereinafter referred to as "BAlq") having a thickness of 10 nm. An electron transport layer was formed on the hole-blocking layer by vacuum deposition of any of the compounds P1 to P16 of the present invention having a thickness of 40 nm. Subsequently, lithium fluoride of an alkali metal halide was deposited in a thickness of 0.2nm in the hole transport layer to form an electron injection layer. Then, aluminum was evaporated to a thickness of 150nm to form a cathode, thereby completing the fabrication of an organic light emitting device.
Comparative example (1)
An organic light-emitting device was produced in the same manner as in the above experimental example except that the compound of the present invention was replaced with comparative compound 1 as an electron transporting layer material.
< comparative Compound 1> Alq3
Figure GDA0002298542140000191
Comparative example (2)
An organic light-emitting device was produced in the same manner as in the above experimental example except that the compound of the present invention was replaced with comparative compound 2 as an electron transporting layer material.
< comparative Compound 2>
Figure GDA0002298542140000201
Comparative example (3)
An organic light-emitting device was produced in the same manner as in the above experimental example except that the compound of the present invention was replaced with comparative compound 3 as an electron transporting layer material.
< comparative Compound 3>
Figure GDA0002298542140000202
The organic light emitting device prepared above was applied with a forward DC bias voltage, and the electroluminescence characteristics were measured by PR-650 photometry equipment of Photo Research corporation at 5000cd/m2The life of T95 was measured using a life measuring device manufactured by McScience, and the results are shown in the table.
The following [ table 2] shows the device preparation and evaluation results of experimental examples (experimental example (1) to (59)) and comparative examples (comparative example (1) to (3)) to which the compound of the present invention was applied.
TABLE 7
Figure GDA0002298542140000203
Figure GDA0002298542140000211
As can be seen from table 7, using the compound of the present invention as an electron transport layer in an organic light emitting device, the following advantages, lower driving voltage, high efficiency and long lifetime, were exhibited as compared to a device prepared with comparative compound 1Alq3 as an electron transport layer.
As compared with the organic light emitting devices of comparative compounds 2 and 3, it is understood that when the compounds of the present invention are used, the devices require lower driving voltages and are significantly improved in yield and lifetime. This can be demonstrated that the compound of the present invention better maintains the charge balance of holes and electrons in the light-emitting layer than comparative compounds 2 and 3.
While the preferred embodiments of the present invention have been described, it will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, but various changes and modifications may be made without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention as hereinafter claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. An organic light-emitting compound having the following structural formula:
Figure FDA0002298542130000011
in the formula:
R1is phenyl;
R2the structure of (A) is as follows:
Figure FDA0002298542130000012
wherein X is oxygen or sulfur; r2The position indicated by "-" and on the benzene ring to which it is attached;
R3is hydrogen;
Ar1is any one of the following structures:
Figure FDA0002298542130000013
wherein
Figure FDA0002298542130000014
Is a connecting part with N;
Ar2and Ar3Each independently selected from hydrogen, phenyl, biphenyl or dibenzothienyl.
2. The organic light-emitting compound of claim 1, wherein the organic light-emitting compound is any one of the following structures:
Figure FDA0002298542130000021
Figure FDA0002298542130000031
3. a method for producing an organic light-emitting compound according to claim 1, comprising the steps of:
mixing a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) for reaction to obtain an organic luminescent compound with a structure shown in a formula (I);
Figure FDA0002298542130000032
in the formula:
R1is phenyl;
R2the structure of (A) is as follows:
Figure FDA0002298542130000033
wherein X is oxygen or sulfur; r2The position indicated by "-" and on the benzene ring to which it is attached;
R3is hydrogen;
Ar1is any one of the following structures:
Figure FDA0002298542130000034
wherein
Figure FDA0002298542130000035
Is a connecting part with N;
Ar2and Ar3Each independently selected from hydrogen, phenyl, biphenyl or dibenzothienyl.
4. An organic light emitting device having the organic light emitting compound according to claim 1 as an electron transport layer material.
CN201810141134.3A 2018-02-11 2018-02-11 Organic light-emitting compound, preparation method thereof and organic light-emitting device Active CN108383842B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810141134.3A CN108383842B (en) 2018-02-11 2018-02-11 Organic light-emitting compound, preparation method thereof and organic light-emitting device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810141134.3A CN108383842B (en) 2018-02-11 2018-02-11 Organic light-emitting compound, preparation method thereof and organic light-emitting device

Publications (2)

Publication Number Publication Date
CN108383842A CN108383842A (en) 2018-08-10
CN108383842B true CN108383842B (en) 2020-03-13

Family

ID=63068663

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810141134.3A Active CN108383842B (en) 2018-02-11 2018-02-11 Organic light-emitting compound, preparation method thereof and organic light-emitting device

Country Status (1)

Country Link
CN (1) CN108383842B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12058930B2 (en) 2018-02-20 2024-08-06 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and electronic apparatus
US20200388768A1 (en) * 2018-02-20 2020-12-10 Idemitsu Kosan Co.,Ltd. Organic electroluminescence device and electronic apparatus
CN112480113B (en) * 2020-11-30 2022-03-08 吉林奥来德光电材料股份有限公司 Spiro nitrogen-containing organic luminescent compound, and preparation method and application thereof
CN112375088B (en) * 2020-11-30 2022-05-20 吉林奥来德光电材料股份有限公司 Spiro nitrogen-containing organic luminescent compound, and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131855A2 (en) * 2009-05-13 2010-11-18 덕산하이메탈(주) Compound containing a 5-membered heterocycle and organic light-emitting diode using same, and terminal for same
KR102427918B1 (en) * 2014-04-29 2022-08-03 롬엔드하스전자재료코리아유한회사 Electron transport material and an organic electroluminescence device comprising the same

Also Published As

Publication number Publication date
CN108383842A (en) 2018-08-10

Similar Documents

Publication Publication Date Title
KR102065989B1 (en) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
KR101974860B1 (en) organic light-emitting diode with low operating voltage and long lifetime
KR102061571B1 (en) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
JP2022507076A (en) New boron compounds and organic light emitting devices containing them
KR102383344B1 (en) Novel organic light-emitting diode including antracene derivatives
KR102144446B1 (en) Organic Compound for organic light emitting diode and an organic light emitting diode including the same with long life
CN108383842B (en) Organic light-emitting compound, preparation method thereof and organic light-emitting device
JP2017515817A (en) Heterocyclic compound containing aromatic amine group and organic light emitting device containing the same
JP7488912B2 (en) NOVEL ANTHRACENE COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE COMPRISING THE SAME
KR20140134884A (en) An electroluminescent compound and an electroluminescent device comprising the same
KR102263822B1 (en) Organic compounds and organic electro luminescence device comprising the same
KR102503217B1 (en) Organic Compound for organic light emitting diode and an organic light emitting diode including the same with long life
KR20100137243A (en) Anthracene derivative and organic electroluminescence device using the same
KR20150145131A (en) Novel heterocyclic compounds and organic light-emitting diode including the same
CN110724062A (en) Fluorene compound, preparation method thereof and organic electroluminescent device
KR20150144121A (en) An organoelectro luminescent compounds and organoelectro luminescent device using the same
JP6498245B2 (en) Compound and organic electronic device using the same
CN108165264A (en) A kind of organic luminescent compounds and its preparation method and application
KR20140103394A (en) Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same
CN112062765B (en) Organic photoelectric luminescent compound and preparation method thereof
CN108373463A (en) Organic luminescent compounds and preparation method thereof and organic electroluminescence device
KR20150114658A (en) An organoelectro luminescent compounds and organoelectro luminescent device using the same
KR20180065934A (en) Compound and organic electronic device using the same
KR102059957B1 (en) Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
JP6539821B2 (en) Compound and organic electronic device using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant