CN111635413B - Compound, organic electronic device including the same, and display device or lighting device including the same - Google Patents

Compound, organic electronic device including the same, and display device or lighting device including the same Download PDF

Info

Publication number
CN111635413B
CN111635413B CN202010556649.7A CN202010556649A CN111635413B CN 111635413 B CN111635413 B CN 111635413B CN 202010556649 A CN202010556649 A CN 202010556649A CN 111635413 B CN111635413 B CN 111635413B
Authority
CN
China
Prior art keywords
compound
group
experimental example
added
emitting device
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
CN202010556649.7A
Other languages
Chinese (zh)
Other versions
CN111635413A (en
Inventor
蒋佐权
廖良生
屈扬坤
郑琦
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.)
Suzhou University
Original Assignee
Suzhou University
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 Suzhou University filed Critical Suzhou University
Priority to CN202010556649.7A priority Critical patent/CN111635413B/en
Publication of CN111635413A publication Critical patent/CN111635413A/en
Application granted granted Critical
Publication of CN111635413B publication Critical patent/CN111635413B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other 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
    • C09K2211/1044—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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The present invention relates to a compound including a compound represented by the following general formula (1):wherein Y, R 0 To R 3 G, A is as defined in the specification. The compound shown in the general formula (1) has main functional elements of realizing intermolecular interaction through space non-conjugated connection, has excellent luminescent performance, and can be used as a material of an organic material layer of an organic luminescent device, in particular a material of a core luminescent layer.

Description

Compound, organic electronic device including the same, and display device or lighting device including the same
Technical Field
The invention relates to a compound, an organic electronic device containing the same, a display device or a lighting device, and belongs to the technical field of organic electronics.
Background
The organic electronic device is typically represented by an organic light emitting device, and a typical example of the organic light emitting device is an organic light emitting diode (Organic Light Emitting Diode, abbreviated as OLED). An organic light emitting diode is a current driven light emitting device using an organic material as an active material, and specifically refers to a technology in which an organic semiconductor material and an organic light emitting material emit light through carrier injection and recombination under the driving of an electric field. Unlike inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable functions, flexibility and good film forming property. And the device based on the organic material is generally simple in manufacturing process, easy to prepare in a large area, environment-friendly, and capable of adopting a film preparation method with lower operation temperature, so that the device has the advantage of low manufacturing cost, has huge application potential and is widely focused and researched by students at home and abroad in the past 30 years.
A large number of materials are currently being developed for use in the field of organic electronic devices, and most of the materials of practical value are phosphorescent materials, which are rare and expensive, and complex to synthesize, and thus have high cost. Therefore, developing pure organic materials with higher efficiency remains a significant problem.
There is a continuing need to develop new, efficient, organic materials that can be used in the OLED field.
Disclosure of Invention
The invention aims to provide an organic compound with a spiro structure, an organic electronic device comprising the organic compound, and a display device or a lighting device.
In order to achieve the above purpose, the present invention provides the following technical solutions: a compound comprising a compound represented by the following general formula (1):
wherein Y is selected from O, S (=o) 2 Any one of CR 'R ", se or P (=o) R';
R、R 0 to R 3 R 'and R' are each independently selected from hydrogen, deuterium, halogen groups, nitrile groups; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; a substituted or unsubstituted alkylsulfonyl group; a substituted or unsubstituted arylsulfonyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; substituted or unsubstituted aryl phosphino; through taking out Substituted or unsubstituted phosphine oxide groups; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl; a substituted or unsubstituted heterocyclic group; or may be bonded to an adjacent group to form a ring;
g is selected from a direct bond, a substituted or unsubstituted C6-C30 arylene, a C4-C30 heteroarylene;
a is selected from hydrogen, deuterium, halogen groups, nitrile groups, sulfone groups, carbonyl groups, ester groups, substituted or unsubstituted aliphatic groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aralkenyl groups, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heterocyclic groups.
Further, in the compound represented by the general formula (1), a is selected from hydrogen, deuterium, halogen groups; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; a substituted or unsubstituted alkylsulfonyl group; a substituted or unsubstituted arylsulfonyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; substituted or unsubstituted aryl phosphino; substituted or unsubstituted phosphine oxide groups; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl; a substituted or unsubstituted heterocyclic group.
The invention also provides an organic light-emitting device, which comprises a first electrode and a second electrode which are oppositely arranged, wherein an organic material layer is arranged between the first electrode and the second electrode, the organic material layer comprises a light-emitting layer, and the light-emitting layer contains the compound.
Further, the light-emitting layer is composed of a sensitizing material, a light-emitting material, and a host material, and the compound is any one or more of the sensitizing material or the light-emitting material or the host material.
Further, the organic material layer further comprises a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer and an electron injection layer, and the organic light emitting device is sequentially provided with the second electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer and the first electrode from the height direction.
Further, the compound is contained in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
Further, the organic light emitting device referred to in the present specification includes front side light emitting, rear side light emitting, and both side light emitting.
Further, "front side" as referred to in the present specification means furthest from the substrate, and "rear side" means closest to the substrate.
The invention also provides a display device or a lighting device comprising the organic light emitting device.
Compared with the prior art, the invention has the beneficial effects that: the compound of the invention can be used as the material of an organic material layer in an organic light-emitting device. The compound according to at least one exemplary embodiment of the present specification as a host material may realize a high-efficiency organic light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a light emitting material can realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a sensitizer may realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a hole transport material may realize a high-efficiency light emitting device while realizing a low driving voltage.
The compounds described in this specification can be used as materials for hole injection, hole transport, hole injection and hole transport, luminescence, electron transport, electron blocking or electron injection. Furthermore, the compounds described in this specification can also be used for materials of organic photovoltaic devices or organic transistors.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, it can be implemented according to the content of the specification, and the following detailed description of the preferred exemplary embodiments of the present invention will be given with reference to the accompanying drawings.
Drawings
Fig. 1 shows an example of an organic light emitting device composed of a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4;
fig. 2 shows an example of an organic light emitting device composed of a substrate 1, a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, an electron transport layer 7, an electron injection layer 9, and a second electrode 4.
Reference numerals
1: substrate
2: first electrode
3: light-emitting layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: electron blocking layer
8: electron transport layer
9: electron injection layer
Detailed Description
The detailed description of the invention is further described below in connection with the accompanying drawings and exemplary embodiments. The following exemplary embodiments are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
Term interpretation in this specification:
"substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, halogen group, nitrile group, nitro group, hydroxyl group, carbonyl group, ester group, imide group, amine group, phosphine oxide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamino group, aralkylamine group, heteroarylamine group, arylamine group, arylphosphine group; and a heterocyclic group, or a substituent which is unsubstituted or linked by two or more substituents among the substituents exemplified above. For example, a "substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl may also be aryl, and may be interpreted as two substituents to which phenyl is attached.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structure, but is not limited thereto.
In the present specification, for the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structure, but is not limited thereto.
In the present specification, the number of carbon atoms of the amide group is not particularly limited, but is preferably 1 to 25. Specifically, the amide group may be a compound having the following structure, but is not limited thereto.
In the present specification, the silyl group may be represented by the formula-SiR a R b R c R represents a 、R b And R is c Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
In the present specification, the boron group may be represented by the formula-BR a R b R represents a 、R b Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the boron group include, but are not limited to, dimethylboronyl, diethylboronyl, t-butylmethylboronyl, diphenylboronyl, phenylboronyl, and the like.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to one exemplary embodiment, the alkyl group has a carbon number of 1 to 20. According to another exemplary embodiment, the alkyl group has a carbon number of 1 to 10. According to yet another exemplary embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
Substituents described in this specification that contain alkyl, alkoxy and other alkyl moieties include both straight chain and branched forms.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to one exemplary embodiment, the alkenyl group has a carbon number of 2 to 20. According to another exemplary embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another exemplary embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 40. According to another exemplary embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 20. According to yet another exemplary embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present specification, the number of carbon atoms of the alkylamino group is not particularly limited, but is preferably 1 to 40. Specific examples of the alkylamino group include, but are not limited to, methylamino group, dimethylamino group, ethylamino group, diethylamino group, phenylamino group, naphthylamino group, biphenylamino group, anthracenylamino group, 9-methyl-anthracenylamino group, diphenylamino group, phenylnaphthylamino group, xylylamino group, phenyltolylamino group, triphenylamino group, and the like.
In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. An arylamine group containing two or more aryl groups can contain a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
Specific examples of the arylamino group include, but are not limited to, a phenylamino group, a naphthylamino group, a biphenylamino group, an anthrylamino group, a 3-methyl-phenylamino group, a 4-methyl-naphthylamino group, a 2-methyl-biphenylamino group, a 9-methyl-anthrylamino group, a diphenylamino group, a phenylnaphthylamino group, a xylylamino group, a phenyltolylamino group, a carbazolyl group, a triphenylamino group, and the like.
In the present specification, examples of the heteroarylamino group include a substituted or unsubstituted mono-heteroarylamino group, a substituted or unsubstituted di-heteroarylamino group, or a substituted or unsubstituted tri-heteroarylamino group. Heteroaryl groups in the heteroarylamine group may be monocyclic heterocyclic groups or polycyclic heterocyclic groups. The heteroarylamine group comprising two or more heterocyclic groups may comprise a monocyclic heterocyclic group, a polycyclic heterocyclic group, or both a monocyclic heterocyclic group and a polycyclic heterocyclic group.
In the present specification, examples of the arylphosphino group include a substituted or unsubstituted monoarylphosphino group, a substituted or unsubstituted diarylphosphino group, or a substituted or unsubstituted triarylphosphino group. The aryl group in the aryl phosphino group may be a monocyclic aryl group or a polycyclic aryl group. An arylphosphino group comprising two or more aryl groups may comprise a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one exemplary embodiment, the aryl group has a carbon number of 6 to 30. According to one exemplary embodiment, the aryl group has 6 to 20 carbon atoms. When the aryl group is a monocyclic aryl group, examples of the monocyclic aryl group include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Examples of polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, indenyl,Radicals, fluorenyl radicals, triphenylene radicals, and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.
When the fluorenyl group is substituted, the fluorenyl group may be And +.>
However, the fluorenyl group is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing one or more of N, O, P, S, si and Se as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. According to one exemplary embodiment, the heterocyclyl has a number of carbon atoms from 1 to 30. Examples of heterocyclyl groups include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, noisyl, indolizinyl, oxazinyl, phthalazinyl, acridinopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, indolocarbazolyl, imidazoyl, phenanthridinyl, and the like.
In this specification, the above description of heterocyclyl groups may be applied to heteroaryl groups, except that heteroaryl groups are aromatic.
In the present specification, the above description of aryl groups can be applied to aryl groups in aryloxy groups, arylthio groups, arylsulfonyl groups, arylphosphino groups, aralkyl groups, aralkylamino groups, aralkenyl groups, alkylaryl groups, arylamino groups, and arylheteroarylamino groups.
In the present specification, the above description of the alkyl group may be applied to the alkyl group in the alkylthio group, the alkylsulfonyl group, the aralkyl group, the aralkylamino group, the alkylaryl group, and the alkylamino group.
In this specification, the above description of heterocyclyl groups may be applied to heteroaryl groups in heteroaryl, heteroarylamine and arylheteroarylamine groups.
In the present specification, the germanium group may be represented by the formula-GeR a R b R c R represents a 、R b And R is c Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the germanium group include trimethylgermanium group, triethylgermanium group, t-butyldimethylgermanium group, and the like, but are not limited thereto.
In the present specification, the above description of alkenyl groups may be applied to alkenyl groups in aralkenyl groups.
In the present specification, the above description of aryl groups can be applied to arylene groups, except that arylene groups are divalent.
In this specification, the above description of heteroaryl groups may be applied to heteroarylene groups, except that the heteroarylene group is divalent.
In the present specification, the meaning of bonding with an adjacent group to form a ring means bonding with an adjacent group to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; a substituted or unsubstituted aromatic heterocycle; or a fused ring thereof.
In the present specification, an aliphatic hydrocarbon ring means a ring of a non-aromatic group constituted of only carbon atoms and hydrogen atoms as a ring. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1, 4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like, but are not limited thereto.
In the present specification, an aromatic hydrocarbon ring means an aromatic ring composed of only carbon atoms and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, benzophenanthrene, phenalene, pyrene, tetracene,Pentacene, fluorene, indene, acenaphthene, benzofluorene, spirofluorene, etc., but is not limited thereto.
In the present specification, an aliphatic heterocyclic ring means an aliphatic ring containing one or more hetero atoms. Specifically, examples of the aliphatic heterocycle include ethylene oxide, tetrahydrofuran, 1, 4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azacyclooctane, thiacyclooctane, and the like, but are not limited thereto.
In this specification, an aromatic heterocycle means an aromatic ring containing one or more heteroatoms. Specifically, examples of the aromatic heterocycle include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, pyrimidine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, acridine, phenanthridine, naphthyridine, triazaindene, indole, indolizine, benzothiazole, benzoxazole, benzimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole, benzocarbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, phenanthridine, indenocarbazole, and the like, but are not limited thereto.
In the present specification, aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic heterocyclic ring and aromatic heterocyclic ring may be monocyclic or polycyclic.
According to an exemplary embodiment of the present specification, the general formula (1) may be represented by any one of the following general formulas (2) to (7).
[ general formula (2) ]
In the general formula (2), R, R 0 To R 3 Identical to those defined in the general formula (1),
[ general formula (3) ]
In the general formula (3), R, R 0 To R 3 Identical to those defined in the general formula (1),
[ general formula (4) ]
In the general formula (4), R, R 0 To R 3 Identical to those defined in the general formula (1),
[ general formula (5) ]
In the general formula (5), R, R 0 To R 3 R 'and R' are the same as those defined in the general formula (1),
[ general formula (6) ]
In the general formula (6), R, R 0 To R 3 Identical to those defined in said general formula (1), and
[ general formula (7) ]
In the general formula (7), R, R 0 To R 3 And R' is the same as those defined in the general formula (1).
In the structural formula, any one carbon is a linking moiety for forming a monovalent group, and the remaining carbons are hydrogen or a group to which one or two or more of substituents (e.g., halogen group, nitrile group, alkyl group, silyl group, arylamino group, arylphosphine group, aryl group, and heteroaryl group) are bonded.
According to an exemplary embodiment of the present invention, in the general formulae (2) to (7), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group.
According to an exemplary embodiment of the present invention, in the general formulae (2) to (7), G may be selected from a direct bond or the following structural formula.
/>
According to an exemplary embodiment of the present invention, in the general formulae (2) to (7), a is selected from the following structural formulae.
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
According to an exemplary embodiment of the invention, Y is O, R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is S, R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the present invention, Y is S (=o) 2 R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is CR 'R', R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is Se, R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the present invention, Y is P (=o) Ph, R is phenyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is O, R is pyridinyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is S, R is pyridinyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the present invention, Y is S (=o) 2 R is pyridyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is CR 'R', R is pyridinyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is Se, R is pyridinyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the present invention, Y is P (=o) R', R is pyridinyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is O, R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is S, R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the present invention, Y is S (=o) 2 R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is CR 'R', R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is Se, R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the present invention, Y is P (=o) R', R is thienyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is O, R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the invention, Y is S, R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the present invention, Y is S (=o) 2 R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is CR 'R', R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
/>
According to an exemplary embodiment of the invention, Y is Se, R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
According to an exemplary embodiment of the present invention, Y is P (=o) R', R is methyl, and R0 to R3 are hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of formula (1) may be any one of the following compounds.
/>
/>
The compound of formula (1) can be prepared by the following reaction scheme.
< reaction No. 1>
In the reaction formula 1, Y is the same as defined in the general formula (1), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
< reaction No. 2>
In reaction formula 2, Y, R is as defined in general formula (1), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
The reaction formula relates to an example in which a specific substituent is introduced, but a person skilled in the art may introduce a substituent without using a technique known in the art, if necessary, and in introducing a substituent, the introduction may be performed by changing the kind or number of substituents. Furthermore, the introduction may be performed by a person skilled in the art by varying the sample, reaction conditions or starting materials of the following reaction formula using techniques known in the art.
For example, the compound represented by the general formula (1) may be prepared according to the above reaction formulae 1 to 2, substituents may be bonded thereto using methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art. The substituent may be bonded according to the above equations 1 to 2, however, the reaction is not limited thereto.
The invention also provides an organic light-emitting device prepared based on the compound of the general formula (1), which comprises a first electrode and a second electrode which are oppositely arranged, wherein one or more organic material layers are arranged between the first electrode and the second electrode, the organic material layers comprise a light-emitting layer, and the light-emitting layer comprises the compound. Wherein the light-emitting layer is composed of any one or more of a sensitizing material, a light-emitting material and a host material, and the compound is used as any one or more of the sensitizing material or the light-emitting material. The organic material layer further comprises a hole injection layer, a hole transmission layer, an electron blocking layer, an electron transmission layer and an electron injection layer, and the anode, the hole injection layer, the hole transmission layer, the electron blocking layer, the light-emitting layer, the electron transmission layer, the electron injection layer and the cathode are sequentially arranged on the organic light-emitting device from the height direction. Of course, the compound may be provided in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer, in addition to the compound described above. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.
In this specification, when one member is provided "on" another member, this includes not only a case where one member is in contact with another member but also a case where another member exists between two members.
In this specification, when a portion "includes" one constituent element, unless specifically described otherwise, this is not meant to exclude another constituent element, but is meant to also include another constituent element.
In one exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or the layer that simultaneously injects and transports holes contains the compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer composed of a host material and a light emitting material, and the light emitting material includes a compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer is composed of a single component of a light emitting material including the compound of formula (1).
In yet another exemplary embodiment, the organic material layer includes a light emitting layer composed of a host material and a light emitting material, the host material including the compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes a compound of formula (1), and further includes a light emitting dopant.
In another exemplary embodiment, the luminescent dopant comprises a fluorescent luminescent material or a phosphorescent luminescent material.
In yet another exemplary embodiment, the phosphorescent light-emitting material comprises an iridium-based phosphorescent light-emitting material.
In yet another exemplary embodiment, the phosphorescent light-emitting material comprises Ir (ppy) 3 Or Ir (MDQ) 2 acac。
In one exemplary embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes an electron blocking layer, and the electron blocking layer includes a compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons contains the compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer and an electron transporting layer, and the electron transporting layer includes a compound of formula (1).
In one exemplary embodiment of the present specification, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor, and an organic transistor.
Under similar principles for use in organic light emitting devices, the compounds according to the present description may also be applied in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like. For example, the organic solar cell may have a structure including a first electrode, a second electrode, and a photoactive layer disposed between the first electrode and the second electrode, and the photoactive layer may include the compound.
An exemplary embodiment of the present specification provides an organic light emitting device, including: a first electrode; a second electrode disposed to face the first electrode; a light emitting layer disposed between the first electrode and the second electrode; and two or more organic material layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers contains a heterocyclic compound. In one exemplary embodiment, the two or more organic material layers may be selected from: an electron transport layer, an electron injection layer, a layer that simultaneously transports and injects electrons, a hole injection layer, a hole transport layer, and a hole blocking layer.
In one exemplary embodiment of the present specification, the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes a heterocyclic compound. Specifically, in one exemplary embodiment of the present specification, the heterocyclic compound may be further included in one of two or more electron transport layers, and may be included in each of the two or more electron transport layers.
Further, in an exemplary embodiment of the present specification, when the heterocyclic compound is included in each of one or more electron transport layers, other materials than the heterocyclic compound may be the same as or different from each other.
In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate, wherein the first electrode is a positive electrode and the second electrode is a negative electrode, i.e., a normal type organic light emitting device.
In still another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate, wherein the first electrode is a negative electrode, and the second electrode is a positive electrode, i.e., an organic light emitting device having a reverse structure (inverted type).
For example, a structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in fig. 1 and 2.
Fig. 1 shows an exemplary embodiment of an organic light emitting device composed of a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4. In the structure as described above, the compound may be contained in the light emitting layer.
Fig. 2 shows an exemplary embodiment of an organic light emitting device composed of a substrate 1, a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a second electrode 4. In the structure as described above, the compound may be contained in one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer.
The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers comprises the compound of the present specification, i.e., the compound of formula (1).
When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by the following method: the positive electrode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the positive electrode, and then depositing a material usable as a negative electrode on the organic material layer. In addition to the method described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.
In addition, in manufacturing an organic light emitting device, the compound of the general formula (1) may be formed into an organic material layer not only by a vacuum deposition method but also by a solution application method. Here, the solution application method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray coating, roll coating, or the like, but is not limited thereto.
In addition to the method described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate (international publication No. 2003/012890). However, the manufacturing method is not limited thereto.
In one exemplary embodiment of the present description, the first electrode is a positive electrode and the second electrode is a negative electrode.
In another exemplary embodiment of the present specification, the first electrode is a negative electrode and the second electrode is a positive electrode.
As the positive electrode material, a material having a large work function is generally preferable to smoothly inject holes into the organic material layer. Specific examples of positive electrode materials that can be used in the present invention include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ZnO: al or SnO 2 : sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, polyaniline, and the like, but is not limited thereto.
As the negative electrode material, a material having a small work function is generally preferable to smoothly inject electrons into the organic material layer. Specific examples of the negative electrode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al, etc., but is not limited thereto.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has an effect of injecting holes in the positive electrode, and has an excellent hole injection effect to 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 also has an excellent thin film forming capability. It is preferred that the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transporting layer is a layer that receives holes from the hole injecting layer and transports the holes to the light emitting layer, and the hole transporting material is such a suitable material: which can receive holes from the positive electrode or the hole injection layer, transfer holes to the light emitting layer, and have high mobility to holes. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which both a common moiety and a non-common moiety exist, and the like, but are not limited thereto.
The electron transporting material is a material that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting material is suitably a material having a large electron mobility that can be proficiently receiving electrons from the negative electrode and can transfer electrons to the light emitting layer. Specific examples thereof include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material used according to the prior art. In particular, suitable examples of cathode materials are typical materials with a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
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 the negative electrode and an excellent effect of injecting electrons into the light emitting layer or the light emitting material, prevents excitons generated by the light emitting layer from migrating to the hole injecting layer, and also has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, thiazole, thiadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives and the like, but are not limited thereto.
The light emitting layer is preferably of such a material: which can receive holes and electrons respectively transported by the hole transport layer and the electron transport layer and combine the holes and electrons to emit light in the visible light region, and has good quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Base groupA compound which is a carbazole; a dimeric styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzoxazole, benzothiazole and benzimidazole based compounds; poly (p-phenylene vinylene) (PPV) based polymers; a spiro compound; polyfluorene, rubrene, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and examples thereof include pyrene, anthracene, naphthalene, bisindenopyrene, and the like having an arylamino group, the styrene amine compound is a compound in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, and one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrylenediamine, styrylenetriamine, styrenetetramine, and the like. Further, examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.
The light emitting layer may comprise a host material and a light emitting material, and the light emitting material may comprise a doped light emitting material and a doped sensitizer material. The host material is preferably an organic compound material, and a host material containing a metal complex may be used. Examples of the host material are not particularly limited, and any host material may be used together with any light-emitting material, and examples of the organic compound used as a host are selected from: a group consisting of the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; a group consisting of the following aromatic heterocyclic compounds: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole pyridobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazineOxazines, triazines, oxazines, oxathiazines, oxadiazines, indoles, benzimidazoles, indoles, indolizines, benzoxazoles, benzisoxazoles, benzothiazoles, quinolines, isoquinolines, cinnolines, quinazolines, quinoxalines, naphthyridines, phthalazines, pteridines, xanthenes, acridines, phenazines, phenothiazines, phenoxazines, benzofuranopyridines, furodipyridines, benzothiophenopyridines, thiophenodipyridines, benzoselenophenopyridines, and selenophenodipyridines; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group, but are not limited thereto. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonephthalenyl, phosphino, and combinations thereof, but are not limited thereto.
Examples of the metal complex include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium bis (2-methyl-8-quinoline) chloride, gallium bis (2-methyl-8-quinoline) (o-cresol), gallium bis (2-methyl-8-quinoline) (1-naphthoic acid), aluminum bis (2-methyl-8-quinoline) (2-naphthoic acid), gallium iridium complex, platinum complex, osmium complex, and the like.
The organic light emitting device according to the present specification includes front side light emitting, rear side light emitting and both side light emitting, depending on the materials used.
The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be specifically described in the following exemplary embodiments. However, the following exemplary embodiments are provided to illustrate the present specification, and the scope of the present specification is not limited thereto.
Preparation example
Synthesis example
The reaction formula relates to an example in which a specific substituent is introduced, but a person skilled in the art may introduce a substituent without using a technique known in the art, if necessary, and in introducing a substituent, the introduction may be performed by changing the kind or number of substituents. Furthermore, the introduction may be performed by a person skilled in the art by varying the sample, reaction conditions or starting materials of the following reaction formula using techniques known in the art.
For example, the compound represented by formula 1 has an intermediate unit according to the following synthesis method.
Synthesis example 1 Synthesis of the following intermediates A-1, B-1, C-1, D-1, E-1, F-1. The definition of Y is the same as in formula 1.
Synthesis example 1-1> Synthesis of the following intermediate A-1
(9-oxo-9H-xanthin-1-yl) boronic acid (3.60 g,15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (4.14 g,30 mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water under nitrogen atmosphere and heated under reflux for 18 hours. After the reaction was stopped, it was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected by using methylene chloride and separated by rotary drying and column chromatography to give intermediate A-1 (6.27 g) in 83% yield.
MS[M+H] + ＝504
Synthesis example 1-2 Synthesis of intermediate B-1 below
(9-oxo-9H-thioxanth-1-yl) boronic acid (3.84 g,15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82 g,15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (4.14 g,30 mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected using methylene chloride and separated by rotary drying and column chromatography to give intermediate B-1 (6.63 g) in 85% yield.
MS[M+H] + ＝520
Synthesis example 1-3 Synthesis of the following intermediate C-1
(10, 10-dimethyl-9-oxo-9, 10-dihydro-anthracene-1-yl) boronic acid (3.99 g,15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82 g,15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (4.14 g,30 mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen atmosphere and heated under reflux for 18 hours. After the reaction was stopped, cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected by using methylene chloride and separated by rotary drying and column chromatography to give intermediate C-1 (6.60 g) in 83% yield.
MS[M+H] + ＝530
Synthesis example 1-4 Synthesis of the following intermediate D-1
(10, 10-Dioxo-9-oxo-9H-thioxan-1-yl) benzoic acid (4.32 g,15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82 g,15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (4.14 g,30 mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected using methylene chloride and separated by rotary drying and column chromatography to give intermediate D-1 (6.46 g) in 78% yield.
MS[M+H] + ＝552
Synthesis example 1-5 Synthesis of intermediate E-1 below
(5-oxo-10-oxo-5-phenyl-10H-acrophosin-1-yl) boron acid (4.54 g,15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82 g,15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (4.14 g,30 mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected using methylene chloride and separated by rotary drying and column chromatography to give intermediate E-1 (6.88 g) in 75% yield.
MS[M+H] + ＝612
Synthesis examples 1 to 6 Synthesis of the following intermediate F-1
(9-oxo-9H-selenofloxacin-1-yl) boronic acid (15 mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82 g,15 mmol), tetrakis (triphenylphosphine) palladium (1.73 g,1.5 mmol) and potassium carbonate (30 mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water under nitrogen atmosphere and heated under reflux for 18 hours. After the reaction was stopped, cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and an organic phase was collected using methylene chloride and separated by rotary drying and column chromatography to give intermediate F-1 (6.8 g) in 80% yield.
MS[M+H] + ＝567
< synthetic example 2> synthesis of the following intermediates a-2, B-2, C-2. The definition of Y is the same as in formula 1.
Intermediates A-2 to C-2 were prepared in the same manner as the process for preparing intermediates A-1 to C-1, except that 4- (4-bromophenyl) -2, 6-diphenylpyrimidine was used as the starting material in Synthesis examples 1-1 to 1-3 in place of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. MS [ M+H ] of intermediates A-2 to C-2] + The values are shown in table 1 below.
TABLE 1
Numbering of compounds MS[M+H] +
A-2 503
B-2 519
C-2 529
< synthetic example 3> Synthesis of the following intermediates A-3, B-3, C-3, D-3, E-3. The definition of Y is the same as in formula 1.
/>
Intermediates a-3 to E-3 were prepared in the same manner as the process for preparing intermediates a-1 to E-1, except that 7-bromo-5, 9-dioxin-13 b-boronaphtho [3,2,1-de was used]Anthracene was substituted for 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine as a starting material in synthesis examples 1-1 to 1-3. MS [ M+H ] of intermediates A-3 to E-3] + The values are shown in table 2 below.
TABLE 2
< synthetic example 4> Synthesis of the following intermediates A-4, B-4, C-4. The definition of Y is the same as in formula 1.
Intermediates a-4 to C-4 were prepared in the same manner as the process for preparing intermediates a-1 to C-4, except that 2-bromothioxanthene 5, 10, 10-tetraoxide was used as the starting material in synthesis examples 1-1 to 1-3 instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. The MS [ M+H ] + values for intermediates A-4 to C-4 are shown in Table 3 below.
TABLE 3 Table 3
Numbering of compounds MS[M+H] +
A-4 475
B-4 491
C-4 501
< synthetic example 5> Synthesis of the following intermediates A-5, B-5, C-5. The definition of Y is the same as in formula 1.
Intermediates A-5 to C-5 were prepared in the same manner as the process for preparing intermediates A-1 to C-5, except that 11- (4-bromophenyl) -6a,14 a-dihydrodibenzo [ a, j ] phenazine was used as the starting material in Synthesis examples 1-1 to 1-3 in place of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. The MS [ M+H ] + values of intermediates A-5 to C-5 are shown in Table 4 below.
TABLE 4 Table 4
< synthetic example 6> Synthesis of the following intermediates A-6, B-6, C-6. The definition of Y is the same as in formula 1.
Intermediates A-6 to C-6 were prepared in the same manner as the process for preparing intermediates A-1 to C-5, except that 17-bromo-5, 9-diphenyl-5, 9-dihydro-5, 9-diaza 13 b-boronaphtho [3,2,1-de was used]Anthracene was substituted for 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine as a starting material in synthesis examples 1-1 to 1-4. MS [ M+H ] of intermediates A-5 to D-5] + The values are shown in table 5 below.
TABLE 5
Numbering of compounds MS[M+H] +
A-6 616
B-6 632
C-6 642
< preparation example 1> Synthesis of Compound 1 below
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-1 (9.67 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 1 (10.37 g,14.21mmol, yield about 74%).
MS[M+H] + ＝731
< preparation example 2> Synthesis of Compound 2 below
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-2 (9.64 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 2 (10.08 g,13, 82mmol, yield about 72%).
MS[M+H] + ＝730
< preparation example 3> Synthesis of Compound 3 below
2-bromo-N, N-diphenylaniline (5.79 g,17.86 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-3 (8.29 g,17.86 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 3 (8.65 g,12.50mmol, yield about 70%).
MS[M+H] + ＝692
< preparation example 4> Synthesis of Compound 4 below
2-bromo-N, N-diphenylaniline (6.08 g,18.75 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-4 (8.90 g,18.75 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 3 (9.22 g,13.13mmol, yield about 70%).
MS[M+H] + ＝703
< preparation example 5> Synthesis of Compound 5 below
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-5 (9.56 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 5 (9.21 g,11.84mmol, yield about 68%).
MS[M+H] + ＝779
< preparation example 6> Synthesis of the following Compound 6
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate A-6 (10.70 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain Compound 6 (11.15 g,13.23mmol, yield about 76%).
MS[M+H] + ＝843
< preparation example 7> Synthesis of the following Compound 7
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate B-1 (9.98 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 7 (11.78 g,15.74mmol, yield about 82%).
MS[M+H] + ＝748
< preparation example 8> Synthesis of Compound 8 below
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate B-2 (9.96 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 8 (10.72 g,14.40mmol, yield about 75%).
MS[M+H] + ＝747
< preparation example 9> Synthesis of the following Compound 9
2-bromo-N, N-diphenylaniline (5.79 g,17.86 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate B-3 (8.57 g,17.86 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 9 (10.12 g,14.29mmol, yield about 80%).
MS[M+H] + ＝709
< preparation example 10> Synthesis of the following Compound 10
2-bromo-N, N-diphenylaniline (6.08 g,18.75 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate B-4 (9.19 g,18.75 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 10 (9.69 g,13.50mmol, yield about 72%).
MS[M+H] + ＝719
< preparation example 11> Synthesis of Compound 11 below
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate B-5 (9.86 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 11 (8.97 g,11.32mmol, yield about 65%).
MS[M+H] + ＝795
< preparation example 12> Synthesis of the following Compound 12
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-6 (10.98 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 12 (12.26 g,14.28mmol, yield about 82%).
MS[M+H] + ＝859
< preparation example 13> Synthesis of Compound 13 below
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-1 (10.18 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 13 (11.63 g,15.36mmol, yield about 80%).
MS[M+H] + ＝758
< preparation example 14> Synthesis of the following Compound 14
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-2 (10.15 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 14 (17.84 g,15.36mmol, yield about 80%).
MS[M+H] + ＝757
< preparation example 15> Synthesis of the following Compound 15
2-bromo-N, N-diphenylaniline (5.79 g,17.86 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-3 (8.76 g,17.86 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 15 (9.61 g,13.40mmol, yield about 75%).
MS[M+H] + ＝619
< preparation example 16> Synthesis of the following Compound 16
2-bromo-N, N-diphenylaniline (6.08 g,18.75 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-4 (9.38 g,18.75 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain Compound 6 (10.64 g,14.62mmol, yield: about 78%).
MS[M+H] + ＝729
< preparation example 17> Synthesis of the following Compound 17
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-5 (10.04 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 17 (9.10 g,11.32mmol, yield about 65%).
MS[M+H] + ＝805
< preparation example 18> Synthesis of the following Compound 18
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate C-6 (12.30 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 18 (12.51 g,14.40mmol, yield about 75%).
MS[M+H] + ＝869
< preparation example 19> Synthesis of the following Compound 19
2-bromo-N, N-diphenylaniline (6.22 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate D-1 (10.59 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 19 (8.97 g,11.52mmol, yield about 60%).
MS[M+H] + ＝780
< preparation example 20> Synthesis of the following Compound 20
2-bromo-N, N-diphenylaniline (6.23 g,19.20 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.80 mL,21.12 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate D-3 (9.84 g,19.20 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 20 (11.08 g,14.98mmol, yield about 78%).
MS[M+H] + ＝741
< preparation example 21> Synthesis of Compound 21 below
2-bromo-N, N-diphenylaniline (5.79 g,17.86 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate E-1 (10.92 g,17.86 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 21 (14.98 g,11.61mmol, yield about 65%).
MS[M+H] + ＝840
< preparation example 22> Synthesis of the following Compound 22
2-bromo-N, N-diphenylaniline (6.08 g,18.75 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate E-3 (11.24 g,18.75 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed using a eluent of dichloromethane and petroleum ether ratio to obtain compound 22 (11.25 g,13.13mmol, yield about 75%).
MS[M+H] + ＝801
< preparation example 23> Synthesis of the following Compound 23
2-bromo-N, N-diphenylaniline (5.64 g,17.41 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the aniline, then the flask was placed at-78℃and 2.4M N-butyllithium solution (8.18 mL,19.64 mmol) was added dropwise, stirring was performed at-78℃for 1 hour, intermediate F-1 (9.86 g,17.41 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the solution. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 23 (10.37 g,13.06mmol, yield about 75%).
MS[M+H] + ＝795
< preparation example 24> Synthesis of the following Compounds 24 to 46
Compounds 24 to 46 were prepared in the same manner as in the preparation of compounds 1 to 23, except that 2-bromo-N- (4-pyridyl) -N-phenylaniline was used as the starting material in preparation examples 1 to 23, instead of 2-bromo-N, N-diphenylaniline. MS [ M+H ] of Compounds 23 to 46] + The values are shown in table 5 below.
TABLE 5
/>
< preparation example 25> Synthesis of the following Compounds 47 to 69
Compounds 47 to 69 were produced in the same manner as in the production methods of compounds 1 to 23, except that 2-bromo-N- (2-thienyl) -N-phenylaniline was used as the starting material in production examples 1 to 23. MS [ M+H ] of Compounds 47 to 69] + The values are shown in table 6 below.
TABLE 6
/>
< preparation example 26> Synthesis of the following Compounds 70 to 92
/>
Compounds 70 to 92 were produced in the same manner as in the production methods of compounds 1 to 23, except that 2-bromo-N-methyl-N-phenylaniline was used as the starting material in production examples 1 to 23, instead of 2-bromo-N, N-diphenylaniline. MS [ M+H ] of Compounds 70 to 92] + The values are shown in table 7 below.
TABLE 7
/>
Comparative exemplary embodiment of the preparation method:
by way of comparison, the synthesis of the following route was performed with the molecules of exemplary embodiment 1
Comparative example 1 Synthesis of Compound 1 below
(10-phenyl-10H-spiro [ acridine-9, 9 '-xanthene ] -1' -yl) boronic acid (10.43 g,22.32 mmol), 2- (4-bromo-phenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.67 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen protection, and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, no new product was obtained by thin plate chromatography, and the yield was 0.
Comparative example 2 Synthesis of Compound 1 below
1 '-bromo-10-phenyl-10H-spiro [ acridine-9, 9' -xanthene ] (11.21 g,22.32 mmol), (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid (7.88 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, no new product was obtained by thin plate chromatography, and the yield was 0.
Experimental examples 1-1 to 1-32
Experimental example 1-1 ]
The compound of the present invention is purified by sublimation in high purity by the existing method, and then an organic light emitting device is manufactured by the following method.
Thin coating with a thickness ofThe glass substrate of Indium Tin Oxide (ITO) was put into distilled water in which a cleaning agent was dissolved and subjected to ultrasonic washing. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed with isopropanol, acetone, and methanol solvents, and drying was performed. The substrate is then transferred to a plasma cleaner. In addition, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
Thermal vacuum deposition of 2,3,6,7, 10, 11-hexacyano-1,4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) of the following chemical formula on the transparent ITO electrode thus prepared to a thickness ofAs a hole injection layer.
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer. />
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was allowed to occur Vacuum depositing on the hole transport layer to form electronsA barrier layer.
Then, the following compound 1 and bis [2- ((oxo) diphenylphosphino) phenyl]Vacuum depositing ether (DPEPO) on electron blocking layer at a weight ratio of 3:7, with thickness ofThereby forming a light emitting layer.
The following electron-transporting materials 1,3, 5-tris [ (3-pyridyl) -3-phenyl ]]Benzene (TmPyPB)And vacuum depositing on the light-emitting layer to form an electron transport layer.
The compound lithium 8-hydroxyquinoline (Liq)And metallic aluminum->Sequentially deposited on the electron transport layer as an electron injection layer and a negative electrode. />
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material Liq are kept atTo->The deposition rate of the organic functional layer material including hole transport layer material, electron blocking layer material, luminescent layer material, electron transport layer material is maintained at +.>To-> The deposition rate of the electrode material metallic aluminium is kept +.>To->And the vacuum degree during deposition is maintained at 1×10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Experimental examples 1-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 2 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 3 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 4
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 4 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 5 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 6
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 6 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 7
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 7 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 8
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 9 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 9
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 13 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 15 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 19 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 12
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 21 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 13
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 23 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 14
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 24 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 15
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 28 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 16
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 30 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 17
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 33 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 18
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 36 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 19
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 42 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 20 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 47 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 21
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 49 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 22
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 53 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 23
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 56 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 24
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 59 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 25
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 66 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 26
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 70 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 27
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 72 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 28
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 74 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 29
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 76 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 30
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 79 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 31
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 82 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 32
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 84 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 33
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 88 was used instead of compound 1 in experimental example 1-1.
Comparative examples 1 to 1 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 1 was used instead of compound 1 in experimental example 1-1.
Comparative examples 1 to 2
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 2 was used instead of compound 1 in experimental example 1-1.
Comparative examples 1 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 3 was used instead of compound 1 in experimental example 1-1.
The results of the following table 8 were obtained when current was applied to the organic light emitting diode devices fabricated in experimental examples 1-1 to 1-32 and comparative examples 1-1, 1-2 and 1-3.
TABLE 8
/>
/>
As shown in the data in table 8, it can be seen that the materials substituted at the 1-position of heterospirofluorene all exhibited higher luminous efficiency, while comparative examples 1-1, 1-2 and 1-3 all exhibited lower external quantum efficiency.
It can be determined that the derivative of the compound of formula according to the present invention has excellent light emitting behavior and thus exhibits high efficiency characteristics, and can be applied to an organic light emitting device.
Experimental example 2-1 ]
The compound prepared in the synthesis example was subjected to high purity sublimation purification by a generally known method, and then a sensitized organic light emitting device was manufactured by the following method.
Thin coating with a thickness ofThe glass substrate of Indium Tin Oxide (ITO) was put into distilled water in which a cleaning agent was dissolved and subjected to ultrasonic washing. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed with isopropanol, acetone, and methanol solvents, and drying was performed. The substrate is then transferred to a plasma cleaner. In addition, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
Thermal vacuum deposition of 2,3,6,7, 10, 11-hexacyano-1,4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) of the following chemical formula on the transparent ITO electrode thus prepared to a thickness of As a hole injection layer.
Make things asThe following compound 4,4' -cyclohexyl-bis [ N, N-bis (4-methylphenyl) aniline as a material for transporting holes](TAPC)Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer. />
Subsequently, the following compound 4,4' -tris (carbazol-9-yl) triphenylamine (TCTA) was reacted as an electron blocking materialVacuum deposition is carried out on the hole transport layer to form an electron blocking layer.
Then, the following 3,3 '-bis (9H-carbazole-9-yl) -1,1' -biphenyl (mCBP) is taken as a main material, the compound 1 is taken as a sensitization material, C545T is taken as a luminescent material, 15 percent of the compound 1 is doped, 1 percent of the C545T is doped, and the materials are vacuum deposited on an electron blocking layer with the thickness ofThereby forming a light emitting layer.
The following electron-transporting materials 1,3, 5-tris [ (3-pyridyl) -3-phenyl ]]Benzene (TmPyPB)And vacuum depositing on the light-emitting layer to form an electron transport layer.
/>
The compound lithium 8-hydroxyquinoline (Liq)And metallic aluminum->Sequentially deposited on the electron transport layer as an electron injection layer and a negative electrode.
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material Liq are kept at To->The deposition rate of the organic functional layer material including hole transport layer material, electron blocking layer material, luminescent layer material, electron transport layer material is maintained at +.>To->Second, the deposition rate of the electrode material metallic aluminum is kept +.>To->And the vacuum degree during deposition is maintained at 1×10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Experimental example 2-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 2 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 3 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 4
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 4 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 5 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 6
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 6 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 7
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 7 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 8
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 9 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 9
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 13 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 15 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 19 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 12
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 21 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 13
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 23 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 14
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 24 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 15
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 28 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 16
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 30 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 17
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 33 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 18
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 36 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 19
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 42 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 20
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 47 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 21
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 49 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 22
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 53 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 23
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 56 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 24
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 59 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 25
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 66 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 26
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 70 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 27
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 72 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 28
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 74 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 29
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 76 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 30
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 79 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 31
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 82 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 32
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 84 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 33
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 88 was used instead of compound 1 in experimental example 2-1.
Comparative example 2-1 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 1 was used instead of compound 1 in experimental example 2-1.
/>
Comparative examples 2 to 2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 2 was used instead of compound 1 in experimental example 2-1.
Comparative examples 2 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 3 was used instead of compound 1 in experimental example 2-1.
The results of the following table 9 are obtained when current is supplied to the organic light emitting diode devices fabricated in experimental examples 2-1 to 2-32 and comparative examples 2-1, 2-2 and 2-3.
TABLE 9
/>
/>
As shown in the data in table 9, comparative example 2-1 has only 2.2% device efficiency without the addition of the compound material, and comparative examples 2-2 to 2-4 demonstrate that the added material has no sensitization effect and no improvement in device performance. Whereas the green organic light emitting devices of experimental examples 2-1 to 2-32 according to the present invention, which are the sensitizing materials for green fluorescent light emitting molecules, exhibited better performance in both current efficiency and driving voltage.
Experimental examples 3-1 to 3-32
Experimental example 3-1 ]
The compound of the present invention is purified by sublimation in high purity by the existing method, and then an organic light emitting device is manufactured by the following method.
Thin coating with a thickness ofThe glass substrate of Indium Tin Oxide (ITO) was put into distilled water in which a cleaning agent was dissolved and subjected to ultrasonic washing. After washing ITOAfter washing for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed with isopropanol, acetone and methanol solvents, and drying was performed. The substrate is then transferred to a plasma cleaner. In addition, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
Thermal vacuum deposition of 2,3,6,7, 10, 11-hexacyano-1,4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) of the following chemical formula on the transparent ITO electrode thus prepared to a thickness ofAs a hole injection layer.
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was allowed to occur Vacuum deposition is carried out on the hole transport layer to form an electron blocking layer.
Then, the following compound 1 and tris (2-phenylpyridine) iridium (III) were vacuum deposited on the electron-blocking layer at a weight ratio of 7:3 to a thickness of Thereby forming a light emitting layer.
The following electron-transporting materials 1,3, 5-tris [ (3-pyridyl) -3-phenyl ]]Benzene (TmPyPB)And vacuum depositing on the light-emitting layer to form an electron transport layer. />
The compound lithium 8-hydroxyquinoline (Liq)And metallic aluminum->Sequentially deposited on the electron transport layer as an electron injection layer and a negative electrode.
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material Liq are kept atTo->Organic functional layer materials including hole transportDeposition rates of the transport layer material, the electron blocking layer material, the light emitting layer material, the electron transport layer material are kept +.>To-> The deposition rate of the electrode material metallic aluminium is kept +.>To->And the vacuum degree during deposition is maintained at 1×10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Experimental example 3-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 2 was used instead of compound 1 in experimental example 3-1.
Experimental example 3-3 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 3 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 4
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 4 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 5 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 6
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 6 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 7
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 7 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 8
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 9 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 9 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 13 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 15 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 19 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 12
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 21 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 13
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 23 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 14
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 24 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 15
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 28 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 16
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 30 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 17
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 33 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 18
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 36 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 19
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 42 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 20 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 47 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 21
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 49 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 22
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 53 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 23
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 56 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 24
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 59 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 25
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 66 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 26
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 70 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 27
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 72 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 28
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 74 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 29
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 76 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 30
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 79 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 31
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 82 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 32
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 84 was used instead of compound 1 in experimental example 3-1.
Experimental examples 3 to 33
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 88 was used instead of compound 1 in experimental example 3-1.
Comparative example 3-1 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that comparative compound 1 was used instead of compound 1 in experimental example 3-1.
Comparative example 3-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that comparative compound 2 was used instead of compound 1 in experimental example 3-1.
Comparative examples 3 to 3 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that comparative compound 3 was used instead of compound 1 in experimental example 3-1.
/>
The following table 10 results were obtained when current was applied to the organic light emitting diode devices fabricated in experimental examples 3-1 to 3-32 and comparative examples 3-1, 3-2 and 3-3.
Table 10
/>
As shown in the data in Table 10, it can be seen that the material in which the 1-position of heterospirofluorene was substituted is the host material, ir (ppy) 3 As a guest material, the light-emitting efficiency of the green light-emitting device is high and the driving voltage is highLower. While comparative examples 3-1, 3-2 and 3-3 all show lower external quantum efficiency and higher driving voltage.
To sum up: the compound of the invention can be used as the material of an organic material layer in an organic light-emitting device. The compound has the main functional element of realizing intermolecular interaction through space non-conjugated connection, has excellent luminescent performance, and can be used as a material of an organic material layer of an organic luminescent device, in particular a material of a core luminescent layer. The compound according to at least one exemplary embodiment of the present specification as a host material may realize a high-efficiency organic light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a light emitting material can realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a sensitizer may realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a hole transport material may realize a high-efficiency light emitting device while realizing a low driving voltage.
The compounds described in this specification can be used as materials for hole injection, hole transport, hole injection and hole transport, luminescence, electron transport, electron blocking or electron injection. Furthermore, the compounds described in this specification can also be used for materials of organic photovoltaic devices or organic transistors.
The technical features of the above-described exemplary embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described exemplary embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be regarded as the scope of the description of the present specification.
The above-described exemplary embodiments represent only a few embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (5)

1. A compound, characterized in that the compound is selected from any one of the following structural formulas:
2. an organic electronic device, characterized in that:
comprising a first electrode and a second electrode;
one or more organic material layers are arranged between the first electrode and the second electrode;
wherein one or more of the layers of organic material contains the compound of claim 1.
3. The organic electronic device according to claim 2, wherein the organic material layer is composed of one or more of a light-emitting material, a sensitizing material, and a host material, and the compound is used as any one or more of the light-emitting material or the sensitizing material or the host material.
4. The organic electronic device according to claim 2, wherein the organic material layer includes a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and the compound is contained in one or more structures among the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
5. A display device or a lighting device comprising the organic electronic device as claimed in any one of claims 2 to 4.
CN202010556649.7A 2020-06-12 2020-06-12 Compound, organic electronic device including the same, and display device or lighting device including the same Active CN111635413B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010556649.7A CN111635413B (en) 2020-06-12 2020-06-12 Compound, organic electronic device including the same, and display device or lighting device including the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010556649.7A CN111635413B (en) 2020-06-12 2020-06-12 Compound, organic electronic device including the same, and display device or lighting device including the same

Publications (2)

Publication Number Publication Date
CN111635413A CN111635413A (en) 2020-09-08
CN111635413B true CN111635413B (en) 2023-08-01

Family

ID=72327089

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010556649.7A Active CN111635413B (en) 2020-06-12 2020-06-12 Compound, organic electronic device including the same, and display device or lighting device including the same

Country Status (1)

Country Link
CN (1) CN111635413B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073445B (en) * 2021-03-11 2024-02-13 中国科学院长春应用化学研究所 Organic luminescent material based on selenohexanthrone and preparation method and application thereof
CN114315878B (en) * 2021-07-09 2023-07-14 陕西莱特迈思光电材料有限公司 Organic compound, electronic component, and electronic device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084091A (en) * 2017-12-26 2018-05-29 南京高光半导体材料有限公司 A kind of novel electroluminescent compound and its application and use its organic electroluminescence device
CN108178765A (en) * 2017-12-26 2018-06-19 南京高光半导体材料有限公司 Organic electroluminescent compounds, organic electroluminescence device and its application
CN110759930A (en) * 2018-12-06 2020-02-07 广州华睿光电材料有限公司 Spiro compounds and uses thereof
CN111635391A (en) * 2020-07-06 2020-09-08 苏州久显新材料有限公司 Fluorene compound and electronic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084091A (en) * 2017-12-26 2018-05-29 南京高光半导体材料有限公司 A kind of novel electroluminescent compound and its application and use its organic electroluminescence device
CN108178765A (en) * 2017-12-26 2018-06-19 南京高光半导体材料有限公司 Organic electroluminescent compounds, organic electroluminescence device and its application
CN110759930A (en) * 2018-12-06 2020-02-07 广州华睿光电材料有限公司 Spiro compounds and uses thereof
CN111635391A (en) * 2020-07-06 2020-09-08 苏州久显新材料有限公司 Fluorene compound and electronic device

Also Published As

Publication number Publication date
CN111635413A (en) 2020-09-08

Similar Documents

Publication Publication Date Title
TWI610920B (en) Fluoranthene compound and organic electronic device comprising the same
CN109912523B (en) Heterocyclic compound and organic light-emitting device comprising same
CN112789273A (en) Novel compound and organic light emitting device comprising same
KR102163070B1 (en) Novel compound and organic light emitting device comprising the same
EP3327024B1 (en) Heterocyclic compound and organic light emitting diode comprising same
CN111620890B (en) Compound, organic electronic device including the same, and display device or lighting device
CN111440122A (en) Thermally activated delayed fluorescence material and organic light emitting device
CN107257787B (en) Heterocyclic compound and organic light-emitting element comprising same
CN111527092A (en) Heterocyclic compound and organic light-emitting device comprising the same
CN111635413B (en) Compound, organic electronic device including the same, and display device or lighting device including the same
CN112266359B (en) Thermally activated delayed fluorescence material and device
EP3369731B1 (en) Heterocyclic compound and organic light emitting element comprising same
KR102537419B1 (en) Novel compound and organic light emitting device comprising the same
CN112969701A (en) Heterocyclic compound and organic light-emitting device comprising the same
KR102495828B1 (en) Novel compound and organic light emitting device comprising the same
KR102474920B1 (en) Novel compound and organic light emitting device comprising the same
CN115867555A (en) Novel compound and organic light emitting device comprising same
KR20210012959A (en) Novel compound and organic light emitting device comprising the same
CN111454263B (en) Thermally activated delayed fluorescence material, organic light emitting device, and display/illumination device
CN111247649A (en) Heterocyclic compound and organic light-emitting device comprising same
KR102549460B1 (en) Novel compound and organic light emitting device comprising the same
KR102578743B1 (en) Novel compound and organic light emitting device comprising the same
KR102529931B1 (en) Novel compound and organic light emitting device comprising the same
KR102564847B1 (en) Novel compound and organic light emitting device comprising the same
CN113166171B (en) Heterocyclic compound and organic light-emitting device comprising the same

Legal Events

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