CN111233861A - Organic light-emitting compound, preparation method thereof and organic electroluminescent device - Google Patents
Organic light-emitting compound, preparation method thereof and organic electroluminescent device Download PDFInfo
- Publication number
- CN111233861A CN111233861A CN202010090237.9A CN202010090237A CN111233861A CN 111233861 A CN111233861 A CN 111233861A CN 202010090237 A CN202010090237 A CN 202010090237A CN 111233861 A CN111233861 A CN 111233861A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- organic
- compound
- organic light
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/16—Peri-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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic luminescent compound, a preparation method thereof and an organic electroluminescent device, belonging to the field of chemical synthesis and photoelectric materials, and the structural general formula is as follows:
Description
Technical Field
The invention relates to the field of chemical synthesis and photoelectric materials, in particular to an organic light-emitting compound, a preparation method thereof and an organic electroluminescent device.
Background
Organic Electroluminescence (EL) has characteristics of self-luminescence, bright and bright color, thin thickness, light weight, etc., and has gradually developed into the most advantageous technology in the field of new generation flat panel display. However, the development of the organic electroluminescent device is restricted by factors such as efficiency and life span. The most important factor determining the luminous efficiency of an organic EL device is a light emitting material. The light emitting material is required to have higher quantum efficiency, higher electron mobility, and higher hole mobility. In addition, a light-emitting layer formed of a light-emitting material needs to be uniform and stable.
Currently, a light emitting material can be prepared by combining a host material with a dopant material to improve color purity, light emitting efficiency, and stability. Among them, 4,4'-N, N' -dicarbazole-biphenyl (CBP) is a relatively wide host material currently used for phosphorescent materials.
However, when CBP is used as a host material of a phosphorescent light-emitting material represented by an iridium complex, CBP has characteristics of easily transporting holes and hardly transporting electrons, so that charge injection balance is disrupted, and excessive holes flow out to the electron transport layer side, which leads to a decrease in light-emitting efficiency of a finally produced organic electroluminescent device.
Disclosure of Invention
An object of an embodiment of the present invention is to provide an organic light emitting compound to solve the problems set forth in the background art described above.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an organic light-emitting compound having a general structural formula of formula I:
wherein Ar is one of substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 10-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 10-membered heteroaryl, substituted or unsubstituted 3-to 10-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, monocyclic or polycyclic C3-C30 aliphatic ring or 3-to 10-membered aromatic ring connected with adjacent substituent;
R1～R8each independently is one of hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted 3-to 10-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 10-membered heteroaryl, 3-to 10-membered aliphatic or 3-to 10-membered aromatic ring connected with adjacent substituents to form a single ring or multiple rings, C3-C30 aliphatic or C6-C30 aromatic ring connected with other substituents on the same ring to form a multiple ring.
Preferably, at least one carbon atom in the monocyclic or polycyclic C3-C30 aliphatic ring or 3-to 10-membered aromatic ring connected to the adjacent substituent(s) is replaced or not replaced by a heteroatom; at least one carbon atom in the C3-C30 aliphatic ring or the C6-C30 aromatic ring which forms a polycyclic ring with other substituents on the same ring is replaced or not replaced by a heteroatom.
Preferably, the heteroatom is independently one of O, S, N and Si.
Wherein the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are connected, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
Preferably, the organic light emitting compound has a chemical structural formula of one of formulas 1 to 80:
another object of an embodiment of the present invention is to provide a method for preparing the organic light emitting compound, including the steps of:
mixing a compound A with a general formula II, a compound B with a general formula III and toluene, placing the mixture in a protective atmosphere, and adding a palladium catalyst, tri-tert-butylphosphine and sodium tert-butoxide to react to obtain an intermediate C;
reacting a compound D with a general formula IV with butyl lithium, and then adding the intermediate C to react to obtain an intermediate E;
dissolving the intermediate E in a mixed solvent, and adding methanesulfonic acid for reaction to obtain an intermediate F;
mixing the intermediate F with a compound G with a general formula V, placing the mixture in a protective atmosphere, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate H;
reacting the intermediate H with triethyl phosphite to obtain an intermediate I;
and mixing the intermediate I, a compound J with a general formula VI and toluene, placing the mixture in a protective atmosphere, and adding a palladium catalyst, tri-tert-butylphosphine and sodium tert-butoxide for reaction to obtain the organic luminescent compound.
Preferably, the mixed solvent is a mixture of tetrahydrofuran and toluene.
The synthetic route of the preparation method is as follows:
another object of an embodiment of the present invention is to provide an organic electroluminescent device, which includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein part or all of the organic layer includes the organic light emitting compound.
Preferably, the organic layer includes a light emitting layer including the organic light emitting compound and a dopant material.
Preferably, the doping material is an iridium-containing compound.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
compared with the existing CBP used as a main material, the organic light-emitting compound provided by the embodiment of the invention can obviously reduce the driving voltage of the organic light-emitting device, improve the light-emitting efficiency and prolong the service life of the organic light-emitting device, thereby improving the practicability of the organic light-emitting device.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 of the embodiments.
Example 1
This example provides an organic light-emitting compound, whose chemical structural formula is formula 1 in the summary of the invention, and the reaction route of the preparation method of the organic light-emitting compound is as follows:
the specific preparation method comprises the following steps:
1) after A-1(128mmol) and B-1(140mmol) were added to a reaction vessel dissolved in toluene (300mL), Pd was added under nitrogen atmosphere2(dba)3(1.28mmol)、P(t-Bu)3(0.64mmol), t-BuONa (256 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate C-1(32.1g, 75.6% yield, MW: 331.8).
2) After addition of reaction D-1(108mmol) and tetrahydrofuran (THF, 500mL) to the reaction vessel, the temperature was reduced to-78 deg.C and butyllithium (n-BuLi, 108.mmol) was slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 2 h, intermediate C-1(90mmol) was added and stirred at room temperature for 5 h. Water was added 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 intermediate E-1(26.9g, 73.2% yield, MW: 409.91).
3) Intermediate E-1(63mmol) and THF (200mL) and toluene (200mL) were added to a reaction vessel and methanesulfonic acid (MSA, 630mmol) was added to the reaction solution. After stirring the mixture at room temperature for 8 hours, the mixture was extracted with distilled water and 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 intermediate F-1(21.0g, 85% yield, MW: 391.9).
4) Intermediate F-1(50mmol), reactant G-1(60mmol), toluene (300mL), ethanol (100mL), and H2O (100mL) was added to the reaction vessel and Pd (PPh) was added under nitrogen atmosphere3)4(0.50mmol), potassium carbonate (150 mmol). After the addition, the reaction temperature was slowly raised to 90 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate H-1(16g, 73.5% yield, MW: 478.55).
5) Intermediate H-1(35mmol) and triethyl phosphite (300mL) were stirred at reflux for 2 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate I-1(13.6g, 86.7% yield, MW: 446.55).
6) After intermediate I-1(28mmol) and reactant J-1(31mmol) were dissolved in toluene, Pd was added under a nitrogen atmosphere2(dba)3(0.28mmol)、P(t-Bu)3(1.4mmol) and t-BuONa (53.6 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. Purifying the remaining substance by column chromatography to obtain the organic luminescent compound (b)10.4g, 71.4% yield, MW: 522.65).
Example 2
This example provides an organic light-emitting compound having a chemical structural formula of formula 9 in the summary of the invention, and the reaction route of the preparation method of the organic light-emitting compound is as follows:
the specific preparation method comprises the following steps:
1) after A-9(128mmol) and B-9(140mmol) were added to a reaction vessel dissolved in toluene (300mL), Pd was added under nitrogen atmosphere2(dba)3(1.28mmol)、P(t-Bu)3(0.64mmol), t-BuONa (256 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate C-9(32.1g, 75.6% yield, MW: 331.8).
2) After addition of the reaction mixture D-9(108mmol) and THF (500mL) to the reaction vessel, the temperature was reduced to-78 deg.C and n-BuLi (108mmol) was slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 2 h, intermediate C-1(90mmol) was added and stirred at room temperature for 5 h. Water was added 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 intermediate E-9(26.9g, 73.2% yield, MW: 409.91).
3) Intermediate E-9(63mmol) was added to a reaction vessel with 200mL THF and 200mL toluene and MSA (630mmol) was added to the reaction solution. After stirring the mixture at room temperature for 8 hours, the mixture was extracted with distilled water and 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 intermediate F-9(21.0g, 85% yield, MW: 391.9).
4) Intermediate F-9(50mmol), reactant G-9(60mmol), toluene (300mL), ethanol (100mL), and H2O (100mL) was added to the reaction vessel and Pd (PPh) was added under nitrogen atmosphere3)4(0.50mmol), potassium carbonate (150 mmol). After the addition, the reaction temperature was slowly raised to 90 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate H-9(16g, 73.5% yield, MW: 478.55).
5) Intermediate H-9(35mmol) and triethyl phosphite (300mL) were stirred at reflux for 2 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate I-9(13.6g, 86.7% yield, MW: 446.55).
6) After intermediate I-9(28mmol) and reactant J-9(33.6mmol) were dissolved in toluene, Pd was added under a nitrogen atmosphere2(dba)3(0.28mmol)、P(t-Bu)3(1.4mmol), t-BuONa (56 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography to obtain the above organic luminescent compound (11.8g, yield 73.8%, MW: 573.22).
Example 3
This example provides an organic light-emitting compound having a chemical structural formula of formula 22 in the summary of the invention, and the reaction route of the preparation method of the organic light-emitting compound is as follows:
the specific preparation method comprises the following steps:
1) after A-22(128mmol) and B-22(140mmol) were added to a reaction vessel dissolved in toluene (300mL), Pd was added under nitrogen atmosphere2(dba)3(1.28mmol)、P(t-Bu)3(0.64mmol), t-BuONa (256 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate C-22(27.1g, 78.5% yield, MW: 269.73).
2) After addition of the reaction mixture D-22(120mmol) and THF (500mL) to the reaction vessel, the temperature was reduced to-78 deg.C and n-BuLi (120mmol) was slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 2 h, intermediate C-22(100mmol) was added and stirred at room temperature for 5 h. Water was added 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 intermediate E-22(20.4g, 71.4% yield, MW: 285.77).
3) Intermediate E-22(70mmol) and THF (200mL) and toluene (200mL) were added to a reaction vessel and MSA (700mmol) was added to the reaction. After stirring the mixture at room temperature for 8 hours, the mixture was extracted with distilled water and 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 intermediate F-22(15.6g, 83.3% yield, MW: 267.76).
4) Intermediate F-22(55mmol), reactant G-22(66mmol), toluene (300mL), ethanol (100mL), and H2O (100mL) was added to the reaction vessel and Pd (PPh) was added under nitrogen atmosphere3)4(0.55mmol), potassium carbonate (165 mmol). After the addition, the reaction temperature was slowly raised to 90 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. By means of a tubular columnThe remaining material was purified by chromatography to afford intermediate H-22(14.7g, 75.6% yield, MW: 354.41).
5) Intermediate H-22(40mmol) and triethyl phosphite (300mL) were stirred at reflux for 2 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate I-22(10.8g, 84% yield, MW: 322.15).
6) After intermediate I-22(32mmol) and reactant J-22(38mmol) were dissolved in toluene, Pd was added under nitrogen atmosphere2(dba)3(0.32mmol)、P(t-Bu)3(1.6mmol), t-BuONa (64 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography to obtain the above organic luminescent compound (15.6g, yield 78.2%, MW: 629.75).
Example 4
This example provides an organic light-emitting compound having a chemical structural formula of formula 36 in the summary of the invention, and the reaction route of the preparation method of the organic light-emitting compound is as follows:
the specific preparation method comprises the following steps:
1) after A-36(128mmol) and B-36(140mmol) were added to a reaction vessel dissolved in toluene (300mL), Pd was added under nitrogen atmosphere2(dba)3(1.28mmol)、P(t-Bu)3(0.64mmol), t-BuONa (256 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried over magnesium sulfate and evaporated using a rotary evaporatorThe solvent is removed. The remaining material was purified by column chromatography to give intermediate C-36(47.1g, 74.2% yield, MW: 471.14).
2) After addition of the reaction mixture D-36(108mmol) and THF (500mL) to the reaction vessel, the temperature was reduced to-78 deg.C and n-BuLi (108.mmol) was slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 2 h, intermediate C-36(90mmol) was added and stirred at room temperature for 5 h. Water was added 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 intermediate E-36(31.1g, 71.0% yield, MW: 487.17).
3) Intermediate E-36(63mmol) and THF (200mL) and toluene (200mL) were added to a reaction vessel and MSA (630mmol) was added to the reaction. After stirring the mixture at room temperature for 8 hours, the mixture was extracted with distilled water and 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 intermediate F-36(24.4g, 82.5% yield, MW: 469.16).
4) Intermediate F-36(50mmol), reactant G-36(60mmol), toluene (300mL), ethanol (100mL), and H2O (100mL) was added to the reaction vessel and Pd (PPh) was added under nitrogen atmosphere3)4(0.50mmol), potassium carbonate (150 mmol). After the addition, the reaction temperature was slowly raised to 90 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate H-36(20.3g, 72.9% yield, MW: 556.22).
5) Intermediate H-36(35mmol) and triethyl phosphite (300mL) were stirred at reflux for 2 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give intermediate I-36(15.8g, 86.1% yield, MW: 524.23).
6) After intermediate I-36(28mmol) and reactant J-36(31mmol) were dissolved in toluene, Pd was added under nitrogen atmosphere2(dba)3(0.28mmol)、P(t-Bu)3(1.4mmol) and t-BuONa (53.6 mmol). After the addition, the reaction temperature was slowly raised to 110 ℃, and the mixture was stirred for 10 hours. Distilled water was then added to the reaction solution and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried with magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining substance was purified by column chromatography to obtain the above organic luminescent compound (14.0g, yield 76.5%, MW: 651.27).
The synthetic routes and principles of the preparation methods of other compounds with the general structural formulas of formula I in the summary of the invention are the same as those of the above-listed examples 1 to 4, so that the description is not exhaustive, and the invention selects 17 compounds (formulas 2, 3, 6, 10, 15, 35, 39, 42, 45, 53, 58, 62, 67, 72, 78, and 80 in the summary of the invention) as examples, and the corresponding mass spectrum test values and molecular formulas are shown in table 1 below.
TABLE 1
The embodiment of the invention also provides an organic electroluminescent device prepared by adopting the organic luminescent compound provided by the embodiment, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.
The organic layer may include a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, and a light-emitting layer, and may also include an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and the like; the organic light-emitting compound provided in the above embodiment can be used as a host material in a light-emitting layer, and a dopant material of the light-emitting layer can be iridium-containingCompounds such as tris (2-phenylpyridine) iridium (Ir (ppy)3)。
The organic electroluminescent device mentioned in the embodiments of the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used. In addition, the organic light emitting compound provided by the embodiment of the present invention may also be used in organic electronic devices, such as organic solar cells, organic photoconductors, organic transistors, etc., using a principle similar to that of organic electroluminescent devices.
Specifically, the method for manufacturing the organic electroluminescent element described above can be referred to example 5.
Example 5
The embodiment provides a method for manufacturing an organic electroluminescent device, which includes the steps of:
(1) coating thickness of Fisher company of
The ITO glass substrate is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30min, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water and is ultrasonically cleaned for 10min, after the cleaning by distilled water is finished, the ITO glass substrate is sequentially ultrasonically cleaned by solvents such as isopropanol, acetone, methanol and the like, then dried, transferred into a plasma cleaning machine, and cleaned for 5min to obtain an ITO transparent electrode which is used as an anode and sent into an evaporation machine.
(2) Sequentially evaporating CuPc on the prepared ITO transparent electrode
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB,
) The organic luminescent compound with the chemical structural formula as formula 1 and a doping material Ir (ppy)3Mixture mixed according to the weight ratio of 95:5
Tris (8-hydroxyquinoline) aluminum electron transport layer (Alq3,
)、LiF
cathode Al
And obtaining the organic electroluminescent device.
Referring to the method provided in example 5, instead of the organic light emitting compound of formula 1, the organic light emitting compound of formula 2, 3, 6, 9, 10, 15, 22, 35, 36, 39, 42, 45, 48, 53, 58, 62, 67, 72, 78, 80 is selected as the host material and the dopant material ir (ppy)3And carrying out mixed evaporation according to the weight ratio of 95:5, and preparing the corresponding organic electroluminescent device.
Comparative example 1
This comparative example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and example 5 is that CBP was used instead of the organic luminescent compound of formula 1 as the host material and the dopant material ir (ppy)3Mixed evaporation is carried out according to the weight ratio of 95: 5. Wherein, the structural formula of CBP is:
the organic electroluminescent devices obtained in example 5 and comparative example 1 were tested for driving voltage, luminous efficiency, and T95 lifetime using a KEITHLEY model 2400 source measuring unit and a CS-2000 spectroradiometer, respectively, and the test results are shown in table 2 below.
TABLE 2
As can be seen from table 2 above, compared with the organic electroluminescent device prepared by using the existing CBP as the host material of the light-emitting layer, the organic electroluminescent device prepared by using the organic luminescent compound provided by the embodiment of the present invention as the host material of the light-emitting layer has significantly reduced driving voltage, and significantly improved luminous efficiency and lifetime.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. An organic light-emitting compound, wherein the structural formula of the organic light-emitting compound is formula I:
wherein Ar is one of substituted or unsubstituted C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 10-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 10-membered heteroaryl, substituted or unsubstituted 3-to 10-membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, monocyclic or polycyclic C3-C30 aliphatic ring or 3-to 10-membered aromatic ring connected with adjacent substituent;
R1～R8independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 ringOne of an alkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted 3-to 10-membered heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-to 10-membered heteroaryl group, a 3-to 10-membered aliphatic or 3-to 10-membered aromatic ring linked to an adjacent substituent to form a single or multiple ring, a C3-C30 aliphatic or a C6-C30 aromatic ring linked to other substituents on the same ring to form multiple rings.
2. An organic light-emitting compound according to claim 1, wherein at least one of the carbon atoms in the monocyclic or polycyclic C3-C30 aliphatic ring or 3-to 10-membered aromatic ring connected to the adjacent substituent is substituted or not substituted with a heteroatom; at least one carbon atom in the C3-C30 aliphatic ring or the C6-C30 aromatic ring which forms a polycyclic ring with other substituents on the same ring is replaced or not replaced by a heteroatom.
3. An organic light-emitting compound according to claim 2, wherein the heteroatom is independently one of O, S, N and Si.
4. The organic light-emitting compound of claim 1, wherein the chemical structural formula of the organic light-emitting compound is one of formula 1 to formula 80:
5. a method for producing an organic light-emitting compound according to any one of claims 1 to 4, comprising the steps of:
mixing a compound A with a general formula II, a compound B with a general formula III and toluene, placing the mixture in a protective atmosphere, and adding a palladium catalyst, tri-tert-butylphosphine and sodium tert-butoxide to react to obtain an intermediate C;
reacting a compound D with a general formula IV with butyl lithium, and then adding the intermediate C to react to obtain an intermediate E;
dissolving the intermediate E in a mixed solvent, and adding methanesulfonic acid for reaction to obtain an intermediate F;
mixing the intermediate F with a compound G with a general formula V, placing the mixture in a protective atmosphere, and adding palladium tetratriphenylphosphine and potassium carbonate to react to obtain an intermediate H;
reacting the intermediate H with triethyl phosphite to obtain an intermediate I;
and mixing the intermediate I, a compound J with a general formula VI and toluene, placing the mixture in a protective atmosphere, and adding a palladium catalyst, tri-tert-butylphosphine and sodium tert-butoxide for reaction to obtain the organic luminescent compound.
6. The method according to claim 5, wherein the mixed solvent is a mixture of tetrahydrofuran and toluene.
7. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer partially or entirely contains the organic luminescent compound according to any one of claims 1 to 4.
8. An organic electroluminescent device according to claim 7, wherein the organic layer comprises a light-emitting layer comprising the organic light-emitting compound and a dopant material.
9. An organic electroluminescent device according to claim 8, wherein the dopant material is an iridium-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010090237.9A CN111233861A (en) | 2020-02-13 | 2020-02-13 | Organic light-emitting compound, preparation method thereof and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010090237.9A CN111233861A (en) | 2020-02-13 | 2020-02-13 | Organic light-emitting compound, preparation method thereof and organic electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111233861A true CN111233861A (en) | 2020-06-05 |
Family
ID=70870435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010090237.9A Withdrawn CN111233861A (en) | 2020-02-13 | 2020-02-13 | Organic light-emitting compound, preparation method thereof and organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111233861A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100108903A (en) * | 2009-03-31 | 2010-10-08 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel compounds for organic electronic material and organic electronic device using the same |
| US20120305903A1 (en) * | 2010-02-12 | 2012-12-06 | Takahiro Kai | Organic electroluminescent device |
| KR20130032414A (en) * | 2011-05-19 | 2013-04-02 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| KR20140034710A (en) * | 2012-09-12 | 2014-03-20 | 에스에프씨 주식회사 | Heterocyclic com pounds and organic light-emitting diode including the same |
| KR20150098977A (en) * | 2014-02-21 | 2015-08-31 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
| CN110746441A (en) * | 2018-07-24 | 2020-02-04 | 北京鼎材科技有限公司 | Compound and application thereof |
-
2020
- 2020-02-13 CN CN202010090237.9A patent/CN111233861A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100108903A (en) * | 2009-03-31 | 2010-10-08 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel compounds for organic electronic material and organic electronic device using the same |
| US20120305903A1 (en) * | 2010-02-12 | 2012-12-06 | Takahiro Kai | Organic electroluminescent device |
| KR20130032414A (en) * | 2011-05-19 | 2013-04-02 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| KR20140034710A (en) * | 2012-09-12 | 2014-03-20 | 에스에프씨 주식회사 | Heterocyclic com pounds and organic light-emitting diode including the same |
| KR20150098977A (en) * | 2014-02-21 | 2015-08-31 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
| CN110746441A (en) * | 2018-07-24 | 2020-02-04 | 北京鼎材科技有限公司 | Compound and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 叶中华，等: "含有吲哚并咔唑基团的热激发延迟荧光双极性主体材料的设计、合成及应用", 《有机化学》 * |
| 唐除痴，等: "杂环的形成", 《有机合成中的有机磷试剂》 * |
| 李似姣，等: "色谱联用技术", 《现代色谱分析》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102170951B1 (en) | Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof | |
| KR101678363B1 (en) | Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof | |
| KR100940938B1 (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| JP5797672B2 (en) | Novel organic electroluminescent compound and organic electroluminescent device using the same | |
| KR100935356B1 (en) | Green electroluminescent compounds and organic electroluminescent device using the same | |
| KR20090073928A (en) | Organic electroluminescent compounds and organic light emitting diode using the same | |
| JP2013538793A (en) | Novel organic electroluminescent compound and organic electroluminescent device containing the same | |
| KR20110132721A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR20120032054A (en) | Novel organic luminescent compounds and organic electroluminescent device using the same | |
| KR20110112098A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| KR101421521B1 (en) | Amine derivative compounds and organic light-emitting diode including the same | |
| KR20090110014A (en) | Novel compounds for electronic material and organic electronic device using the same | |
| KR20140072295A (en) | Deuteriated organometallic complex and organic light-emitting diode including the same | |
| CN113620819A (en) | Heteroatom-containing fused ring amine compound and application thereof | |
| CN110804053B (en) | Electronic transmission material of imidazoazacycle and preparation method and application thereof | |
| CN112457278B (en) | Organic electroluminescent compound and preparation method and application thereof | |
| KR101780699B1 (en) | Spiro compound and organic electroluminescent devices comprising the same | |
| CN112047872B (en) | Organic electroluminescent fluorene compound and preparation method and application thereof | |
| KR20130093541A (en) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof | |
| CN112939993B9 (en) | Benzopyran luminescent auxiliary material, preparation method thereof and organic electroluminescent device | |
| CN112830900B (en) | Phosphorescent compound, method of preparing the same, and organic electroluminescent device comprising the same | |
| KR20150114658A (en) | An organoelectro luminescent compounds and organoelectro luminescent device using the same | |
| JP2024521294A (en) | Heterocyclic compound and organic light-emitting device including same | |
| CN111233875A (en) | Luminescent host compound, preparation method thereof and organic electroluminescent device | |
| CN111233862A (en) | Phosphorescent organic compound, preparation method thereof and organic electroluminescent device |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200605 |