CN112442027B - Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device - Google Patents

Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device Download PDF

Info

Publication number
CN112442027B
CN112442027B CN201910803839.1A CN201910803839A CN112442027B CN 112442027 B CN112442027 B CN 112442027B CN 201910803839 A CN201910803839 A CN 201910803839A CN 112442027 B CN112442027 B CN 112442027B
Authority
CN
China
Prior art keywords
formula
organic
organic compound
electroluminescent device
organic electroluminescent
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
CN201910803839.1A
Other languages
Chinese (zh)
Other versions
CN112442027A (en
Inventor
吕瑶
冯美娟
吴卫娜
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.)
Beijing Green Guardee Technology Co ltd
Original Assignee
Beijing Green Guardee 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 Beijing Green Guardee Technology Co ltd filed Critical Beijing Green Guardee Technology Co ltd
Priority to CN201910803839.1A priority Critical patent/CN112442027B/en
Publication of CN112442027A publication Critical patent/CN112442027A/en
Application granted granted Critical
Publication of CN112442027B publication Critical patent/CN112442027B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C07D471/02—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 two hetero rings
    • C07D471/04—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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking 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
    • H10K85/649—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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • C09K2211/1018—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the field of organic electroluminescent devices, and discloses an organic compound containing a nitrogen fluorene group, application thereof and an organic electroluminescent device. The organic compound containing the nitrogen fluorene group has lower driving voltage, higher luminous efficiency and longer service life when being used in an organic electroluminescent device. A-B-L-C formula (I)
Figure DDA0002183064610000011

Description

Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to an organic compound containing nitrogen fluorene groups, application of the organic compound in an organic electroluminescent device and an organic electroluminescent device containing one or more than two compounds in the organic compound.
Background
Organic light-emitting diodes (OLEDs) have the following advantages compared to Liquid Crystal Displays (LCDs):
(1) Self-luminous, surface light source, without need of backlight source;
(2) the cost is low, and the process is simple;
(3) low-voltage driving, low energy consumption and high efficiency;
(4) the response is fast, in microsecond level, 1000 times of the response of the LCD, the wide viewing angle is provided, and the viewing angle width of the upper, lower, left and right sides exceeds 170 degrees;
(5) the wide temperature range can work normally from minus 40 ℃ to plus 80 ℃;
(6) high brightness, high contrast and bright and fine display effect.
At present, great manpower and material resources are invested in various international companies for research and development, and the full arrival of the OLED display era is shown.
The principle of organic electroluminescence is to convert electric energy into light energy by using organic substances, an organic light emitting element generally comprises a cathode and an anode and a structure of an organic layer between the cathode and the anode, and the organic layer mainly comprises a hole injection material, a hole transport material, an electron blocking material, a light emitting material, an electron transport material, an electron injection material and the like.
In the organic electroluminescent device, the conventional electron transport layer material Alq3Has a low electron mobility, so that the electron transport properties of the electroluminescent device are reduced. In order to obtain a high-performance electron transport material, the material is required to have high electron mobility, and simultaneously, the material has a high triplet state energy level to block excitons, so that the luminous efficiency and the service life of the device are improved.
In addition, the current organic electroluminescent device has the problems of high driving voltage, low current efficiency and short service life, so that the organic electroluminescent device with better performance cannot be obtained.
Disclosure of Invention
The present invention is directed to overcome the disadvantages of high driving voltage, low efficiency and short service life of the organic electroluminescent device provided by the prior art, and to provide a novel organic compound containing a nitrogen-containing fluorene group, so as to enable the organic electroluminescent device containing the organic compound containing the nitrogen-containing fluorene group to have a lower driving voltage, a higher luminous efficiency and a longer service life compared to the organic electroluminescent device of the prior art.
In order to achieve the above object, a first aspect of the present invention provides an organic compound containing a nitrogen-containing fluorene group, the organic compound having a structure represented by formula (I),
A-B-L-C is formula (I),
Figure GDA0003472886550000021
Figure GDA0003472886550000022
wherein, in the formula (I),
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is selected from phenyl and biphenyl, or L is not existed, and C is a group shown in formula (C); and the A and the B or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
In the group of formula (c), X1、X2And X3Each independently selected from C and N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl, and the group of formula (c) contains at least two N atoms.
In the present invention, when L is present, the L may connect the two side groups in an arbitrary connection manner, for example, when L is phenyl, it may be a para-connection manner, a meta-connection manner, or an ortho-connection manner. And L may be connected to any connectable position in the parent nucleus ring in which it is located. Also, the number of L is one or absent according to the definition of the present invention.
When the organic compound is used in an organic electroluminescent device, the organic electroluminescent device obtained by the organic compound has high electron injection capability.
In addition, the organic compound has higher electron transfer capability, so when the organic compound is used in an organic electroluminescent device, electrons in the organic electroluminescent device can be efficiently combined with holes to form exciton luminescence, and the luminous efficiency of the organic electroluminescent device is improved.
Meanwhile, when the organic compound is used in an organic electroluminescent device, the organic electroluminescent device can have a lower driving voltage.
Several preferred embodiments of the nitrogen-containing fluorene group-containing organic compounds of the present invention are provided below.
Embodiment mode 1:
in the formula (I), the compound represented by the formula (I),
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
in the group of formula (c), X1、X2And X3Each independently selected from C and N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl, and the group of formula (c) contains at least two N atoms.
Embodiment mode 2:
in the formula (I), the compound represented by the formula (I),
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
In the group of formula (c), X1、X2And X3Each independently selected from C and N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl, and the group of formula (c) contains at least two N atoms; and
a and L directly connected with B, or A and C directly connected with B are connected on the same benzene ring structure of B.
Embodiment mode 3:
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
in the group of formula (c), X1、X2And X3Each independently selected from C and N, and X1、X2And X3At least two of which are N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl; and
a and L directly connected with B, or A and C directly connected with B are connected on the same benzene ring structure of B.
Embodiment 4:
A is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
in the group of formula (c), X1、X2And X3Are all C; r1And R2Are all pyridyl; and
a and L directly connected with B, or A and C directly connected with B are connected on the same benzene ring structure of B.
Embodiment 5:
the organic compound with the structure shown in the formula (I) is selected from at least one of the following specific compounds:
Figure GDA0003472886550000051
Figure GDA0003472886550000061
embodiment 6:
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
In the group of formula (c), X1、X2And X3Each independently selected from C and N, and X1、X2And X3At least two of which are N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl; and
a and L directly connected with B, or A and C directly connected with B are respectively connected with different benzene ring structures of B.
Embodiment 7:
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
in the group of formula (c), X1、X2And X3Are all C; r1And R2Are all pyridyl; and
a and L directly connected with B, or A and C directly connected with B are respectively connected with different benzene ring structures of B.
Embodiment mode 8:
the organic compound with the structure shown in the formula (I) is selected from at least one of the following specific compounds:
Figure GDA0003472886550000071
Figure GDA0003472886550000081
Figure GDA0003472886550000091
Figure GDA0003472886550000101
embodiment mode 9:
the organic compound with the structure shown in the formula (I) is selected from at least one of the following specific compounds:
Figure GDA0003472886550000102
Figure GDA0003472886550000111
Figure GDA0003472886550000121
Figure GDA0003472886550000131
Figure GDA0003472886550000141
Embodiment mode 10:
the organic compound with the structure shown in the formula (I) is selected from at least one of the following specific compounds:
Figure GDA0003472886550000142
Figure GDA0003472886550000151
the invention also provides the following preferred embodiments:
embodiment mode 11:
in the formula (I), the compound has the following structure,
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
in the group of formula (c), X1、X2And X3Each independently selected from C and N, and X1、X2And X3At least two of which are N atoms; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl.
Embodiment mode 12:
in the formula (I), the compound represented by the formula (I),
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
In the group of formula (c), X1、X2And X3Are all C; r1And R2Are all pyridyl.
The inventors of the present invention have found in their studies that the compounds provided in the above-mentioned embodiments 1 to 12 of the present invention, when used in an organic electroluminescent device, give an organic electroluminescent device having a significantly lower driving voltage and higher luminous efficiency.
In addition, the inventors of the present invention have also found that the organic compounds provided in the above-described embodiments 8 and 9 of the present invention, particularly embodiment 9, can optimize the performance of the organic electroluminescent device thus obtained.
The organic compound provided by the invention can be used as an electron type main body material, a hole blocking layer material or an electron transport layer material in an organic electroluminescent device.
Preferably, the organic compound provided by the invention can be used as an electron transport material in an organic electroluminescent device.
The method for synthesizing the organic compound provided by the present invention is not particularly limited, and those skilled in the art can determine an appropriate synthesis method according to the structural formula of the organic compound provided by the present invention and the preparation method of the preparation example.
Further, some preparation methods of the organic compound are exemplarily given in the preparation examples of the present invention, and those skilled in the art can obtain the organic compound provided by the present invention according to the preparation methods of these exemplary preparation examples. The present invention will not be described in detail herein with respect to specific methods of preparing the various compounds of the present invention, which should not be construed as limiting the invention to those skilled in the art.
A second aspect of the invention provides the use of an organic compound according to the first aspect in an organic electroluminescent device.
A third aspect of the present invention provides an organic electroluminescent device comprising one or two or more of the organic compounds according to the first aspect of the present invention, wherein the organic compounds are present in at least one of an electron transport layer, a light emitting layer and a hole blocking layer of the organic electroluminescent device.
Preferably, the organic compound is present in an electron transport layer of the organic electroluminescent device.
The organic compound is particularly preferred as an electron transport material in an electron transport layer of the organic electroluminescent device.
Particularly, when the organic compound provided by the invention is used in at least one of an electron transport layer, a light emitting layer and a hole blocking layer of an organic electroluminescent device, the LUMO energy level of an organic electroluminescent material can be adjusted and the electron mobility is enhanced, and the organic compound has a high T1 energy level.
According to a preferred embodiment, the present invention provides an organic electroluminescent device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the one or more organic material layers comprise the organic compound of the present invention.
According to an embodiment of the present specification, the organic material layer of the organic electroluminescent device of the present specification may also be formed in a multilayer structure of two or more organic material layers. The organic electroluminescent device of the present invention includes a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron injection layer, etc. as organic material layers. However, the structure of the organic device is not limited thereto and a smaller or greater number of organic layer materials may be included.
According to an embodiment of the present invention, the organic electroluminescent device of the present invention further comprises a first capping layer and/or a second capping layer, the first capping layer being disposed on the outer surface of the anode, and the second capping layer being disposed on the outer surface of the cathode.
For example, the organic electroluminescent device may sequentially stack a first capping layer, an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), a cathode, and a second capping layer.
Particularly preferably, the organic electroluminescent device according to the present invention includes a first capping layer, an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), a cathode, and a second capping layer, which are sequentially stacked.
Preferably, the organic compound of the present invention is contained in each of the first capping layer and the second capping layer independently.
The substrate of the present invention may use a glass substrate, a plastic substrate, or a metal substrate.
The anode material forming the anode, generally preferably a material having a large work function, may be a hole injection-facilitating organic material layer, and anode materials that can be used in the present disclosure are selected from one or more of the following materials, metals such as vanadium, chromium, copper, and gold, or other alloys: metal oxides, such as: zinc oxide, indium tin oxide, indium zinc oxide and tin dioxide, combinations of metals and oxides, such as: zinc oxide: but is not limited thereto.
The material forming the hole injection layer is a hole injection material, and a compound preferable as the hole injection material has an ability to transport holes, and thus has a hole effect of injecting into the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and further, has an excellent thin film forming ability. The HOMO of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.
The material forming the hole transport layer is a hole transport material capable of receiving holes from the anode or the hole injection layer, moving the holes to the light emitting layer, and having high mobility to the holes.
The hole injection material and the hole transport material include aromatic amine derivatives (e.g., NPB, SqMA1), hexaazatriphenylene derivatives (e.g., HACTN), indolocarbazole derivatives, conductive polymers (e.g., PEDOT/PSS), phthalocyanine or porphyrin derivatives, dibenzoindenofluorenamine, spirobifluorenamine, but are not limited thereto.
The hole injection layer and the hole transport layer can be formed using, for example, an aromatic amine derivative of the following general formula:
Figure GDA0003472886550000181
the groups R1 to R9 in the above general formula are each independently selected from a single bond, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, triphenylene, pyrene, fluorene, dimethylfluorene, spirobifluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine.
The material for forming the electron blocking layer is not particularly limited, and in general, any compound capable of satisfying the following conditions 1 and/or 2 can be considered:
1, a first step: the higher LUMO energy level is provided, and the purpose is to reduce the number of electrons leaving the light-emitting layer, thereby improving the recombination probability of electrons and holes in the light-emitting layer.
And (2): the light emitting device has larger triplet energy, and the purpose of the triplet energy is to reduce the number of excitons leaving the light emitting layer, thereby improving the efficiency of exciton conversion light emission.
Materials forming the electron blocking layer include, but are not limited to, aromatic amine derivatives (e.g., NPB), spirobifluorene amines (e.g., SpMA2), in which the structures of a portion of the electron blocking material and the hole injecting material and the hole transporting material are similar.
The light-emitting material of the light-emitting layer is a material capable of emitting light in the visible light region by receiving holes and electrons from the hole-transport layer and the electron-transport layer, respectively, and combining the holes and the electrons, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. The light emitting layer may include a host material and a dopant material.
The main material includes anthracene derivatives, carbazole derivatives, fluorene derivatives, arylamine derivatives, organosilicon derivatives, carbazole-triazine derivatives, and phosphorus-oxygen derivatives, but is not limited thereto.
Preferably, the anthracene derivative has the general formula shown below:
Figure GDA0003472886550000191
Preferably, the phosphorus oxy derivative has the following general formula:
Figure GDA0003472886550000192
in the general formulae of the anthracene derivatives and the phosphorus oxy derivatives, R11、R12、R13、R14、R15And R16Each independently selected from the group represented by a single bond, hydrogen, deuterium, an alkyl group, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, triphenylene, pyrene, fluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine, and a substituent thereof.
The guest material is a compound that produces emission via at least one of phosphorescence, fluorescence, TADF (thermally activated delayed fluorescence), MLCT (metal to ligand charge transfer), HLCT (with hybrid CT states), and triplet-triplet annihilation methods.
The guest material in the light-emitting layer may include perylene derivatives, anthracene derivatives, fluorene derivatives, distyrylaryl derivatives, arylamine derivatives, silicone derivatives, organoboron derivatives, carbazole-triazine derivatives, acridine derivatives, ketone-containing derivatives, sulfone-based derivatives, cyano derivatives, and xanthene derivatives, but is not limited thereto.
Preferably, the sulfone-based derivative has a general formula as shown below:
Figure GDA0003472886550000201
preferably, the ketone derivative has the general formula shown below:
Figure GDA0003472886550000202
in the above general formulae of the sulfone-based derivatives and ketone-based derivatives, R20、R21、R22And R23Each independently selected from the group represented by a single bond, hydrogen, deuterium, an alkyl group, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, triphenylene, pyrene, fluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine, and a substituent thereof.
The material of the hole blocking layer is preferably a compound having the following conditions 1 and/or 2:
1, the method comprises the following steps: the organic electroluminescent device has a higher HOMO energy level, and the purpose of the organic electroluminescent device is to reduce the number of holes leaving a light-emitting layer, so that the recombination probability of electrons and holes in the light-emitting layer is improved.
And 2, a step of: the light emitting layer has larger triplet energy, and the purpose of the light emitting layer is to reduce the number of excitons which leave the light emitting layer, thereby improving the efficiency of exciton conversion and light emission.
The material forming the hole blocking layer may include phenanthroline derivatives (e.g., Bphen, BCP), triphenylene derivatives, benzimidazole derivatives, but is not limited thereto.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and as an electron transport material, a material that is capable of receiving electrons from the cathode, moving the electrons to the light emitting layer, and having high mobility to the electrons is suitable. The electron transport material comprises an Al complex of 8-hydroxyquinoline; comprising Alq3The complex of (1); an organic radical compound; hydroxyflavone-metal complexes, and the like, but are not limited thereto.
The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from a cathode, has an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to a hole injection layer, and has an excellent thin film forming ability. The electron injection layer material comprises LiF and Al2O3MnO, but not limited thereto.
The organic electroluminescent device of the invention is preferably coated in one layer or in a plurality of layers by means of a sublimation process. In this case, in the vacuum sublimation system, the temperature is less than 10 DEG-3Pa, preferably less than 10-6The organic compound provided by the present invention is applied by vapor deposition at an initial pressure of Pa.
The organic electroluminescent device of the invention is preferably coated with one or more layers by means of an organic vapor deposition process or sublimation with the aid of a carrier gas. In this case, 10-6The material is applied under a pressure of Pa to 100 Pa. A particular example of such a process is an organic vapor deposition jet printing process, wherein the compounds provided by the present invention are applied directly through a nozzle and form a device structure.
The organic electroluminescent device of the present invention is preferably formed into one or more layers by photo-induced thermal imaging or thermal transfer.
The organic electroluminescent device of the invention is preferably prepared by formulating the organic compounds of the invention in a solution to form the layer or the layer structure by spin coating or by means of any printing means, such as screen printing, flexographic printing, ink-jet printing, lithographic printing, more preferably ink-jet printing. However, when a plurality of layers are formed by this method, the layers are easily damaged, that is, when one layer is formed and another layer is formed by using a solution, the formed layer is damaged by a solvent in the solution, which is not favorable for device formation. The organic compound provided by the invention can be substituted by structural modification, so that the organic compound provided by the invention can generate a crosslinking effect under the condition of heating or ultraviolet exposure, and a complete layer can be kept without being damaged. The organic compounds according to the invention can additionally be applied from solution and fixed in the respective layer by subsequent crosslinking in the polymer network.
Preferably, the organic electroluminescent device of the invention is manufactured by applying one or more layers from a solution and one or more layers by a sublimation method.
Preferred solvents for the preparation of organic electroluminescent devices according to the invention are selected from the group consisting of toluene, anisole, o-xylene, m-xylene, p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, phenoxytoluene, in particular 3-phenoxytoluene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, benzothiazole, butyl benzoate, isopropanol, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, cyclohexanol, Methyl benzoate, NMP, p-methylisobenzene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, 2-heptanol, 3-heptanol, or a mixture of these solvents.
Preferably, in the preparation of the organic electroluminescent device according to the invention, the organic compound according to the invention or other compounds are first mixed thoroughly and then applied by the above-described application method to form a layer or layers. More preferably, in a vacuum sublimation system, less than 10-3Pa, preferably less than 10-6Pa, to form a layer or layers by applying the respective compounds by vapour deposition.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
The present invention provides methods for preparing a portion of the compounds of the following specific structural formulae, and methods for preparing the remaining compounds may be performed with reference to the methods provided below, and those skilled in the art should not be construed as limiting the present invention.
Figure GDA0003472886550000231
Synthesis of intermediate A-1-1: adding 0.1mol of 2-bromo-1, 10-phenanthroline and 0.35mol of KOH into 1.3L of water, stirring and heating to reflux reaction, and dropwise adding 0.3mol of KMnO after about 1h4Hot solution in water (1L). The mixture was refluxed for an additional 2h and then filtered while hot. The filtrate was cooled and extracted with chloroform three times, dried over anhydrous sodium sulfate and filtered, and the filtrate was spin-dried under reduced pressure and subjected to column chromatography to give intermediate a-1-1 (yield 50%).
Synthesis of intermediate A-1-2: 0.05mol of intermediate A-1-1 was added to 130ml of N2H4·H2O, heating at 150 deg.C for 5h, cooling to room temperature, extracting with chloroform for three times, drying the organic phase with anhydrous sodium sulfate, spin-drying under reduced pressure, and performing column chromatography to obtain intermediate A-1-2 (yield: 80%).
Synthesis of intermediate A-1: 0.04mol of intermediate A-1-2 and 0.2mol of potassium tert-butoxide are dissolved in 130mL of anhydrous THF, 0.13mol of bromobenzene is added, heating is carried out to reflux, after 4 hours the completion of the reaction of the starting materials is detected, the reaction solution is quenched with water, extracted three times with chloroform, the organic phase is dried over anhydrous sodium sulfate, dried under reduced pressure and subjected to column chromatography to give intermediate A-1 (yield: 40%).
Figure GDA0003472886550000232
Synthesis of intermediate A-2-1: the synthesis method was the same as that of intermediate A-1-1, to obtain intermediate A-2-1 (yield: 50%).
And (3) synthesis of an intermediate A-2-2: the synthesis method was the same as that of intermediate A-1-2, to obtain intermediate A-2-2 (yield: 78%).
Synthesis of intermediate A-2: the synthesis method was the same as that of intermediate A-1 to obtain intermediate A-2 (yield: 43%).
Figure GDA0003472886550000241
Synthesis of intermediate A-3-1: the synthesis method was the same as that of intermediate A-1-1, to obtain intermediate A-3-1 (yield: 53%).
And (3) synthesizing an intermediate A-3-2: 0.1mol of p-bromoiodobenzene is added into 280ml of anhydrous THF and stirred, N2Cooling to-78 deg.C under protection, adding 0.14mol of 2.5mol/L n-butyllithium dropwise, keeping at-78 deg.C for 1 hr, heating to room temperature, keeping for 2 hr, cooling to-78 deg.C, and adding 0.1mol of intermediate A-3-1. After the reaction of the starting materials was detected to be completed after warming to room temperature for 5 hours, 1mol/L diluted hydrochloric acid aqueous solution was dropped into the reaction solution, and stirred for 5 hours to precipitate a solid, and the residue was filtered to obtain an intermediate A-3-2 by column chromatography (yield: 51%).
Synthesis of Compound A-3: dissolving 0.01mol of A-3-2 in 340ml of dichloromethane, dropwise adding 0.15mol of boron trifluoride-diethyl ether complex at room temperature, reacting for 1h, adding ethanol and water to quench the reaction, extracting with dichloromethylamine, drying with anhydrous sodium sulfate, rotary-evaporating to remove the solvent, passing through a neutral silica gel column by using petroleum ether as an eluent, and recrystallizing the mixed solvent of ethanol and dichloromethane in a volume ratio of 1:1 to obtain the compound A-3 (yield: 78%).
Figure GDA0003472886550000242
Synthesis of intermediate A-4-1: the synthesis method was the same as that of intermediate A-3-2, to obtain intermediate A-4-1 (yield: 54%).
Synthesis of Compound A-4: the synthesis method was the same as that of Compound A-3, giving Compound A-4 (yield: 76%).
Preparation example 1: synthesis of Compound 1-1
Figure GDA0003472886550000251
Synthesis of intermediate 1-1-1: dissolving 0.1mol of 2-bromo-4-iodo dibenzofuran in 372ml of 1, 4-dioxane solvent, introducing nitrogen, stirring, sequentially adding 0.1mol of pinacol diboron diboride, 0.25mol of potassium acetate and 0.001mol of ferrocene palladium dichloride, heating to reflux reaction, detecting basic reaction of raw materials by HPLC after 4 hours, decompressing and spin-drying reaction liquid, and performing column chromatography on residues to obtain an intermediate 1-1-1 (yield: 81%).
Synthesis of intermediate 1-1-2: dissolving 0.1mol of intermediate 1-1-1 in 375ml of 1, 4-dioxane solvent, stirring under nitrogen, sequentially adding 0.1mol of intermediate A-3, 0.25mol of K2CO3 and 0.001mol of tetrakis (triphenylphosphine) palladium, heating to reflux reaction, after 5h, detecting basic reaction of raw materials by HPLC, decompressing and spin-drying reaction liquid, and carrying out column chromatography on residues to obtain intermediate 1-1-2 (yield: 72%).
Synthesis of intermediates 1-1-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-1-3 was obtained (yield: 79%).
Synthesis of Compound 1-1: the synthesis method was the same as that of the intermediate 1-1-2, to obtain the compound 1-1 (yield: 75%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.11-7.15 (2H, m), 7.26-7.51 (17H, m), 7.63-7.67 (3H, m), 7.89-7.91 (1H, m), 8.28-8.31 (4H, m), 8.51-8.51 (2H, m).
Preparation example 2: synthesis of Compounds 1 to 7
Figure GDA0003472886550000261
Synthesis of intermediate 1-7-1: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-7-1 was obtained (yield: 83%).
Synthesis of intermediates 1-7-2: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 1-7-2 was obtained (yield: 73%).
Synthesis of intermediates 1-7-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-7-3 was obtained (yield: 81%).
Synthesis of Compounds 1-7: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-7 (yield: 75%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (1H, m), 7.11-7.15 (4H, m), 7.26-7.51 (15H, m), 7.66-7.67 (1H, m), 7.81-7.89 (4H, m), 8.28-8.31 (4H, m), 8.51-8.51 (1H, m), 8.79-8.79 (1H, d).
Preparation example 3: synthesis of Compounds 1-11
Figure GDA0003472886550000271
Synthesis of Compounds 1-11: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-11 (yield: 71%).
Mass spectrum: C56H35N5O, theoretical value: 793.28, found: 793.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.11-7.15 (2H, m), 7.26-7.51 (19H, m), 7.63-7.67 (3H, m), 7.85-7.89 (3H, m), 8.28-8.31 (4H, m), 8.51-8.53 (2H, m).
Preparation example 4: synthesis of Compounds 1-17
Figure GDA0003472886550000272
Synthesis of intermediate 1-17-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 1-17-1 was obtained (yield: 70%).
Synthesis of intermediates 1-17-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-17-2 was obtained (yield: 83%).
Synthesis of Compounds 1-17: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-17 (yield: 75%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.11-7.15 (2H, m), 7.26-7.51 (17H, m), 7.63-7.67 (3H, m), 7.87-7.89 (1H, m), 8.28-8.31 (4H, m), 8.51-8.53 (2H, m).
Preparation example 5: synthesis of Compounds 1-20
Figure GDA0003472886550000281
Synthesis of intermediate 1-20-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 1-20-1 was obtained (yield: 72%).
Synthesis of intermediates 1-20-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-20-2 was obtained (yield: 81%).
Synthesis of Compounds 1-20: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-20 (yield: 74%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (3H, m), 7.26-7.51 (15H, m), 7.66-7.67 (1H, m), 7.79-7.89 (4H, m), 8.28-8.31 (4H, m), 8.51-8.53 (2H, m).
Preparation example 6: synthesis of Compounds 1-30
Figure GDA0003472886550000291
Synthesis of intermediate 1-30-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 1-30-1 was obtained (yield: 75%).
Synthesis of intermediates 1-30-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-30-2 was obtained (yield: 81%).
Synthesis of Compounds 1-30: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-30 (yield: 72%).
Mass spectrum: C51H32N4O, theoretical value: 716.26, found: 716.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (3H, m), 7.26-7.51 (15H, m), 7.63-7.67 (3H, m), 7.79-7.83 (5H, m), 7.89-7.81 (1H, m), 8.23-8.23 (1H, s), 8.51-8.53 (2H, m).
Preparation example 7: synthesis of Compounds 1-40
Figure GDA0003472886550000301
Synthesis of intermediate 1-40-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 1-40-1 was obtained (yield: 73%).
Synthesis of intermediates 1-40-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 1-40-2 was obtained (yield: 80%).
Synthesis of Compounds 1-40: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 1-40 (yield: 74%).
Mass spectrum: C51H32N4O, theoretical value: 716.26, found: 716.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (3H, m), 7.26-7.66 (15H, m), 7.79-7.89 (3H, m), 8.42-8.45 (2H, m), 8.51-8.53 (2H, m), 8, 70-8.73 (3H, m), 9.24-9.24 (2H, d).
Preparation example 8: synthesis of Compound 2-2
Figure GDA0003472886550000311
Synthesis of intermediate 2-2-1: the synthesis method was the same as that of intermediate 1-1-1 to obtain intermediate 2-2-1 (yield: 83%).
Synthesis of intermediate 2-2-2: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-2-2 was obtained (yield: 73%).
Synthesis of intermediate 2-2-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-2-3 was obtained (yield: 82%).
Synthesis of Compound 2-2: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 2-2 (yield: 71%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (3H, m), 7.26-7.66 (13H, m), 7.71-7.81 (7H, m), 8.28-8.33 (4H, m), 8.51-8.53 (2H, m).
Preparation example 9: synthesis of Compounds 2-5
Figure GDA0003472886550000321
Synthesis of intermediate 2-5-1: the synthesis method was the same as that of the intermediate 1-1-1, and the intermediate 2-5-1 was obtained (yield: 85%).
And (3) synthesis of an intermediate 2-5-2: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-5-2 was obtained (yield: 73%).
And (3) synthesis of an intermediate 2-5-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-5-3 was obtained (yield: 81%).
Synthesis of Compounds 2-5: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 2-5 (yield: 70%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (2H, m), 7.26-7.66 (16H, m), 7.71-7.73 (2H, m), 7.81-7.85 (3H, m), 8.28-8.33 (4H, m), 8.51-8.53 (2H, m).
Preparation example 10: synthesis of Compounds 2-24
Figure GDA0003472886550000331
Synthesis of intermediate 2-24-1: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-24-1 was obtained (yield: 85%).
Synthesis of intermediate 2-24-2: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-24-2 was obtained (yield: 73%).
Synthesis of intermediates 2-24-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-24-3 was obtained (yield: 80%).
Synthesis of Compounds 2-24: the synthesis method was the same as that of intermediate 1-1-2, and compound 2-24 was obtained at 0.072mol (yield: 72%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (1H, m), 7.10-7.13 (4H, m), 7.20-7.51 (14H, m), 7.62-7.64 (2H, m), 7.75-7.78 (1H, m), 7.95-7.98 (2H, m), 8.15-8.17 (1H, m), 8.26-8.28 (5H, m), 8.51-8.53 (1H, m).
Preparation example 11: synthesis of Compounds 2-44
Figure GDA0003472886550000341
Synthesis of intermediate 2-44-1: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-44-1 was obtained (yield: 83%).
Synthesis of intermediate 2-44-2: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-44-2 was obtained (yield: 73%).
Synthesis of intermediates 2-44-3: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-44-3 was obtained (yield: 79%).
Synthesis of Compounds 2-44: the synthesis method was the same as that of the intermediate 1-1-2, and the compound 2-44 was obtained (yield: 72%).
Mass spectrum: C50H31N5O, theoretical: 717.25, found: 717.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (1H, m), 7.10-7.13 (4H, m), 7.20-7.51 (16H, m), 7.62-7.68 (2H, m), 7.81-7.85 (2H, m), 8.26-8.28 (5H, m), 8.51-8.53 (1H, m).
Preparation example 12: synthesis of Compounds 2-69
Figure GDA0003472886550000351
Synthesis of intermediate 2-69-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-69-1 was obtained (yield: 73%).
Synthesis of intermediate 2-69-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-69-2 was obtained (yield: 80%).
Synthesis of Compounds 2-69: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 2-69 (yield: 74%).
Mass spectrum: C50H32N4O, theoretical value: 716.26, found: 716.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (2H, m), 7.20-7.51 (15H, m), 7.64-7.68 (2H, m), 7.75-7.79 (6H, m), 7.95-7.99 (2H, m), 8.23-8.23 (1H, d), 8.51-8.53 (2H, m).
Preparation example 13: synthesis of Compounds 2-89
Figure GDA0003472886550000352
Synthesis of intermediate 2-89-1: the synthesis method was the same as that of intermediate 1-1-2, and intermediate 2-89-1 was obtained (yield: 73%).
Synthesis of intermediate 2-89-2: the synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-89-2 was obtained (yield: 79%).
Synthesis of Compounds 2-89: the synthesis method was the same as that of intermediate 1-1-2, to obtain compound 2-89 (yield: 74%).
Mass spectrum: C62H39N5O, theoretical value: 869.32, found: 869.2. 1H-NMR (400MHz, CDCl3) (ppm) delta is 6.81-6.83 (2H, m), 7.10-7.13 (2H, m), 7.26-7.52 (23H, m), 7.71-7.72 (4H, m), 7.81-7.85 (6H, m), 8.51-8.53 (2H, m).
Example 1: preparation of organic light emitting device
After ultrasonically washing a glass substrate having an Indium Tin Oxide (ITO) electrode (first electrode, anode) of about 1500 angstroms thickness with distilled water and methanol in sequence, the washed glass substrate was dried, moved to a plasma cleaning system, and then cleaned using oxygen plasma for about 5 minutes. The glass substrate is then loaded into a vacuum deposition apparatus.
Vacuum depositing HAT-CN onto the ITO electrode of the glass substrate to form a HIL having a thickness of about 100 angstroms; TAPC was vacuum deposited to a thickness of 400 angstroms onto the hole injection layer to form an HTL.
Mixing DMIC-TRZ with Ir (mppy)3And (3) at a speed of 94: a ratio of 6 was deposited on the hole transport region to form an EML having a thickness of about 300 angstroms.
Subsequently, compound 1-1 was vacuum deposited on the EML to form an ETL having a thickness of about 350 angstroms. Then, LiF was deposited on the ETL to form an EIL having a thickness of about 10 angstroms, and Al was deposited on the EIL to a thickness of about 1000 angstroms to form a second electrode (cathode), thereby completing the fabrication of the organic light emitting device.
Figure GDA0003472886550000361
Other embodiments
Organic light-emitting devices of the remaining examples were prepared in a similar manner to example 1, except that the compounds shown in table 1 were used instead of compound 1-1 in example 1.
Comparative example 1
An organic light-emitting device was produced in a similar manner to that in example 1, except that compound M-1 was used instead of compound 1-1 in example 1.
The structural formula of the compound is as follows:
Figure GDA0003472886550000371
evaluation: evaluation of characteristics of organic light-emitting device
The driving voltage, emission efficiency and lifetime of the organic light emitting devices in examples and comparative examples were measured using a current-voltage source meter (Keithley 2400) and a Minolta CS-1000A spectroradiometer.
(1) Measurement of current density change with respect to voltage change
A current value flowing through each of the organic light emitting devices was measured while increasing a voltage from 0 volt (V) to about 10V by using a current-voltage source meter (Keithley 2400), and then divided by an area of the corresponding light emitting device to obtain a current density.
(2) Measurement of brightness variation with respect to voltage variation
The brightness of the organic light emitting device was measured while increasing the voltage from about 0V to about 10V by using a Minolta CS-1000A spectroradiometer.
(3) Measurement of emission efficiency
The organic light emitting device was calculated at 20mA/cm based on the current density, voltage and luminance obtained by the above-described measurements (1) and (2)2Current efficiency at a current density of (a).
The results are shown in Table 1.
TABLE 1
Figure GDA0003472886550000381
From the experimental results shown in table 1, it can be seen that the organic compound of the present invention has low driving voltage and high current efficiency when used as an electron transport material of an organic electroluminescent device.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. An organic compound containing a nitrogen fluorene group, which has a structure shown in formula (I),
A-B-L-C is of formula (I),
Figure FDA0003628245780000011
Figure FDA0003628245780000012
wherein, in the formula (I),
a is a group provided by the structure shown in formula (a), B is a group provided by the structure shown in formula (B), L is phenyl, or L is absent, C is a group shown in formula (C); and the A and the B, or the B and the L are connected in pairs through any positions capable of forming bonds, and the group shown in the formula (c) is connected to any position capable of forming bonds in the B or the L; and, A is optionally substituted with one or two or more groups selected from phenyl, biphenyl;
In the group of formula (c), X1、X2And X3Each independently selected from C and N; r1And R2Each independently selected from phenyl, biphenyl, pyridyl, and naphthyl, and the group of formula (c) contains at least two N atoms.
2. The organic compound according to claim 1, wherein, in formula (I), a and L directly connected to B, or a and C directly connected to B, are connected to the same benzene ring structure of B.
3. The organic compound according to claim 1 or 2, wherein the organic compound having a structure represented by formula (I) is selected from at least one of the following compounds:
Figure FDA0003628245780000021
Figure FDA0003628245780000031
4. the organic compound according to claim 1, wherein, in formula (I), a and L directly connected to B, or a and C directly connected to B, are respectively connected to different benzene ring structures of B.
5. The organic compound according to claim 1 or 4, wherein the organic compound having a structure represented by formula (I) is selected from at least one of the following compounds:
Figure FDA0003628245780000032
Figure FDA0003628245780000041
Figure FDA0003628245780000051
Figure FDA0003628245780000061
6. the organic compound according to claim 1, wherein the organic compound having a structure represented by formula (I) is selected from at least one of the following compounds:
Figure FDA0003628245780000062
Figure FDA0003628245780000071
Figure FDA0003628245780000081
Figure FDA0003628245780000091
Figure FDA0003628245780000101
Figure FDA0003628245780000111
7. the organic compound according to claim 6, wherein the organic compound having a structure represented by formula (I) is at least one selected from the following compounds:
Figure FDA0003628245780000112
8. Use of an organic compound according to any one of claims 1 to 7 in an organic electroluminescent device.
9. An organic electroluminescent device comprising one or two or more of the organic compounds according to any one of claims 1 to 7, wherein the organic compounds are present in at least one of an electron transport layer, a light emitting layer and a hole blocking layer of the organic electroluminescent device.
10. The organic electroluminescent device according to claim 9, wherein the organic compound is present in an electron transport layer of the organic electroluminescent device.
11. The organic electroluminescent device according to claim 9, wherein the organic compound serves as an electron transport material in an electron transport layer of the organic electroluminescent device.
12. The organic electroluminescent device according to any one of claims 9 to 11, wherein the organic electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light emitting layer, an optional hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, which are sequentially stacked.
CN201910803839.1A 2019-08-28 2019-08-28 Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device Active CN112442027B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910803839.1A CN112442027B (en) 2019-08-28 2019-08-28 Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910803839.1A CN112442027B (en) 2019-08-28 2019-08-28 Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device

Publications (2)

Publication Number Publication Date
CN112442027A CN112442027A (en) 2021-03-05
CN112442027B true CN112442027B (en) 2022-06-28

Family

ID=74742341

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910803839.1A Active CN112442027B (en) 2019-08-28 2019-08-28 Organic compound containing nitrogen fluorene group, application thereof and organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN112442027B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150005331A (en) * 2013-07-05 2015-01-14 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR20150110101A (en) * 2014-03-24 2015-10-02 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
WO2018225940A1 (en) * 2017-06-07 2018-12-13 주식회사 엘지화학 Novel heterocyclic compound and organic light-emitting element using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150005331A (en) * 2013-07-05 2015-01-14 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR20150110101A (en) * 2014-03-24 2015-10-02 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
WO2018225940A1 (en) * 2017-06-07 2018-12-13 주식회사 엘지화학 Novel heterocyclic compound and organic light-emitting element using same

Also Published As

Publication number Publication date
CN112442027A (en) 2021-03-05

Similar Documents

Publication Publication Date Title
CN107112439B (en) Material for electronic devices
CN106132910B (en) The material of electronic device
KR102318136B1 (en) Multicyclic compound and organic light emitting device comprising the same
CN109206431B (en) Organic electroluminescent compound, application thereof and organic electroluminescent device
CN109535138B (en) Triazine compound containing deuterated phenyl, application thereof and organic electroluminescent device
TW201829414A (en) Compounds having diazadibenzofuran or diazadibenzothiophene structures
CN108409774B (en) Organic electroluminescent compound, application thereof and organic electroluminescent device
CN107108623A (en) Heterocyclic compound with the tall and erect structure of dibenzazepine
TW201945374A (en) Cycloalkyl-substituted polycyclic aromatic compound
TW201808917A (en) Compounds having spirobifluorene structures
CN111039800B (en) Organic compound containing condensed ring structure and organic electroluminescent device
TW201638087A (en) Carbazoles having two dibenzofuran or dibenzothiophene substituents
TWI754152B (en) Heterocyclic compound, organic light emitting device comprising the same, manufacturing method of the same and composition for organic material layer of organic light emitting device
TW202039417A (en) Materials for electronic devices
JP2022514880A (en) Materials for electronic devices
CN103772264A (en) Compound and organic light emitting device comprising the same
CN114890996B (en) Heterocyclic compound and organic light-emitting element comprising same
CN110734448B (en) Organic compound, application thereof and organic electroluminescent device
CN111138418B (en) Organic heterocyclic compound, application thereof and organic electroluminescent device
CN109659448B (en) Organic mixture, composition and organic electronic device
CN110759939A (en) Organic compound, application thereof and organic electroluminescent device
CN111961054B (en) Organic compound containing nitrogen heterocycle, application thereof and organic electroluminescent device
KR20220057778A (en) Novel compound, coating composition comprising same, organic light emitting device using same and method of manufacturing same
CN113429348B (en) Anthracene imidazole derivative, organic electroluminescent material and consumer product
CN111961055B (en) Organic compound containing nitrogen spiro structure, application 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
GR01 Patent grant
GR01 Patent grant