CN112979616B - Benzimidazole compound and preparation method and application thereof - Google Patents

Benzimidazole compound and preparation method and application thereof Download PDF

Info

Publication number
CN112979616B
CN112979616B CN202110251987.4A CN202110251987A CN112979616B CN 112979616 B CN112979616 B CN 112979616B CN 202110251987 A CN202110251987 A CN 202110251987A CN 112979616 B CN112979616 B CN 112979616B
Authority
CN
China
Prior art keywords
group
compound
organic electroluminescent
benzimidazole
layer
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
CN202110251987.4A
Other languages
Chinese (zh)
Other versions
CN112979616A (en
Inventor
李祥智
蔡烨
丁欢达
魏定纬
陈志宽
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.)
Ningbo Dingsheng New Material Co ltd
Ningbo Lumilan Advanced Materials Co Ltd
Original Assignee
Ningbo Dingsheng New Material Co ltd
Ningbo Lumilan Advanced Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Dingsheng New Material Co ltd, Ningbo Lumilan Advanced Materials Co Ltd filed Critical Ningbo Dingsheng New Material Co ltd
Priority to CN202110251987.4A priority Critical patent/CN112979616B/en
Publication of CN112979616A publication Critical patent/CN112979616A/en
Application granted granted Critical
Publication of CN112979616B publication Critical patent/CN112979616B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • 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

Landscapes

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

Abstract

The invention provides a benzimidazole compound and a preparation method and application thereof, wherein the structure of the benzimidazole compound is shown as a formula I. The benzimidazole compound provided by the invention can be used as a bipolar material, not only can transmit electrons and holes, but also has balanced transmission capability of the holes and the electrons, and avoids the influence of excessive holes or excessive electrons on current efficiency.

Description

Benzimidazole compound and preparation method and application thereof
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to a benzimidazole compound and a preparation method and application thereof, in particular to a benzimidazole compound with high luminous efficiency and a preparation method and application thereof.
Background
Recently, as the size of displays increases, there is an increasing interest in flat display elements that occupy less space. In the art, the technology of organic light emitting displays including Organic Light Emitting Diodes (OLEDs) as flat display elements has been rapidly developed. The organic light emitting diode realizes light emission by annihilation of hole and electron pairs generated by injecting holes and electrons from a hole injection electrode (anode) and an electron injection electrode (cathode) into an emission layer interposed between the anode and the cathode. Such an organic light emitting diode can be formed on a flexible transparent substrate such as plastic, can operate at a low voltage, consumes relatively low power, and has good color reproduction.
CN108780853A discloses various host materials and organic electroluminescent devices comprising the various host materials. By including a plurality of host compounds in a specific combination, the organic electroluminescent device can have improved lifetime properties. The main compound has the following structure:
Figure BDA0002966439330000011
CN108290875A discloses a novel compound capable of improving the luminous efficiency, stability and lifetime of the device, an organic electronic device using the compound, and an electronic device using the organic electronic device. The compound can improve the high luminous efficiency, low driving voltage, high heat resistance of the element, and can improve the color purity and the service life, and the structure of the compound is as follows:
Figure BDA0002966439330000012
as the demand of people for organic electroluminescent devices is gradually increased, the demand for new materials for organic electroluminescent devices is more urgent. Therefore, how to provide a material for an organic electroluminescent device with high efficiency and long lifetime becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a benzimidazole compound and a preparation method and application thereof, and particularly provides a benzimidazole compound with high luminous efficiency and a preparation method and application thereof. The benzimidazole compound provided by the invention can be used as a bipolar material, not only can transmit electrons and holes, but also has balanced transmission capability of the holes and the electrons, and avoids the influence of excessive holes or excessive electrons on current efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a benzimidazole compound, wherein the structure of the benzimidazole compound is shown in formula I:
Figure BDA0002966439330000021
wherein R is1Selected from any one of substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 cycloalkenyl, substituted or unsubstituted C-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C-C30 heteroaryl, said substituted substituent group being selected from any one or combination of at least two of deuterium, tritium, cyano, nitro, or halogen, e.g., a combination of deuterium and tritium, tritium and cyano, or a combination of cyano and nitro, and the like, but not limited thereto, other combinations not listed within the above combinations are equally applicable.
N is selected from an integer of 0 to 3, e.g. 0, 1, 2 or 3, and when n is 0 (R)1)nEach R being hydrogen when n is 2 or 31Identical or different, each R1Independently exist or are connected with each other to form a ring C.
The ring C is selected from phenyl or naphthyl.
L1、L2、L3、L4Independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C3-C30 heteroarylene group.
Ar1、Ar2、Ar3、Ar4Independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl.
Said L3And Ar3Optionally linked by a single bond to form ring I-1, Ar3And Ar4Optionally linked by a single bond to form ring I-2.
The benzimidazole compound with the specific structure can be used as a bipolar material, not only can transmit electrons and holes, but also has balanced transmission capability of the holes and the electrons, so that the current efficiency is prevented from being influenced by excessive holes or excessive electrons, the triplet state energy level of the material is higher and reaches more than 2.25eV, a current carrier used in an organic electroluminescent device is limited in a light-emitting layer, the light-emitting efficiency is prevented from being influenced by overflow, the service life is prolonged, the current efficiency is high and reaches more than 21Cd/A, and the service life is long and reaches more than 113 h.
Preferably, the benzimidazole compound has the structure of
Figure BDA0002966439330000022
Wherein R is1、n、L1、L2、L3、L4、Ar1、Ar2、Ar3、Ar4Having the same limitations as described above.
Preferably, said L1、L2、L3、L4Independently selected from a single bond or any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, or carbazolyl.
Preferably, the substituted substituent group is selected from deuterium, halogen, cyano, nitro, unsubstituted or R 'substituted C1-C30 linear alkyl, unsubstituted or R' substituted C1-C30 branched alkyl, unsubstituted or R 'substituted C1-C30 cycloalkyl, unsubstituted or R' substituted C6-C20 aryl, unsubstituted or R 'substituted C3-C20 heteroaryl or C6-C20 arylamine, or any one or combination of at least two thereof, such as deuterium and halogen, halogen and cyano, or nitro and R' substituted C1-C30 linear alkyl, and the like, but is not limited to the combinations listed above, and other combinations not listed within the above combination range are also applicable.
R' is selected from any one of deuterium, halogen, cyano or substituted C1-C30 straight-chain alkyl, substituted C1-C30 branched-chain alkyl or substituted C1-C30 cycloalkyl, and the substituted substituent group is selected from any one or combination of at least two of deuterium, halogen or cyano, such as combination of deuterium and halogen, combination of halogen and cyano or combination of deuterium and cyano, etc., but is not limited to the above-listed combinations, and other combinations not listed within the above-listed combinations are also applicable.
Preferably, Ar is1、Ar2、Ar3、Ar4Independently selected from a hole transporting group or an electron transporting group.
Preferably, the hole-transporting group is selected from
Figure BDA0002966439330000031
Figure BDA0002966439330000032
Any one of them.
Wherein, T1Selected from O, S, NR2Or CR3R4，X1Selected from N or CRX1，X2Selected from N or CRX2，X3Selected from N or CRX3，X4Selected from N or CRX4，X5Selected from N or CRX5，X6Selected from N or CRX6，X7Selected from N or CRX7，X8Selected from N or CRX8Preferably X1Selected from the group consisting of CRX1、X2Selected from the group consisting of CRX2、X3Selected from the group consisting of CRX3、X4Selected from the group consisting of CRX4、X5Selected from the group consisting of CRX5、X6Selected from the group consisting of CRX6、X7Selected from the group consisting of CRX7、X8Selected from the group consisting of CRX8Or X1-X8And only one of them is selected from N.
The R isa1、Ra2、Ra3、Ra4、Ra5、RX1、RX2、RX3、RX4、RX5、RX6、RX7、RX8、R2、R3、R4Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 straight-chain alkoxy, substituted or unsubstituted C1-C30 branched-chain alkoxy, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl.
The R isa1、Ra2、Ra3、Ra4、Ra5、RX1、RX2、RX3、RX4、RX5、RX6、RX7、RX8Independently or adjacently connected to form a ring E.
The R is3、R4Independently exist or are connected to form a ring G.
Preferably, the ring E is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted pyridyl, preferably phenyl.
Preferably, the ring G is selected from a substituted or unsubstituted fluorene ring.
Preferably, said R isa1、Ra2、Ra3、Ra4、Ra5、RX1、RX2、RX3、RX4、RX5、RX6、RX7、RX8、R2、R3、R4Independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C4 straight chain alkyl, substituted or unsubstituted C1-C4 branched chain alkyl, substituted or unsubstituted C1-C4 cycloalkyl, substituted or unsubstituted C1-C4 straight chain alkoxy, substituted or unsubstituted C1-C4 branched chain alkoxy or substituted or unsubstitutedAny one of the following unsubstituted groups:
Figure BDA0002966439330000033
Figure BDA0002966439330000041
Figure BDA0002966439330000042
wherein, the substituted groups in the following groups are selected from any one or combination of at least two of deuterium, tritium, cyano, nitro or halogen, such as deuterium and tritium combination, cyano and nitro combination or nitro and halogen combination, but not limited to the above-listed combinations, and other combinations not listed in the above combination range are also applicable.
Preferably, the electron-transporting group is selected from
Figure BDA0002966439330000043
Figure BDA0002966439330000044
Any one of them.
Wherein, T2Selected from O, S, NR5Or CR6R7，Y1Selected from N or CRY1，Y2Selected from N or CRY2，Y3Selected from N or CRY3，Y4Selected from N or CRY4，Y5Selected from N or CRY5，Y6Selected from N or CRY6，Y7Selected from N or CRY7，Y8Selected from N or CRY8，Y9Selected from N or CRY9，Y10Selected from N or CRY10，Y11Selected from N or CRY11，Y12Selected from N or CRY12，Y13Selected from N or CRY13，Y14Selected from N or CRY14，Y15Selected from N or CRY15，Y16Selected from N or CRY16，Y17Selected from N or CRY17，Y18Selected from N or CRY18，Y19Selected from N or CRY19Preferably Y1-Y4And only two of them are selected from N.
Preferably, Y2、Y4Is selected from N.
Preferably, Y1、Y3Is selected from N.
The R isY1、RY2、RY3、RY4、RY5、RY6、RY7、RY8、RY9、RY10、RY11、RY12、RY13、RY14、RY15、RY16、RY17、RY18、RY19、R3、R4、R5、R6、R7Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 straight-chain alkoxy, substituted or unsubstituted C1-C30 branched-chain alkoxy, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl.
Said R isY1、RY2、RY3、RY4、RY5、RY6、RY7、RY8、RY9、RY10、RY11、RY12、RY13、RY14、RY15、RY16、RY17、RY18、RY19Independently or adjacently linked to form a ring F, said R6、R7Independently exist or are linked to form a ring H.
Preferably, the ring F is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted pyridyl, preferably phenyl.
Preferably, the ring H is a substituted or unsubstituted fluorene ring.
Preferably, said R isY1、RY2、RY3、RY4、RY5、RY6、RY7、RY8、RY9、RY10、RY11、RY12、RY13、RY14、RY15、RY16、RY17、RY18、RY19、R5、R6、R7Independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C4 linear alkyl, substituted or unsubstituted C1-C4 branched alkyl, substituted or unsubstituted C1-C4 linear alkoxy, substituted or unsubstituted C1-C4 branched alkoxy, or any one of the following substituted or unsubstituted groups:
Figure BDA0002966439330000051
Figure BDA0002966439330000052
wherein, the substituted groups in the following groups are selected from any one or combination of at least two of deuterium, tritium, cyano, nitro or halogen, such as deuterium and tritium combination, cyano and nitro combination or nitro and halogen combination, but not limited to the above-listed combinations, and other combinations not listed in the above combination range are also applicable.
Preferably, Ar is1Is an electron transport group.
Preferably, Ar is2、Ar3、Ar4Is a hole-transporting group.
Preferably, Ar is2Is selected from Ra1、Ra2、Ra3、Ra4、Ra5And substituted phenyl.
Preferably, Ar is1Is an electron-transporting group, said Ar2、Ar3、Ar4Is a hole-transporting group.
Preferably, n is 0.
Preferably, n is 2, and R is1The connection between the two forms a benzene ring.
Preferably, the benzimidazole compound is selected from any one of the compounds of the following structures:
Figure BDA0002966439330000061
Figure BDA0002966439330000071
Figure BDA0002966439330000081
Figure BDA0002966439330000091
Figure BDA0002966439330000101
Figure BDA0002966439330000111
Figure BDA0002966439330000121
Figure BDA0002966439330000131
Figure BDA0002966439330000141
Figure BDA0002966439330000151
Figure BDA0002966439330000161
Figure BDA0002966439330000171
Figure BDA0002966439330000181
Figure BDA0002966439330000191
Figure BDA0002966439330000201
Figure BDA0002966439330000211
Figure BDA0002966439330000221
Figure BDA0002966439330000231
Figure BDA0002966439330000241
Figure BDA0002966439330000251
Figure BDA0002966439330000261
Figure BDA0002966439330000271
Figure BDA0002966439330000281
Figure BDA0002966439330000291
Figure BDA0002966439330000301
Figure BDA0002966439330000311
Figure BDA0002966439330000321
Figure BDA0002966439330000331
Figure BDA0002966439330000341
Figure BDA0002966439330000351
Figure BDA0002966439330000361
Figure BDA0002966439330000371
Figure BDA0002966439330000381
Figure BDA0002966439330000391
Figure BDA0002966439330000401
Figure BDA0002966439330000411
Figure BDA0002966439330000421
Figure BDA0002966439330000431
Figure BDA0002966439330000441
Figure BDA0002966439330000451
Figure BDA0002966439330000461
Figure BDA0002966439330000471
Figure BDA0002966439330000481
Figure BDA0002966439330000491
Figure BDA0002966439330000501
Figure BDA0002966439330000511
Figure BDA0002966439330000521
Figure BDA0002966439330000531
Figure BDA0002966439330000541
Figure BDA0002966439330000551
Figure BDA0002966439330000561
the above-mentioned term "substituted" means that hydrogen in the substituted group or compound is substituted with at least one substituent group, or with at least two substituent groups, or with a group in which at least two substituent groups are linked, or with at least two substituent groups, wherein adjacent two groups are bonded to each other to form a ring.
The group in which at least two substituent groups are linked is a group in which at least two substituent groups are linked by a covalent bond.
The halogen includes any one of fluorine, chlorine, bromine or iodine.
The above-mentioned straight-chain alkyl and branched-chain alkyl include, but are not limited to, any of methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl or tert-butyl.
The cycloalkyl group means a cyclic saturated hydrocarbon group including, but not limited to, any one of cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl or cyclooctyl.
The alkenyl group represents an unsaturated hydrocarbon group, and may be a straight chain or branched chain, including but not limited to any of a vinyl group, an allyl group, an isopropenyl group, or a 2-butenyl group.
The aryl group includes monocyclic, polycyclic and condensed ring aryl groups, the rings may be connected by non-aromatic groups, and the aryl group includes, but is not limited to, any one of phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthryl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, chrysenyl, tetracenyl, fluoranthenyl and spirobifluorenyl.
The above-mentioned heteroaryl group is an aryl group containing any one or at least two of N, O, S or Se as a heteroatom, the heteroaryl group includes, but is not limited to, any one of furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, or dihydroacridinyl.
The above definitions of the groups define the range of carbon atoms, and the number of carbon atoms is any integer within the defined range, such as C1-C30 straight chain alkyl, wherein C1-C30 respectively indicate that the structure includes one carbon atom, two carbon atoms, three carbon atoms, four carbon atoms, and the like, and so on, and thus, the description is omitted.
In a second aspect, the present invention provides a preparation method of the benzimidazole compound as described above, wherein the preparation method comprises the following steps:
(1) the compound
Figure BDA0002966439330000571
And compounds
Figure BDA0002966439330000572
Mixing and reacting to obtain the compound
Figure BDA0002966439330000573
(2) The compound obtained in step (1)
Figure BDA0002966439330000574
And compounds
Figure BDA0002966439330000575
And mixing and reacting to obtain the benzimidazole compound.
Wherein R is1、n、L1、L2、L3、L4、Ar1、Ar2、Ar3、Ar4Having the same limits as described above, X is selected from halogen.
In a third aspect, the invention provides an application of the benzimidazole compound in preparing an organic electroluminescent device or an organic electroluminescent material.
In a fourth aspect, the present invention provides an organic electroluminescent composition comprising any one or a combination of at least two of the benzimidazole compounds as described above.
In a fifth aspect, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, which are oppositely disposed.
The organic layer comprises any one or a combination of at least two of the benzimidazole compounds.
Preferably, the organic layer includes a light-emitting layer, and the light-emitting layer includes any one or a combination of at least two of the benzimidazole compounds described above.
Preferably, the light emitting layer includes a host material and a guest material.
Preferably, the host material comprises any one of or a combination of at least two of the benzimidazole compounds described above.
Preferably, the guest material comprises a phosphorescent dopant.
Preferably, the phosphorescent dopant is a metal complex comprising any one of Ir, Pt, Ni, Au, Os, Re, Rh, Zn, Ag, Fe or W.
Preferably, the organic layer includes any one or a combination of at least two of a hole injection layer, a hole transport layer, an auxiliary hole transport layer, an emission layer, a hole blocking layer, an electron injection layer, or an electron transport layer, for example, a combination of a hole injection layer and a hole transport layer, a combination of a hole transport layer and an auxiliary hole transport layer, or a combination of an electron injection layer and an electron transport layer, and the like, but is not limited to the above-listed combinations, and other combinations not listed within the above-mentioned combination range are also applicable.
Preferably, the materials of the auxiliary hole transport layer, the emission layer and the hole blocking layer are independently selected from any one or a combination of at least two of the benzimidazole compounds.
In a sixth aspect, the present invention provides an organic electroluminescent assembly comprising a series structure formed by stacking at least two organic electroluminescent devices as described above.
In a seventh aspect, the invention also provides an optoelectronic product comprising the organic electroluminescent device as described above.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a benzimidazole compound which is used as a bipolar material, can transmit electrons and holes, has balanced transmission capability of the holes and the electrons, avoids the influence of excessive holes or excessive electrons on current efficiency, has a high triplet state energy level of more than 2.25eV, can be limited in a light-emitting layer when used in an organic electroluminescent device, avoids the influence of overflow on the light-emitting efficiency and the service life, has high current efficiency of more than 21Cd/A and long service life of more than 113 h.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
Preparation example 1 Synthesis of Compound 1
The synthetic route for compound 1 is as follows:
Figure BDA0002966439330000581
the preparation steps are as follows:
(1) synthesis of intermediate 1-1: A25-mL round-bottom flask was charged with S1(1mmol), benzaldehyde (1mmol) and 8 mL of 1, 4-dioxane, heated to 100 deg.C, and after completion of the reaction, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (dichloromethane/n-hexane/methanol (volume ratio 20:10:1)) to give intermediate 1-1 (yield 78%).
(2) Synthesis of intermediate 2-1: in a 25 ml round bottom two-necked flask, intermediate 1-1(1mmol), compound S2(1mmol), potassium carbonate (1.2mmol), toluene (8 ml), water (1 ml), tetrakis (triphenylphosphine) palladium (0.05mmol) were added, heated to 100 ℃ under nitrogen, quenched with water after completion of the reaction, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, spun-dried, and the crude product was purified by column chromatography (dichloromethane/n-hexane/methanol (volume ratio 20:10:1)) to give intermediate 2-1 (yield 88%).
(3) Synthesis of Compound 1: in a 25 ml two-necked round-bottomed flask, intermediate 2-1(1mmol), compound S3(1mmol), cesium carbonate (1.2mmol), tris (dibenzylideneacetone) dipalladium (0.05mmol), and 2-dicyclohexylphosphorus-2 ', 4 ', 6 ' -triisopropylbiphenyl (0.055mmol) were added, 10 ml of toluene was heated to reflux, after completion of the reaction, cooled to 25 ℃, the solvent was removed, and the crude product was purified by column chromatography (dichloromethane/n-hexane/methanol (volume ratio 20:10:1)) to obtain compound 1 (yield 85%).
Elemental analysis: C45H31N5, theoretical value: c, 84.22, H, 4.87, N, 10.91, found: c, 84.28, H, 4.85, N, 10.87, HRMS (ESI) M/z (M)+): theoretical value: 641.2579, found: 641.2585.
preparation examples 2-4 Synthesis of Compounds 2-4
Reaction of intermediate 2-1 from preparation 1 with compound S4, compound S5, and compound S6, respectively, in the table below, following the procedure of step (3) from preparation 1 (wherein compound S3 is replaced with equal amounts of compound S4, compound S5, and compound S6, respectively) affords compound 2, compound 3, and compound 4, with the specific structures and characterizations as follows:
Figure BDA0002966439330000591
Figure BDA0002966439330000601
preparation example 5 Synthesis of Compound 5
The synthetic route for compound 5 is as follows:
Figure BDA0002966439330000602
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 5: the remaining procedure was identical to procedure (1) of preparation example 1, substituting compound S1 for the equivalent of compound S7, to afford intermediates 1-5 (77% yield).
(2) Synthesis of intermediates 2 to 5: the same amount of intermediate 1-1 as intermediate 1-5 and the same amount of compound S2 as compound S8 were substituted for intermediate 1-1, and the remaining steps were identical to step (2) of preparation example 1, to give intermediates 2-5 (yield 87%).
(3) Synthesis of Compound 5: the intermediate 2-1 was replaced with an equivalent amount of intermediate 2-5, and the remaining steps were identical to the step (3) of preparation example 1 to obtain compound 5 (yield 84%).
Elemental analysis: C49H33N5, theoretical value: c, 85.07, H, 4.81, N, 10.12, found: c, 85.11, H, 4.80, N, 10.09, HRMS (ESI) M/z (M)+): theoretical values are as follows: 691.2736, found: 691.2744.
preparation example 6 Synthesis of Compound 6
The synthetic route for compound 6 is as follows:
Figure BDA0002966439330000603
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 6: the remaining procedure, identical to procedure (1) of preparation example 1, was carried out substituting the equivalent amount of compound S9 for compound S1 to give intermediates 1-6 (73% yield).
(2) Synthesis of intermediates 2 to 6: the same amount of intermediate 1-1 as intermediate 1-6 and the same amount of compound S2 as compound S10 were substituted for intermediate 1-1, and the remaining steps were identical to step (2) of preparation example 1, to give intermediates 2-6 (yield 88%).
(3) Synthesis of Compound 6: the intermediate 2-1 was replaced with an equivalent amount of the intermediate 2-6, and the remaining steps were identical to the step (3) of preparation example 1 to obtain the compound 6 (yield 79%).
Elemental analysis: C51H33N5O, theoretical value: c, 83.70, H, 4.55, N, 9.57, found: c, 83.74, H, 4.53, N, 9.54, HRMS (ESI) M/z (M)+): theoretical value: 731.2685, found: 731.2690.
preparation example 7 Synthesis of Compound 7
The synthetic route for compound 7 is as follows:
Figure BDA0002966439330000611
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 7: the same amount of intermediate 1-6 as intermediate 1-1 and the same amount of compound S12 as compound S2 were substituted for intermediate 1-1, and the remaining steps were identical to step (2) of preparation example 1, to give intermediates 1-7 (yield 86%).
(2) Synthesis of compound 7: the intermediate 2-1 was replaced with an equivalent amount of the intermediate 1-7, and the remaining steps were identical to the step (3) of preparation example 1 to obtain compound 7 (yield 79%).
Elemental analysis: C53H35N5, theoretical value: c, 85.80, H, 4.76, N, 9.44, found: c, 85.74, H, 4.78, N, 9.48, HRMS (ESI) M/z (M)+): theoretical values are as follows: 741.2892, found: 741.2897.
preparation example 8 Synthesis of Compound 8
The synthetic route for compound 8 is as follows:
Figure BDA0002966439330000612
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 8: the same amount of intermediate 1-1 as intermediate 1-6 and the same amount of compound S2 as compound S13 were substituted for intermediate 1-1, and the remaining steps were identical to step (2) of preparation example 1, to give intermediates 1-8 (yield 88%).
(2) Synthesis of compound 8: the intermediate 2-1 was replaced with an equivalent amount of the intermediate 1-8, and the remaining steps were identical to the step (3) of preparation example 1 to obtain the compound 8 (yield 80%).
Elemental analysis: C55H35N5O, theoretical value: c, 84.49, H, 4.51, N, 8.96, found: c, 84.54, H, 4.50, N, 8.92, HRMS (ESI) M/z (M)+): theoretical values are as follows: 781.2842, found: 781.2847.
preparation example 9 Synthesis of Compound 9
The synthetic route for compound 9 is as follows:
Figure BDA0002966439330000621
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 9: the same procedures as in the step (1) of production example 1 were repeated except that the equivalent amount of compound S9 was substituted for compound S1 and the equivalent amount of compound S14 was substituted for benzaldehyde, to obtain intermediates 1-,9 (yield 79%).
(2) Synthesis of intermediates 2 to 9: the intermediate 1-1 was replaced with an equivalent amount of the intermediate 1-9, and the remaining steps were identical to the step (2) of preparation example 1 to give the intermediates 2-9 (yield 88%).
(3) Synthesis of compound 9: the intermediate 2-1 was replaced with an equivalent amount of intermediate 2-9, and the remaining steps were identical to the step (3) of preparation example 1 to obtain compound 9 (yield 81%).
Elemental analysis: C50H32N6, theoretical value: c, 83.78, H, 4.50, N, 11.72, found: c, 83.82, H, 4.48, N, 11.70, HRMS (ESI) M/z (M)+): theoretical values are as follows: 716.2688, found: 716.2693.
preparation example 10 Synthesis of Compound 10
The synthetic route for compound 10 is as follows:
Figure BDA0002966439330000622
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 10: the remaining procedure was identical to the procedure (2) of preparation example 1, substituting compound S2 for the equivalent of compound S15, to give intermediates 1-10 (yield 90%).
(2) Synthesis of compound 10: the intermediate 2-1 was replaced with an equivalent amount of the intermediate 1-10, and the remaining steps were identical to the step (3) of preparation example 1 to obtain the compound 10 (yield 89%).
Elemental analysis: C49H31N5, theoretical value: c, 85.32, H, 4.53, N, 10.15, found: c, 85.31, H, 4.51, N, 10.18, HRMS (ESI) M/z (M)+): theoretical value: 689.2579, found: 689.2585.
preparation example 11 Synthesis of Compound 11
The synthetic route for compound 11 is as follows:
Figure BDA0002966439330000631
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 11: the remaining procedure was identical to the procedure (2) of preparation example 1, substituting compound S2 for the equivalent of compound S16, to give intermediates 1 to 11 (yield 91%).
(2) Synthesis of compound 11: the same amount of intermediate 1-11 as intermediate 2-1 and the same amount of compound S17 as compound S3 were substituted for intermediate 2-1, and the remaining steps were identical to step (3) of production example 1, whereby Compound 11 was obtained (yield 83%).
Elemental analysis: C52H34N6, theoretical value: c, 84.07, H, 4.61, N, 11.31, found: c, 84.01, H, 4.63, N, 11.36, HRMS (ESI) M/z (M)+): theoretical values are as follows: 742.2845, found: 742.2853.
preparation example 12 Synthesis of Compound 12
The synthetic route for compound 12 is as follows:
Figure BDA0002966439330000632
the preparation steps are as follows:
(1) synthesis of intermediates 1 to 12: the same amount of compound S18 as compound S2 and the same amount of compound S19 as intermediate 1-1 were substituted, and the remaining steps were identical to step (2) of preparation example 1, to give intermediates 1 to 12 (yield 87%).
(2) Synthesis of compound 12: the intermediate 2-1 was replaced with an equivalent amount of the intermediate 1-12, and the remaining steps were identical to the step (3) of preparation example 1 to obtain compound 12 (yield 80%).
Elemental analysis: C49H31N5, theoretical value: c, 85.32, H, 4.53, N, 10.15, found: c, 85.38, H, 4.51, N, 10.11, HRMS (ESI) M/z (M)+): theoretical value: 689.2579, found: 689.2584.
application examples 1-12 and comparative application example 1
Application examples 1-12 and comparative application example 1 each provide an OLED having the following structure in a stacked arrangement in order: the structure of the composite material comprises a substrate (indium tin oxide (ITO) coated glass substrate)/a Hole Injection Layer (HIL)/a Hole Transport Layer (HTL)/a light-emitting layer (EML)/an Electron Transport Layer (ETL)/an Electron Injection Layer (EIL)/a cathode, wherein the cathode material is a mixed material of metal Mg and Ag, the mass ratio of the metal Mg to the Ag is 9:1, the thickness of the cathode is 80nm, main materials in the light-emitting layer are a compound 1-a compound 12 and a compound Ref-1 obtained in preparation examples 1-12 respectively, and the structures of the compound Ref-1 and other required compounds are as follows:
Figure BDA0002966439330000641
the OLED layer parameters provided in application examples 1-12 and comparative application example 1 are as follows:
Figure BDA0002966439330000642
Figure BDA0002966439330000651
the preparation method comprises the following steps:
1) substrate cleaning:
carrying out ultrasonic treatment on the glass substrate coated with the ITO transparent electrode in an aqueous cleaning agent (the components and concentration of the aqueous cleaning agent are 10 wt% of glycol solvent and 1 wt% of triethanolamine), washing in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (volume ratio is 1: 1), baking in a clean environment until water is completely removed, and then cleaning by using ultraviolet light and ozone to obtain a glass substrate with an anode;
2) evaporation:
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-6To 2X 10-4Pa, performing vacuum evaporation on the anode layer film by using a co-evaporation mode to evaporate a hole injection layer material, wherein the evaporation thickness is 10 nm;
3) evaporating a hole transport layer on the hole injection layer, wherein the thickness of the evaporated film is 80 nm;
4) evaporating a luminescent layer on the hole transport layer, and evaporating a luminescent host material and an object material in vacuum in a co-evaporation mode, wherein the total film thickness of the evaporation is 30 nm;
5) vacuum evaporating an electron transport layer on the luminescent layer, wherein the total film thickness of the evaporation is 30 nm;
6) vacuum evaporating an electron injection layer on the electron transport layer, wherein the total film thickness of the evaporation is 1 nm;
7) and (4) evaporating a cathode on the electron injection layer, wherein the total film thickness of evaporation is 80nm, and obtaining an OLED finished product.
LUMO and HOMO energy level testing of materials:
the LUMO and HOMO levels of the compounds 1 to 12 prepared in examples 1 to 12 were tested using an electrochemical workstation using cyclic voltammetry (CV shanghai chenhua CHI-600E), with a platinum wire (Pt) as a counter electrode and silver/silver chloride (Ag/AgCl) as a reference electrode, in a dichloromethane electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate under a nitrogen atmosphere at a scanning rate of 100mV/s, with ferrocene for potential calibration, and the absolute level of the potential of ferrocene under vacuum was set to-4.8 eV:
HOMO energy order-E (Eox-E)1/2,ferrocene)+(-4.8)eV；
LUMO energy order-E (E)re-E1/2,ferrocene)+(-4.8)eV；
Wherein EoxTo oxidation potential, EreTo reduce the potential, E1/2,ferroceneIs the ferrocene potential.
Triplet state energy level test conditions: the compounds to be tested were formulated as solutions (concentration 2X 10) in toluene as solvent- 5mol/L) was measured at-78 ℃ using a fluorescence spectrophotometer (Hitachi F-4600). Wherein ET1(eV) represents the triplet level of the compound, which is calculated using the following formula:
ET11240/shortest absorption wavelength.
The test results were as follows:
Figure BDA0002966439330000652
Figure BDA0002966439330000661
the results show that the benzimidazole compound provided by the invention has higher triplet state energy level and proper HOMO and LUMO energy levels, and is beneficial to combining electrons and holes in a light-emitting layer.
Testing the performance of the device:
the OLEDs provided in application examples 1-12 and comparative application example 1 were tested for current, voltage, and brightness using a PR 650 spectral scanning luminance meter and a Keithley K2400 digital source meter system, with the following results and test conditions: the current density is 20mA/cm2At 25 ℃ C; wherein the life test is as follows: recording time (in hours) when device brightness dropped to 95% of original brightness:
group of Drive voltage V Current efficiency Cd/A Life/h
Application example 1 4.4 21 164
Application example 2 4.5 22 115
Application example 3 4.4 22 142
Application example 4 4.4 23 138
Application example 5 4.4 25 166
Application example 6 4.5 22 141
Application example 7 4.4 27 161
Application example 8 4.4 26 170
Application example 9 4.4 27 159
Application example 10 4.5 24 132
Application example 11 4.5 21 113
Application example 12 4.5 25 137
Comparative application example 1 4.7 19 88
The data show that the organic electroluminescent device prepared from the benzimidazole compound provided by the invention has higher current efficiency and longer service life.
The applicant states that the benzimidazole compounds of the present invention and the preparation method and application thereof are illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention is implemented only by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (17)

1. A benzimidazole compound, wherein the structure of the benzimidazole compound is shown as formula I:
Figure FDA0003629228160000011
wherein n is selected from 0 or 2, and when n is 0 (R)1)nIs hydrogen, n is 2 or R1Are connected to form a ring C;
ring C is selected from phenyl;
said L1Selected from single bonds or phenyl;
said L2Selected from single bonds;
said L3Selected from any one of the following groups: phenyl, biphenyl, or naphthyl;
said L is4Selected from single bonds;
ar is1Selected from electron transport groups;
ar is2Is selected from
Figure FDA0003629228160000012
Ar is3、Ar4Is independently selected from
Figure FDA0003629228160000013
Wherein, T1Selected from O, X1Selected from the group consisting of CRX1，X2Selected from the group consisting of CRX2，X3Selected from the group consisting of CRX3，X4Selected from the group consisting of CRX4，X5Selected from the group consisting of CRX5，X6Selected from the group consisting of CRX6，X7Selected from the group consisting of CRX7，X8Selected from the group consisting of CRX8；
The R isa1、Ra2、Ra3、Ra4、Ra5Independently selected from any one of hydrogen, deuterium, tritium and cyano;
said R isX1、RX2、RX3、RX4、RX5、RX6、RX7、RX8Independently selected from any one of hydrogen, deuterium and tritium;
the R isa1、Ra2、Ra3、Ra4、Ra5Independently exist or are connected with two adjacent rings to form a ring E, and the ring E is selected from phenyl;
the electron-transporting group is selected from
Figure FDA0003629228160000014
Any one of them;
wherein, T2Selected from O, Y1Selected from N or CRY1，Y2Selected from N or CRY2，Y3Selected from N or CRY3，Y4Selected from N or CRY4，Y5Selected from the group consisting of CRY5，Y6Selected from the group consisting of CRY6，Y7Selected from the group consisting of CRY7，Y8Selected from the group consisting of CRY8，Y9Is selected from N, Y10Is selected from N, Y11Is selected from N, Y12Selected from N or CRY12，Y13Selected from N or CRY13，Y14Selected from N or CRY14，Y15Selected from N or CRY15，Y16Selected from the group consisting of CRY16，Y17Selected from the group consisting of CRY17，Y18Selected from the group consisting of CRY18，Y19Selected from the group consisting of CRY19，Y1-Y4And only two of them are selected from N;
the R isY1、RY2、RY3、RY4Independently selected from hydrogen, deuterium, tritium or
Figure FDA0003629228160000021
Any one of them;
the R isY5、RY6、RY7、RY8Independently selected from any one of hydrogen, deuterium and tritium;
the R isY12、RY13、RY14、RY15Independently selected from hydrogen, deuterium, tritium or any one of the following groups:
Figure FDA0003629228160000022
said R isY16、RY17、RY18、RY19Independently selected from any one of hydrogen, deuterium and tritium;
R3、R4independently selected from phenyl or
Figure FDA0003629228160000023
Ar is3And Ar4Optionally linked by a single bond to form a ring.
2. The benzimidazole compound of claim 1, wherein n is 0.
3. The benzimidazole compound of claim 1, wherein n is 2, and R is1The connection between them forms benzene ring.
4. The benzimidazole compound of claim 1, wherein the benzimidazole compound is selected from any one of the compounds of the following structures:
Figure FDA0003629228160000024
Figure FDA0003629228160000031
5. a process for the preparation of benzimidazoles according to any one of claims 1 to 4, wherein said process comprises the following steps:
(1) the compound
Figure FDA0003629228160000032
And compounds
Figure FDA0003629228160000033
Mixing and reacting to obtain the compound
Figure FDA0003629228160000034
(2) The compound obtained in step (1)
Figure FDA0003629228160000035
And compounds
Figure FDA0003629228160000036
Mixing and reacting to obtain the benzimidazole compound;
wherein R is1、n、L1、L2、L3、L4、Ar1、Ar2、Ar3、Ar4Having the same limits as stated in any of claims 1 to 4, X is selected from the group consisting of halogen.
6. Use of the benzimidazole compounds according to any one of claims 1 to 4 for the preparation of organic electroluminescent devices or organic electroluminescent materials.
7. An organic electroluminescent composition comprising any one or a combination of at least two of the benzimidazole compounds as claimed in any one of claims 1 to 4.
8. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, which are oppositely arranged;
the organic layer comprises any one or a combination of at least two of the benzimidazole compounds of any one of claims 1 to 4.
9. The organic electroluminescent device according to claim 8, wherein the organic layer comprises a light-emitting layer comprising any one or a combination of at least two of the benzimidazole compounds according to any one of claims 1 to 4.
10. The organic electroluminescent device of claim 9, wherein the light-emitting layer comprises a host material and a guest material.
11. The organic electroluminescent device according to claim 10, wherein the host material comprises any one or a combination of at least two of the benzimidazole compounds according to any one of claims 1 to 4.
12. The organic electroluminescent device of claim 10, wherein the guest material comprises a phosphorescent dopant.
13. The organic electroluminescent device according to claim 12, wherein the phosphorescent dopant is a metal complex comprising any one of Ir, Pt, Ni, Au, Os, Re, Rh, Zn, Ag, Fe or W.
14. The organic electroluminescent device of claim 8, wherein the organic layer comprises any one of or a combination of at least two of a hole injection layer, a hole transport layer, an auxiliary hole transport layer, an emission layer, a hole blocking layer, an electron injection layer, or an electron transport layer.
15. The organic electroluminescent device according to claim 14, wherein the materials of the auxiliary hole transport layer, the emission layer and the hole blocking layer are independently selected from one or a combination of at least two of the benzimidazole compounds defined in any one of claims 1 to 4.
16. An organic electroluminescent assembly comprising a tandem structure formed by stacking at least two organic electroluminescent devices according to any one of claims 8 to 15.
17. An optoelectronic article comprising the organic electroluminescent device of any one of claims 8 to 15.
CN202110251987.4A 2021-03-08 2021-03-08 Benzimidazole compound and preparation method and application thereof Active CN112979616B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110251987.4A CN112979616B (en) 2021-03-08 2021-03-08 Benzimidazole compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110251987.4A CN112979616B (en) 2021-03-08 2021-03-08 Benzimidazole compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112979616A CN112979616A (en) 2021-06-18
CN112979616B true CN112979616B (en) 2022-07-12

Family

ID=76336038

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110251987.4A Active CN112979616B (en) 2021-03-08 2021-03-08 Benzimidazole compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112979616B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429395B (en) * 2021-07-27 2023-07-25 北京八亿时空液晶科技股份有限公司 Imidazole derivative, organic electroluminescent material, light-emitting element, and consumer product
CN115772160B (en) * 2021-09-06 2024-05-31 宁波卢米蓝新材料有限公司 Compound, organic electroluminescent material, organic electroluminescent element and electronic equipment

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111689949A (en) * 2014-04-30 2020-09-22 默克专利有限公司 Material for electronic devices
CN108203407A (en) * 2017-12-20 2018-06-26 李现伟 Pyrene class electroluminescent organic material, luminescent device and display
TWI664267B (en) * 2018-08-17 2019-07-01 Yuan Ze University Tricarbazole-n-benzimidazole bipolar materials and organic light emitting diodes
CN112300146B (en) * 2019-07-30 2022-02-01 江苏三月科技股份有限公司 Organic compound taking carbazole as core and organic electroluminescent device comprising organic compound
CN111892586B (en) * 2020-09-08 2021-08-24 长春海谱润斯科技股份有限公司 Benzo five-membered N-containing heterocyclic heteroaryl amine compound and organic electroluminescent device thereof
CN112239452B (en) * 2020-10-14 2022-05-10 武汉尚赛光电科技有限公司 Electron transport type heteroanthracene derivative and organic electroluminescent device thereof

Also Published As

Publication number Publication date
CN112979616A (en) 2021-06-18

Similar Documents

Publication Publication Date Title
CN110862381B (en) Organic electroluminescent compound and preparation method and application thereof
TWI461507B (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
TWI461509B (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
JP2016178326A (en) Deuterated compounds for electronic applications
JP2015216382A (en) New organic electroluminescent compound and organic electroluminescent element using the same
KR101790854B1 (en) Deuterated compounds for luminescent applications
KR20110097784A (en) Aromatic amine derivative, and organic electroluminescent element
CN112159412B (en) Organic nitrogen-containing heterocyclic compound and application thereof
CN112979616B (en) Benzimidazole compound and preparation method and application thereof
TWI641598B (en) Compound and organic electronic device using the same
CN111777614B (en) Organic electroluminescent compound and application thereof
CN112209937B (en) Organic nitrogen-containing heterocyclic compound and application thereof
JP7376892B2 (en) Polycyclic aromatic compounds
CN114685503A (en) Organic electroluminescent compound and application thereof
WO2023138254A1 (en) Heterocyclic compound, and organic electroluminescent material and element
WO2023093094A1 (en) Organic electroluminescent device and display apparatus
KR20150005331A (en) Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
CN114685482A (en) Organic electroluminescent compound and application thereof
CN110872310A (en) Condensed ring aryl compound, organic electronic device and application thereof
KR20150045141A (en) Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
CN114685483B (en) Organic electroluminescent compound and application thereof
KR20150017523A (en) Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR20230044349A (en) Organic Material Composition and Applications Thereof
JP2023085205A (en) Organic electroluminescence element using polycyclic aromatic compound having triazinyl group
JP2023148087A (en) metal complex

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