CN114920748B - Organic compound and application thereof in OLED device - Google Patents

Organic compound and application thereof in OLED device Download PDF

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CN114920748B
CN114920748B CN202210621667.8A CN202210621667A CN114920748B CN 114920748 B CN114920748 B CN 114920748B CN 202210621667 A CN202210621667 A CN 202210621667A CN 114920748 B CN114920748 B CN 114920748B
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CN114920748A (en
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李万宾
邢程程
李贵芳
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Shanghai Tianma Microelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—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 three hetero rings
    • C07D491/16—Peri-condensed systems
    • 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
    • C07D495/12—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 three hetero rings
    • C07D495/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention provides an organic compound and application thereof, wherein the organic compound has a structure shown in a formula I. According to the organic compound provided by the invention, the larger conjugated structure containing the hetero atom is introduced, and the lone pair electrons in the nitrogen atom are conjugated into the benzene ring, so that the charge transmission balance of material molecules is improved, and the stability of the material is improved. The organic compound can be used as a luminescent layer material, and can improve the luminous efficiency and the service life of the prepared electroluminescent device by matching with other suitable materials, thereby providing a solution for manufacturing the luminescent device with low cost, high efficiency and long service life.

Description

Organic compound and application thereof in OLED device
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an organic compound and application thereof in an OLED device.
Background
Organic semiconductor materials have structural versatility, low cost, and excellent electro-optical properties, and in particular Organic Light Emitting Diodes (OLEDs) have great potential and space for applications in electro-optical devices such as flat panel displays and lighting. At present, a mixed system of a main body material/a doping agent is generally used as a luminescent material for a luminescent layer of the organic electroluminescent device, so that the color purity, the luminous efficiency and the stability can be improved. In general, the choice of host material is critical with host material/dopant systems, as host material greatly affects the efficiency and stability of the OLED device. The preferred host materials should have suitable molecular weights for deposition under vacuum, while also having high glass transition temperatures and thermal decomposition temperatures to ensure thermal stability, high electrochemical stability to ensure long service life, easy formation of amorphous films, good interfacial interactions with adjacent functional layer materials, and low probability of molecular motion. Particularly, as a red light host material, the material is required to have good carrier transport capability and appropriate triplet energy level, so that energy can be effectively transferred to a guest material in a light emitting process, and higher efficiency is realized.
The red light main body material reported at present is usually a large conjugated system aromatic ring, and the problems of low device efficiency and poor stability are generally presented in the aspect of devices. This is because the triplet energy level is low due to the large conjugated structure, which does not efficiently transfer exciton energy to the guest, while ignoring the equilibrium problem of host material carrier transport in the device.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an organic compound and its application in an OLED device, which can effectively improve the efficiency and lifetime of the device.
The invention provides an organic compound, which has a structure shown in a formula I:
wherein A, B, C is independently selected from substituted or unsubstituted C6-C30 aryl and C5-C30 heteroaryl, and the C ring contains at least one electron withdrawing group;
l is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a C2-C30 heteroarylene group, a C3-C30 cycloaliphatic group, and combinations thereof;
R 1 selected from H, D, cyano, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, cl, br, F, I, substituted or unsubstituted C1-C20 linear alkyl, alkoxy, thioalkoxy, silyl or keto, substituted or unsubstituted C3-C20 branched alkyl, cycloalkyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C7-C20 aryloxycarbonyl, substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, aryloxy or heteroaromatic group having 5 to 60 ring atomsA heteroaryloxy group or a combination thereof;
n is an integer of 0 to 6, and when n is 2 to 6, R which may be the same or different and are plural at the same time 1 Exists, and adjacent two R 1 The ring may be condensed.
The invention provides an organic light-emitting device, which comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode, wherein the organic thin film layer comprises a light-emitting layer, and the light-emitting layer contains at least one organic compound.
The invention provides a display panel comprising the organic light-emitting device.
Compared with the prior art, the invention provides an organic compound which has a structure shown in a formula I. According to the organic compound provided by the invention, the larger conjugated structure containing the hetero atom is introduced, and the lone pair electrons in the nitrogen atom are conjugated into the benzene ring, so that the charge transmission balance of material molecules is improved, and the stability of the material is improved. The organic compound can be used as a luminescent layer material, and can improve the luminous efficiency and the service life of the prepared electroluminescent device by matching with other suitable materials, thereby providing a solution for manufacturing the luminescent device with low cost, high efficiency and long service life.
Drawings
FIG. 1 is a schematic diagram of an OLED device according to the present invention;
wherein 110 is a glass substrate, 120 is an anode, 130 is a hole injection layer, 140 is a hole transport layer A, and 150 is a hole transport layer B;160 is a light emitting layer, 170 is an electron transporting layer, 180 is a cathode.
Detailed Description
The invention provides an organic compound, which has a structure shown in a formula I:
wherein A, B, C is independently selected from substituted or unsubstituted C6-C30 aryl and C5-C30 heteroaryl, and the C ring contains at least one electron withdrawing group;
l is selected from single bond, substituted or unsubstituted arylene of C6-C30, heteroarylene of C2-C30, alicyclic of C3-C30, and combinations thereof;
R 1 selected from H, D, cyano, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, cl, br, F, I, substituted or unsubstituted C1-C20 linear alkyl, alkoxy, thioalkoxy, silyl or keto, substituted or unsubstituted C3-C20 branched alkyl, cycloalkyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C7-C20 aryloxycarbonyl, substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms, aryloxy or heteroaryloxy groups having 5 to 60 ring atoms, or combinations thereof;
n is an integer of 0 to 6, and when n is 2 to 6, R which may be the same or different and are plural at the same time 1 Exists, and adjacent two R 1 The ring may be condensed.
In the present invention, the above-mentioned aryl group having 6 to 30 carbon atoms includes monocyclic and condensed ring aryl groups.
In the present invention, the above-mentioned C5-C30 heteroaryl group includes a monocyclic or condensed ring heteroaryl group.
In the present invention, the above combination refers to a group formed by connecting each group by a single bond, a C atom or a hetero atom (including but not limited to N, O, S, P, si) or a group formed by fusing each group.
In the present invention, each of C6 to C30 may be, independently, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.
In the present invention, C5-C30 may each independently be C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.
In the present invention, each of C3 to C30 may be, independently, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.
In the present invention, each of C2 to C30 may be, independently, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, etc.
In the present invention, C1-C20 may each independently be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20.
In the present invention, C3-C20 may each independently be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20.
In the present invention, C2-C20 may each independently be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20.
In the present invention, C7-C20 may each independently be C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20.
Optionally, the A, B, C, L, R 1 The substituent of (C) is independently selected from any one or more of deuterium, halogen, cyano, C1-C10 straight-chain or branched alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C20 aryl, C2-C20 heteroaryl or C6-C18 arylamine.
Optionally, the A, B, C, L, R 1 The substituent groups of the (C) are independently selected from one or more of deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, dibenzofuranyl, dibenzothienyl, carbazolyl, fluorenyl, 9 '-dimethylfluorenyl, 9' -diphenylfluorenyl, spirobifluorenyl, pyridyl, deuterated phenyl and cyanophenyl.
The above groups may be further substituted with one or more of deuterium, cyano, halogen.
Optionally, the aryl of C6-C30 is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, fluorenyl, 9 '-dimethylfluorenyl, 9' -diphenylfluorenyl, spirobifluorenyl, benzocyclopentenyl and benzocyclohexenyl.
Alternatively to this, the method may comprise, the C5-C30 heteroaryl is selected from carbazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, imidazolyl, oxazolyl, thiazolyl, pyranyl, furanyl, pyrrolyl, thienyl, benzofuranyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzothienyl, dibenzothienyl, dibenzofuranyl, naphthazolyl, naphthapyrazinyl, naphthaimidazolyl, naphthazolyl, phenanthropyridinyl, phenanthropyrazinyl, any one of phenanthroimidazolyl, phenanthrooxazolyl, phenanthrothiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1, 5-naphthyridinyl, acridinyl, indolocarbazolyl, indolofluorenyl, benzothiophenopyrazinyl, benzothiophenopyrimidinyl, benzofuranopyrazinyl, benzofuranopyrimidinyl, benzofuranocarbazolyl, benzothiophenocarbazolyl, indolopyrazinyl, indenopyrazinyl, or indenopyrimidinyl.
Optionally, the arylene group of C6 to C30 is selected from any one of phenylene group, biphenylene group, terphenylene group, naphthylene group, anthrylene group, phenanthrylene group, pyrenylene group, fluorenylene group, 9 '-dimethylfluorenylene group, 9' -diphenylfluorenylene group, spirobifluorenylene group, benzocyclopentylene group, and benzocyclohexenylene group.
Optionally, the C2-30 heteroarylene is selected from carbazolylene, triazinylene, pyridylene, pyrimidinylene, pyrazinylene, pyridazinylene, imidazolylene, oxazolylene, thiazolylene, pyranylene, furanylene, pyrrolylene, thiophenylene, benzofuranylene, benzimidazolylene, benzoxazolylene, benzothiazolylene, benzothiophenylene, dibenzothiophenylene, dibenzofuranylene, naphthazolopyridinylene, naphthazolopyrazinyl, naphthazolylene, naphthazoloxazolylene, naphthazolyl, phenanthropyrazinyl, phenanthroimidazolyl, phenanthroizolyl, phenanthroiothiazolyl, quinolinylene, isoquinolinyl, quinoxalinyl, quinazolinylene, 1, 5-diazanaphtalenyl, benzazolyl, indolocarbazolyl, indolopyrenyl, benzothiophenyl, benzopyrimidinyl, naphthazinopyrazinyl, benzonaphthazolyl, benzofuranyl, naphthazolyl, benzofuranyl, or any of the benzofuranyl.
Optionally, the A, B, C is independently selected from Ry1 substituted or unsubstituted phenyl, pyrrolyl, furanyl, thienyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, quinoxalinyl, isoquinolinyl, quinazolinyl, 1, 5-naphthyridinyl, anthracenyl, phenanthrenyl, pyrenyl, acridinyl, carbazolyl, fluorenyl, benzofuranyl, benzocyclopentenyl, benzocyclohexenyl, dibenzofuranyl, dibenzothienyl, or any of the following structures:
the Ry1 is selected from any one or more of deuterium, halogen, cyano, C6-C20 aryl or C2-C20 heteroaryl, and the C ring contains at least one electron withdrawing group.
Optionally, the A, B is independently selected from substituted or unsubstituted phenyl, naphthyl, pyrrolyl, furanyl, thienyl, biphenyl, benzofuranyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzothienyl, benzocyclopentenyl, or benzocyclohexenyl;
the A, B substituent is independently selected from phenyl, naphthyl or biphenyl.
Optionally, the electron withdrawing group in the C is selected from one or more of F, cl, br, I and cyano.
Optionally, the C has any one of the following structures:
wherein m is 1, 2 or 3; x is X 1 -X 8 Selected from CR 8 Or N, and at least one is N, while any two adjacent positions may form a mono-or polycyclic aliphatic or aromatic ring system; m is M 1 、M 2 、M 3 Respectively and independently represent N (R) 9 )、C(R 10 ) 2 、Si(R 11 ) 2 、O、C＝N(R 12 )、C＝C(R 13 ) 2 、P(R 14 )、P(＝O)R 15 、S、S＝O、SO 2 Or a single bond;
R 2 ～R 15 independently selected from H, D, cyano, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, cl, br, F, I, substituted or unsubstituted C1-C20 linear alkyl, alkoxy, thioalkoxy, silyl or keto, substituted or unsubstituted C3-C20 branched alkyl, cycloalkyl, substituted or unsubstituted C2-C20 alkoxycarbonyl, substituted or unsubstituted C7-C20 aryloxycarbonyl, substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms, aryloxy or heteroaromatic groups having 5 to 60 ring atoms, or combinations thereof.
Optionally, L is selected from a single bond, a substituted or unsubstituted monocyclic aryl, a monocyclic heteroaryl, 2 to 3 ring-fused ring aryl, 2 to 3 ring-fused ring heteroaryl; alternatively, the monocyclic aryl is selected from phenyl; optionally, the ring forming the fused ring aryl is phenyl; alternatively, the ring forming the fused ring heteroaryl includes at least one monocyclic heteroaryl group including, but not limited to, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, pyrrolyl, furyl, thienyl, pyrazolyl, thiazolyl, oxazolyl; optionally, the ring forming the fused ring heteroaryl further comprises 1 or 2 phenyl groups.
Optionally, the L is selected from a single bond, substituted or unsubstituted phenyl, triazinyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, imidazolyl, oxazolyl, thiazolyl, pyranyl, furanyl, pyrrolyl, thienyl, benzofuranyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzothienyl, dibenzothienyl or dibenzofuranyl.
Optionally, the organic compound has any one of the following structures:
the invention provides an organic light-emitting device, which comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode, wherein the organic thin film layer comprises a light-emitting layer, and the light-emitting layer contains at least one organic compound.
Optionally, the organic compound is used as a red light host material.
The invention provides a display panel comprising the organic light-emitting device.
The organic light-emitting device provided by the invention can be an organic light-emitting device well known to a person skilled in the art, and optionally comprises a substrate, an ITO anode, a first hole transport layer, a second hole transport layer, an electron blocking layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (magnesium-silver electrode, magnesium-silver mass ratio of 1:9) and a capping layer (CPL).
Alternatively, the anode material of the organic light-emitting device may be selected from metal-copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof; such as metal oxide-indium oxide, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; such as the conductive polymers polyaniline, polypyrrole, poly (3-methylthiophene), and the like, include materials known to be suitable as anodes in addition to facilitating hole injection materials and combinations thereof.
The cathode material of the organic light-emitting device can be selected from metal-aluminum, magnesium, silver, indium, tin, titanium and the like and alloys thereof; such as multi-layer metal material LiF/Al, liO 2 /Al、BaF 2 Al, etc.; materials suitable for use as cathodes are also known in addition to the above materials that facilitate electron injection and combinations thereof.
The organic optoelectronic device, such as an organic light emitting device, has at least one light emitting layer (EML), and may further include other functional layers including a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
According to the invention, the organic light-emitting device is prepared according to the following method:
an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer.
Alternatively, the organic thin layer may be formed by known film forming methods such as evaporation, sputtering, spin coating, dipping, ion plating, and the like.
The invention provides a display device which comprises the display panel.
In the present invention, an organic light emitting device (OLED device) may be used in a display apparatus, wherein the organic light emitting display apparatus may be a mobile phone display screen, a computer display screen, a television display screen, a smart watch display screen, a smart car display panel, a VR or AR helmet display screen, display screens of various smart devices, or the like.
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Raw material A (18 g), raw material B (25 g), palladium chloride (0.5 g), copper acetate (2.5 g) and ferric trichloride (1.5 g) are sequentially added into a 1000mL three-neck reaction flask under a nitrogen environment, 500mL DMF is injected into the flask and vacuumized, nitrogen is replaced for three times, the reaction is heated to 120 ℃ for 8 hours, after the reaction is finished, the solvent is removed by rotary evaporation, dichloromethane and deionized water are used for extraction three times, organic phases are combined, and 30.7g of intermediate 1-1 is obtained by separating and purifying through silica gel column chromatography (eluting agent is petroleum ether), and the yield is 82.6%.
Intermediate 1-1 (29.8 g), raw material C (15.2 g), tetrakis (triphenylphosphine) palladium (0.8 g) and X-phos (0.8) are sequentially added into a 1000mL three-necked flask under a nitrogen environment, 500mL of dry toluene is injected into the flask and vacuumized, nitrogen is replaced for three times, the mixture is heated to 110 ℃ for reflux reaction for 12 hours, after the reaction is finished, the reaction mixture is poured into 500mL of deionized water and stirred rapidly, the product is separated out continuously, after suction filtration, the product is dissolved again with methylene chloride and extracted with saturated saline for three times, the organic phases are combined, and the mixture is separated and purified by chromatography on a silica gel column (eluent methylene chloride: petroleum ether=1:20), so as to obtain 28.4g of intermediate 1-2, and the yield is 81.2%.
Under nitrogen environment, sequentially adding the intermediate 1-2 (26.2 g) and sodium tert-butoxide (44 g) into a 500mL three-neck flask, then injecting 200mL of dry toluene into the flask, vacuumizing, replacing with nitrogen for three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring the reaction mixture into 500mL of deionized water after the reaction is finished, stirring rapidly, continuously separating out the product, dissolving the product with dichloromethane again after suction filtration, extracting with saturated saline for three times, separating and purifying the combined organic phases by silica gel column chromatography (eluent dichloromethane: petroleum ether=1:20), thus obtaining 17.6g of intermediate 1-3 with the yield of 70.3%.
Under nitrogen environment, sequentially adding an intermediate 1-3 (10.5 g), a raw material D (9.7 g), palladium trifluoroacetate (0.35 g) and cesium carbonate (12 g) into a 500mL three-neck flask, then injecting 200mL of dry toluene into the flask, vacuumizing and replacing three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring a reaction mixture into 500mL of deionized water after the reaction is finished, rapidly stirring, continuously precipitating a product during the reaction, leaching, dissolving the product again by using dichloromethane, extracting the product by using saturated saline for three times, combining organic phases, and separating and purifying by using a silica gel column chromatography (leaching agent dichloromethane: petroleum ether=1:20), thereby obtaining 13.3g of solid powder which is the compound 1, and the yield is 73.4%. MS [ M+H ]] + calcd for C 53 H 32 N 4 :724.26,found:724.16.Elem.Anal.:C,87.82；H,4.43；N,7.72。
Example 2
Raw material A (18 g), raw material B (25 g), palladium chloride (0.5 g), copper acetate (2.5 g) and ferric trichloride (1.5 g) are sequentially added into a 1000mL three-neck reaction flask under a nitrogen environment, 500mL DMF is injected into the flask and vacuumized, nitrogen is replaced for three times, the reaction is heated to 120 ℃ for 8 hours, after the reaction is finished, the solvent is removed by rotary evaporation and extracted three times by methylene dichloride and deionized water, organic phases are combined, and 31.3g of intermediate 2-1 is obtained by separating and purifying through silica gel column chromatography (eluting agent is petroleum ether), and the yield is 84.2%.
Under nitrogen environment, adding intermediate 2-1 (29.8 g), raw material C (15.2 g), tetra (triphenylphosphine) palladium (0.8 g) and X-phos (0.8) into a 1000mL three-neck flask in sequence, then injecting 500mL dry toluene into the flask and vacuumizing, replacing nitrogen for three times, heating to 110 ℃ for reflux reaction for 12 hours, after finishing the reaction, pouring the reaction mixture into 500mL deionized water and stirring rapidly, continuously precipitating the product during the reaction, leaching, dissolving the product again with dichloromethane and extracting with saturated saline for three times, merging organic phases, separating and purifying by silica gel column chromatography (eluent dichloromethane: petroleum ether=1:20), thus obtaining 27.9g intermediate 2-2, and the yield is 79.8%.
Under nitrogen environment, adding intermediate 2-2 (26.2 g) and sodium tert-butoxide (44 g) into a 500mL three-neck flask in sequence, then injecting 200mL of dry toluene into the flask and vacuumizing, replacing with nitrogen for three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring the reaction mixture into 500mL of deionized water after the reaction is finished, stirring rapidly, separating out the product continuously, dissolving the product with dichloromethane again after suction filtration, extracting with saturated saline for three times, separating and purifying the combined organic phases by silica gel column chromatography (eluent dichloromethane: petroleum ether=1:20), thus obtaining 18.6g of intermediate 2-3 with the yield of 74.5%.
Under nitrogen environment, sequentially adding an intermediate 2-3 (10.5 g), a raw material D (9.7 g), palladium trifluoroacetate (0.35 g) and cesium carbonate (12 g) into a 500mL three-neck flask, then injecting 200mL of dry toluene into the flask, vacuumizing and replacing three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring a reaction mixture into 500mL of deionized water after the reaction is finished, rapidly stirring, continuously precipitating a product, leaching, dissolving the product again with dichloromethane, extracting with saturated saline for three times, combining organic phases, and separating and purifying by silica gel column chromatography (eluent dichloromethane: petroleum ether=1:20), thereby obtaining 12.7g of solid powder, namely the compound 2, and the yield is 70.1%. MS [ M+H ]] + calcd for C 53 H 32 N 4 :724.26,found:724.38.Elem.Anal.:C,87.82；H,4.45；N,7.72。
Example 3
Raw material A (18 g), raw material B (25 g), palladium chloride (0.5 g), copper acetate (2.5 g) and ferric trichloride (1.5 g) are sequentially added into a 1000mL three-neck reaction flask under a nitrogen environment, 500mL DMF is injected into the flask and vacuumized, nitrogen is replaced for three times, the reaction is heated to 120 ℃ for 8 hours, after the reaction is finished, the solvent is removed by rotary evaporation, dichloromethane and deionized water are used for extraction three times, organic phases are combined, and 30.7g of intermediate 3-1 is obtained by separating and purifying through silica gel column chromatography (eluting agent is petroleum ether), and the yield is 82.6%.
Under nitrogen environment, adding 3-1 (29.8 g) of intermediate, C (15.2 g) of raw material, tetra (triphenylphosphine) palladium (0.8 g) and X-phos (0.8) into a 1000mL three-neck flask in sequence, then injecting 500mL of dry toluene into the flask, vacuumizing, replacing nitrogen for three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring the reaction mixture into 500mL of deionized water after finishing the reaction, stirring rapidly, continuously precipitating the product during the reaction, leaching, dissolving the product again with methylene chloride, extracting with saturated saline for three times, merging organic phases, and separating and purifying by silica gel column chromatography (eluting agent methylene chloride: petroleum ether=1:20), thus obtaining 28.4g of intermediate 3-2 with the yield of 81.2%.
Under nitrogen environment, adding 3-2 (26.2 g) intermediate and sodium tert-butoxide (44 g) into a 500mL three-neck flask in turn, then injecting 200mL dry toluene into the flask and vacuumizing, replacing with nitrogen for three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring the reaction mixture into 500mL deionized water after the reaction is finished, stirring rapidly, continuously precipitating the product during the reaction, dissolving the product with dichloromethane again after suction filtration, extracting with saturated saline for three times, separating and purifying the combined organic phases by silica gel column chromatography (eluent dichloromethane: petroleum ether=1:20), thus obtaining 17.6g intermediate 3-3 with the yield of 70.3%.
Under a nitrogen environment, sequentially adding 3-3 (10.5 g) of an intermediate, D (7.2 g) of a raw material, palladium trifluoroacetate (0.35 g) and cesium carbonate (12 g) into a 500mL three-neck flask, then injecting 200mL of dry toluene into the flask, vacuumizing and replacing three times, heating to 110 ℃ for reflux reaction for 12 hours, pouring reaction mixture into 500mL of deionized water after the reaction is finished, rapidly stirring, continuously precipitating a product during the reaction, leaching, dissolving the product again by using dichloromethane, extracting the product by using saturated saline for three times, combining organic phases, and separating and purifying by using a silica gel column chromatography (eluting agent dichloromethane: petroleum ether=1:20), thus obtaining 11.7g of solid powder, namely the compound 3, and the yield is 75.6%. MS [ M+H ]] + calcd for C 46 H 27 N 3 :621.22,found:621.17.Elem.Anal.:C,87.83；H,4.38；N,6.78。
Comparative examples
(1) Preparation of Compound 4-3
Under the protection of nitrogen, adding compound 4-1 (20.2 g,50 mmol), compound 4-2 (17.2 g,100 mmol), tetra (triphenylphosphine) palladium (3.5 g,3 mmol), tetrabutylammonium bromide (8.1 g,25 mmol) and sodium hydroxide (4 g,100 mmol) into a 500mL three-necked flask in sequence, adding 200mL toluene and 50mL deionized water, vacuumizing, replacing three times with nitrogen, and heating to 110 ℃ to stir and react for 24h; after the reaction was completed, most of the solvent was rotary evaporated, dissolved in methylene chloride and washed three times with water, and the combined organic phases were separated and purified by silica gel column chromatography (eluent petroleum ether) to give 18.7g of compound 4-3 in 75% yield.
(2) Preparation of Compounds 4-4
Compound 4-3 (14.9 g,30 mmol) and 100mL of N, N-dimethylformamide were added to a 250mL single-necked flask, a 30mmol N, N-dimethylformamide solution of NBS was added dropwise under ice bath, the reaction was stirred in a dark place for 12 hours, the reaction was completed, the reaction solution was poured into 300mL of water, suction filtration and recrystallization of the filter residue was carried out, 17.3g of compound 4-4 was obtained, and the yield was 90%.
(3) Synthesis of Compound N1
Compounds 4 to 4 (34.4 g,20 mmol), 4 to 5 (11.5 g,20 mmol), tetrakis (triphenylphosphine) palladium (0.7 g,0.6 mmol), tetrabutylammonium bromide (3.2 g,10 mmol) and sodium hydroxide (1.6 g,40 mmol) were successively added to a 500mL three-necked flask under nitrogen protection, 200mL toluene and 50mL deionized water were then injected into the flask and evacuated, nitrogen was displaced three times, heated to 110℃for reflux reaction for 12h, the solvent was removed by rotary evaporation after completion of the reaction, the product was dissolved with dichloromethane, extracted three times with saturated brine, and the combined organic phases were purified by silica gel column chromatography (eluent V dichloromethane: V petroleum ether=1:10) to give 18.7g of comparative compound N1 (solid powder) in 85% yield.
Application example 1
The application example provides an OLED device ITO/HI/HI-1/HT-2/EML/ET, liq/Liq/Al, as shown in FIG. 1, the organic light emitting device comprises a glass substrate 110, an anode 120, a hole injection layer 130, a hole transport layer A140, a hole transport layer B150, a light emitting layer 160, an electron transport layer 170 and a cathode 180;
the OLED device was prepared as follows:
(1) Cutting the glass substrate 110 into 50mm×50mm×0.7mm sizes, respectively sonicating in isopropyl alcohol and deionized water for 30min, and then exposing to ozone for about 10min for cleaning; mounting the resulting glass substrate with the ITO anode 120 onto a vacuum deposition apparatus;
(2) Vacuum evaporating a compound HI with a thickness of 30nm on the ITO anode 120 to form a hole injection layer 130;
(3) Vacuum evaporating a compound HT-1 on the hole injection layer 130 to a thickness of 60nm as a hole transport layer A140;
(4) Vacuum evaporating a compound HT-2 on the hole transport layer A140 to obtain a hole transport layer B150 with a thickness of 10 nm;
(5) Vacuum evaporating a compound 1 (provided in example 1) and a red light guest material RD having a weight ratio of 100:3 on the hole transport layer B150 to a thickness of 40nm as a light emitting layer 160;
(6) Vacuum evaporating compounds ET and Liq with a weight ratio of 50:50 on the light-emitting layer 160, wherein the thickness is 30nm, and the compounds ET and Liq are used as an electron transport layer 170;
(6) An aluminum electrode was vacuum-deposited on the electron transport layer 170 to a thickness of 100nm as a cathode 180.
The structures of the above-mentioned compounds HI, HT-1, HT-2, red guest materials RD, ET and Liq are as follows:
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application example 2
The present application example provides an OLED device differing from application example 1 only in that the organic compound 1 in step (5) is replaced with the organic compound 2 provided in example 2 of the same quality; the other preparation steps were identical.
Application example 3
The present application example provides an OLED device differing from application example 1 only in that the organic compound 1 in step (5) is replaced with the organic compound 3 provided in example 3 of the same quality; the other preparation steps were identical.
Comparative application example 1
The present application example provides an OLED device differing from application example 1 only in that the organic compound 1 in step (5) is replaced with the compound N1 provided in comparative example 1 of the same quality; the other preparation steps were identical.
Test example 1
Analog calculation of compounds
The simulation calculation method comprises the following steps: by applying the Density Functional Theory (DFT), the distribution condition and the energy level of the molecular front-line orbitals HOMO and LUMO are optimized and calculated at the calculation level of B3LYP/6-31G (d) through a Guassian 09 program package (Guassian Inc.), and meanwhile, the lowest singlet energy level S1 and the lowest triplet energy level T1 of the compound molecule are calculated based on the time-containing density functional theory (TD-DFT) simulation, and the results are shown in the table 1:
TABLE 1
Test example 2
Evaluation of the Performance of OLED devices
The testing method comprises the following steps: the life test method is to start the continuous operation time of the device when the luminous brightness of the device is reduced to 95% of the initial value under the constant current density corresponding to 1000 nits.
The current efficiency testing method adopts I-V-L testing equipment to measure the corresponding current density under the condition that the brightness is 1000nits, and calculates to obtain the current efficiency.
The test results are shown in Table 2.
TABLE 2
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (5)

1. An organic compound having the structure of formula i:
wherein A, B is naphthyl;
R 1 is H;
l is a single bond or phenylene;
c is selected from Ry1 substituted triazinyl or quinazolinyl;
ry1 is phenyl;
n is an integer of 0 to 6.
2. An organic compound characterized by having any one of the following structures:
3. an organic light-emitting device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode, the organic thin film layer comprising a light-emitting layer containing at least one organic compound according to any one of claims 1 to 2.
4. The organic light-emitting device according to claim 3, wherein the organic compound is used as a red light host material.
5. A display panel comprising the organic light emitting device of any one of claims 3 to 4.
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