CN112979549B - Organic compound, electroluminescent material, OLED device and display panel - Google Patents

Organic compound, electroluminescent material, OLED device and display panel Download PDF

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CN112979549B
CN112979549B CN202110199700.8A CN202110199700A CN112979549B CN 112979549 B CN112979549 B CN 112979549B CN 202110199700 A CN202110199700 A CN 202110199700A CN 112979549 B CN112979549 B CN 112979549B
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organic compound
oled device
aryl
cyano
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CN112979549A (en
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张磊
高威
冉佺
代文朋
翟露
邓东阳
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Wuhan Tianma Microelectronics Co Ltd
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Abstract

The invention provides an organic compound, an electroluminescent material, an OLED device and a display panel, wherein the organic compound has a structure shown in a formula I, is a small molecular compound containing cyano, has proper HOMO and LUMO energy levels through the design and matching of a mother nucleus structure and a substituent, effectively improves the electron transmission capability and electron mobility, and has excellent thermal stability and film stability, thereby improving the luminous efficiency. The organic compound is particularly suitable for being used as an electron transport material, can improve the luminous efficiency of an OLED device, prolongs the service life and reduces the threshold voltage.

Description

Organic compound, electroluminescent material, OLED device and display panel
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an organic compound, an electroluminescent material, an OLED device and a display panel.
Background
Organic Electroluminescence (EL) technology is one of the most promising technologies in the field of optoelectronics, and compared with inorganic electroluminescent devices, organic electroluminescent devices (Organic Light Emitting Diode, OLED) have the characteristics of low power consumption, fast response speed, flexibility, wide viewing angle, large-area display, full luminescent color, etc., and can be compatible with various existing standards and technologies to make low-cost light emitting devices, so that they are widely used in the fields of flexible display, flat panel display, solid state lighting and vehicle-mounted display.
At present, the OLED has entered an industrialization stage, and the growing display demand drives the rapid development of OLED devices, materials forming the devices are continuously updated, and meanwhile, the device structure is continuously optimized. Taking a classical organic electroluminescent device as an example, the organic film layer in the stacked structure may include a light emitting layer, an electron transporting layer, a hole injecting layer, an electron injecting layer, and the like. The electron transport layer has good electron receiving capability and can effectively transport electrons, and the structure and the property of the electron transport material affect the service performance of the device.
The electron transport material of conventional OLED devices is 8-hydroxyquinoline aluminum (Alq 3 )，Alq 3 Is a bidentate chelate, has a stable five-membered ring structure, and can be used for preparing a film by a vacuum evaporation method. However, alq 3 Relatively low, about 10 -6 cm 2 Vs, such that the electron transport and hole transport of the device are unbalanced. With the development of the commercialization and the practicability of OLED devices, alq 3 The performance requirements of electroluminescent devices have not been met.
With the continuous development of display technology, more electron transport materials including phenanthroline (BPhen,) Bathocuproine (BCP,) And TmPyPB ()>) And the like, the electron transport materials can generally meet the market demands of the organic electroluminescent panel, but the glass transition temperature of the electron transport materials is lower and is generally lower than 85 ℃, and when the device is operated, the generated joule heat can cause molecular degradation and change of molecular structure, so that the panel has lower efficiency and poorer thermal stability. Meanwhile, the symmetry of the molecular structure is regular, and the molecular structure is easy to crystallize after a long time. Once the electron transport material is crystallized, the charge transition mechanism between molecules is different from the amorphous film mechanism which normally operates, so that the electron transport performance is reduced, the mobility of electrons and holes of the whole device is unbalanced, the exciton formation efficiency is greatly reduced, and the exciton formation is concentrated at the interface of the electron transport layer and the light emitting layer, so that the device efficiency and the service life are seriously reduced.
Based on the current state of development, an electron transport material having higher transport efficiency and better service performance is desired, and thus many researchers have been devoted to the study of electron transport materials. In the electron transport compounds disclosed in CN101003508A and organic light emitting devices comprising the same, a series of pyrenyl electron transport compounds were specifically designed, exhibiting good electron transport efficiency and deposition characteristics. CN107935936a discloses a benzimidazole compound and derivative, an organic electronic transmission material, and preparation and application thereof, which have good thermal stability and film morphology stability, and are beneficial to improving the stability of devices. However, the current electron transport material has a planar molecular structure, and has large intermolecular attraction, which is unfavorable for evaporation and application; meanwhile, the electron transport material has the defects of low electron mobility, unsatisfactory energy level matching, poor thermal stability, short service life, doping property and the like, and limits the further development of OLED display devices.
Therefore, development of a wider variety of higher performance electron transport materials to meet the application requirements of OLED display devices is an important research in the art.
Disclosure of Invention
In order to develop a wider variety of electron transport materials with more perfect properties, it is an object of the present invention to provide an organic compound having a structure as shown in formula I:
in the formula I, X is selected from O, S or N-R N 。
R N Selected from any one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
Wherein, the C6-C30 can be C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26 or C28, etc.
The C3-C30 may be C3, C4, C5, C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, or the like.
In the formula I, L 1 、L 2 、L 3 、L 4 Each independently selected from any one of a substituted or unsubstituted C6-C40 arylene group, a substituted or unsubstituted C3-C40 heteroarylene group.
Wherein, the C6-C40 can be C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36 or C38, etc.
The C3-C40 may be C3, C4, C5, C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, or the like.
In the formula I, ar 1 、Ar 2 Each independently selected from any one of substituted or unsubstituted C2-C40 heteroaryl, cyano-substituted C6-C30 aryl; and Ar is Ar 1 、Ar 2 Comprises at least one cyano-substituted C6-C30 aryl group.
The C2-C40 may be C2, C3, C4, C5, C6, C8, C10, C12, C13, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, or the like.
The C6-C30 may be C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, or the like.
In the present invention, "cyano-substituted C6-C30 aryl" means a C6-C30 aryl group having at least 1 cyano substituent, i.e., the number of cyano groups is 1 or more, and may be 1, 2, 3 or 4, etc.
In formula I, a, b, c, d, e, f are each independently selected from integers from 0 to 3, e.g., each independently may be 0, 1, 2 or 3; and a and f are not 0 at the same time, and a+b+c+d+e+f is not less than 2.
The organic compound provided by the invention contains at least 1 cyano group, and is particularly suitable for being used as an electron transport material through the mutual cooperation of a mother nucleus structure and a substituent group. The electrochemical reducibility of the organic compound is reversible, has high enough reduction potential and electron mobility, is beneficial to electron transmission, ensures that electrons can be recombined in a light-emitting layer, and improves the generation rate of excitons; meanwhile, the HOMO/LUMO energy level of the organic compound is proper, so that the injection barrier of electrons is reduced, the opening and working voltage is reduced, and the organic compound has a certain hole blocking capability. The organic compound also has high glass transition temperature and thermal decomposition stability, effectively avoids the influence of Joule heat generated during working on the service life and efficiency of the device, can form an amorphous uniform film, and avoids degradation or attenuation caused by light scattering or crystallization induction, thereby improving the stability of the device.
It is a second object of the present invention to provide an electroluminescent material comprising an organic compound according to one of the objects.
It is a further object of the present invention to provide an OLED device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode, the material of the organic thin film layer comprising an electroluminescent material as defined in the second object.
It is a fourth object of the present invention to provide a display panel comprising an OLED device as described in the third object.
Compared with the prior art, the invention has the following beneficial effects:
the organic compound provided by the invention is a small molecular compound containing cyano, has proper HOMO and LUMO energy levels through the design and coordination of a mother nucleus structure and a substituent, effectively improves the electron transmission capacity and electron mobility, and has excellent thermal stability and film stability, thereby improving the luminous efficiency. The organic compound is used as an electron transport material, so that the luminous efficiency of the OLED device can be improved, the service life is prolonged, and the threshold voltage is reduced.
Drawings
FIG. 1 is a schematic diagram of an OLED device according to the present invention;
wherein 101-anode, 102-cathode, 103-light emitting layer, 104-first organic thin film layer, 105-second organic thin film layer.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
It is an object of the present invention to provide an organic compound having a structure as shown in formula I:
in the formula I, X is selected from O, S or N-R N 。
R N Selected from any one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
Wherein the C6-C30 aryl may be an aryl of C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, or C28, etc., exemplary including but not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl, indenyl, or the like.
The C3-C30 heteroaryl group may be a heteroaryl group such as C3, C4, C5, C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26 or C28, and the hetero atom in the heteroaryl group may be O, S, N, P, si or B, etc.
In the formula I, L 1 、L 2 、L 3 、L 4 Each independently selected from any one of a substituted or unsubstituted C6-C40 arylene group, a substituted or unsubstituted C3-C40 heteroarylene group.
Wherein the C6-C40 arylene group may be an arylene group of C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, or C38, etc., exemplary including but not limited to: phenylene, biphenylene, naphthylene, phenanthrylene, anthracenylene, and the like.
The C3-C40 heteroarylene group may be a heteroarylene group of C3, C4, C5, C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36 or C38, etc., and the hetero atom in the heteroarylene group may be O, S or N, etc.
In the formula I, ar 1 、Ar 2 Each independently selected from any one of substituted or unsubstituted C2-C40 heteroaryl, cyano-substituted C6-C30 aryl; and Ar is Ar 1 、Ar 2 Comprises at least one cyano-substituted C6-C30 aryl group.
The C2-C40 heteroaryl can be C2, C3, C4, C5, C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36 or C38 and the like heteroaryl, and the heteroatom in the heteroaryl can be O, S, N, P, si or B and the like; exemplary include, but are not limited to: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, pyrrolyl, thienyl, furanyl, oxadiazolyl, pyrazolyl, thiadiazolyl, imidazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenanthroline, carbazolyl, benzofuranyl, benzothienyl, indolyl, acridinyl, and the like, preferably nitrogen-containing heteroaryl.
The C6-C30 aryl group may be an aryl group of C6, C8, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, or C28, etc., exemplary including but not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, anthryl, pyrenyl, perylenyl, triphenylenyl, and the like.
In the present invention, "cyano-substituted C6-C30 aryl" means a C6-C30 aryl group having at least 1 cyano substituent, i.e., the number of cyano groups is 1 or more, and may be 1, 2, 3 or 4, etc.
In formula I, a, b, c, d, e, f are each independently selected from integers from 0 to 3, e.g., each independently may be 0, 1, 2 or 3; and a and f are not 0 at the same time, and a+b+c+d+e+f is not less than 2.
The organic compound provided by the invention contains at least 1 cyano group, has proper HOMO and LUMO energy levels through the mutual cooperation of a mother nucleus structure and a specific substituent group, has good electron transmission capability and high electron migration rate, and is particularly suitable for being used as an electron transmission material. Meanwhile, the organic compound also has excellent thermal stability and film stability, can form an amorphous uniform film without pinholes, and is beneficial to improving the luminous efficiency of the device.
In one embodiment, the substituents in the substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene are each independently selected from deuterium, halogen, cyano, C1-C20 (e.g., C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C19, etc.), straight or branched alkyl, C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.), aryl, C2-C18 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.), heteroaryl, C1-C20 (e.g., C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C19, etc.), alkoxy, or C1-C20 (e.g., C2, C3, C4, C5, C6, C12, C10, C18, or C18, etc.), or at least one of the sulfur groups.
In the present invention, the halogen includes fluorine, chlorine, bromine or iodine. The following description refers to the same descriptions, all with the same meaning.
In one embodiment, the organic compound has a structure as shown in formula II:
in formula II, X, L 1 、L 2 、L 3 、L 4 、Ar 1 、Ar 2 Each of a, b, c, d, e, f independently has the same defined range as in formula I.
In one embodiment, the R N Any one selected from phenyl, biphenyl, naphthyl, anthryl or phenanthryl.
In one embodiment, the L 1 、L 2 、L 3 、L 4 Each independently selected from any one of phenylene, biphenylene, naphthylene, pyridylene or terphenylene.
In one embodiment, the cyano-substituted C6-C30 aryl is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
L 5 Selected from any one of single bond, phenylene, naphthylene, pyridylene or biphenylene.
Ar 3 Any one of cyano, substituted or unsubstituted C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) aryl, substituted or unsubstituted C2-C18 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.) heteroaryl.
Ar 3 Is a Chinese style of instituteThe substituted substituents are each independently selected from at least one of deuterium, halogen, cyano, C1-C20 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.), straight or branched alkyl, C1-C20 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.), alkoxy, or C1-C20 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.) alkylthio.
n is an integer selected from 1 to 3, and may be, for example, 1, 2 or 3.
In one embodiment, the cyano-substituted C6-C30 aryl is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
In one embodiment, the substituted or unsubstituted C2 to C40 heteroaryl is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
R A Selected from any of deuterium, halogen, cyano, C1-C20 (e.g., C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C19, etc.), straight or branched alkyl, C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.), aryl, C2-C18 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.), heteroaryl, C1-C20 (e.g., C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C19, etc.), alkoxy, or C1-C20 (e.g., C2, C3, C4, C5, C6, C8, C10, C12, C14, C16, C18, or C19, etc.), alkylthio.
s 1 An integer selected from 0 to 4 may be, for example, 0, 1, 2, 3 or 4.
s 2 An integer selected from 0 to 3 may be, for example, 0, 1, 2 or 3.
s 3 An integer selected from 0 to 2 may be, for example, 0, 1 or 2.
s 4 An integer selected from 0 to 6 may be, for example, 0, 1, 2, 3, 4, 5 or 6.
s 5 An integer selected from 0 to 5 may be, for example, 0, 1, 2, 3, 4 or 5.
In one embodiment, the substituted or unsubstituted C2-C40 heteroaryl is selected from any one of the following groups, or any one of the following groups substituted with a substituent:
wherein the dotted line represents the attachment site of the group.
The substituents are selected from deuterium, halogen, cyano, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) straight or branched chain alkyl, C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) aryl, C2-C18 (e.g., C3, C4, C5, C6, C8, C10, C12, C14, C16, or C18, etc.) heteroaryl, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) (e.g., at least one of C2, C3, C4, C5, C6, C7, C8, or C9) alkoxy, or C1-C10 alkylthio.
In a preferred embodiment, the substituents are selected from deuterium, halogen, cyano, phenyl, naphthyl, biphenyl, and the like.
In one embodiment, the organic compound is selected from any one of the following compounds M1 to M60:
in the invention, the organic compound with the structure shown in the formula I can be prepared by the following synthetic route:
in the above synthetic route, X, L 1 、L 2 、L 3 、L 4 、Ar 1 、Ar 2 Each independently having the same defined ranges as in formula I;
when a, b, c, d, e, f is independently selected from integers of 0 to 3, and a and f are not simultaneously 0, a+b+c is not less than 1, d+e+f is not less than 1, U 1 、U 2 Each independently selected from halogen (e.g., chlorine, bromine, or iodine); the order of the two-step coupling reaction is not particularly limited;
when a, b and c are all 0, f is selected from integers from 1 to 3, d and e are each independently selected from integers from 0 to 3, d+e+f is not less than 2, U 1 Is hydrogen, U 2 Selected from halogen (e.g., chlorine, bromine or iodine), the above synthetic route is a one-step coupling reaction;
when d, e and f are all 0, a is selected from integers of 1-3, b and c are each independently selected from integers of 0-3, a+b+c is more than or equal to 2, U 1 Selected from halogen (e.g. chlorine, bromine or iodine), U 2 The synthetic route is one-step coupling reaction.
It is a second object of the present invention to provide an electroluminescent material comprising an organic compound according to one of the objects.
It is a further object of the present invention to provide an OLED device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode, the material of the organic thin film layer comprising an electroluminescent material as defined in the second object.
In one embodiment, the organic thin film layer comprises an electron transport layer, the material of which comprises the electroluminescent material as described for the second purpose.
In one embodiment, the organic thin film layer comprises a light emitting layer, the material of which comprises the electroluminescent material as described in the second object.
In one embodiment, the organic thin film layer comprises a hole blocking layer, and the material of the hole blocking layer comprises the electroluminescent material as described in the second object.
In one embodiment, the organic thin film layer further includes any one or a combination of at least two of a hole transport layer, a hole injection layer, an electron blocking layer, or an electron injection layer.
In the OLED device provided by the invention, the anode material can be metal, metal oxide or conductive polymer; wherein the metal comprises copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum and the like and alloys thereof, the metal oxide comprises Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide, indium Gallium Zinc Oxide (IGZO) and the like, and the conductive polymer comprises polyaniline, polypyrrole, poly (3-methylthiophene) and the like. In addition to the above-described materials that facilitate hole injection and combinations thereof, materials known to be suitable as anodes are included.
In the OLED device, the cathode material may be a metal or a multi-layer metal material; wherein the metal comprises aluminum, magnesium, silver, indium, tin, titanium, etc. and their alloys, and the multilayer metal material comprises LiF/Al, liO 2 /Al、BaF 2 Al, etc. In addition to the above-described materials that facilitate electron injection and combinations thereof, materials known to be suitable as cathodes are included.
In the OLED device, the organic thin film layer includes at least one light emitting layer (EML) and an Electron Transport Layer (ETL) disposed on two sides of the light emitting layer, and any one or a combination of at least two of a Hole Transport Layer (HTL), a Hole Injection Layer (HIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL) or an Electron Injection Layer (EIL), wherein the hole injection layer, the electron injection layer, and the hole transport layer may be carbazole compounds, arylamine compounds, benzimidazole compounds, metal compounds, and the like. A cap layer (CPL) may also optionally be provided on the cathode (the side remote from the anode) of the OLED device.
The schematic diagram of the OLED device is shown in fig. 1, and includes an anode 101 and a cathode 102, a light emitting layer 103 disposed between the anode 101 and the cathode 102, and a first organic thin film layer 104 and a second organic thin film layer 105 disposed on two sides of the light emitting layer 103, wherein the first organic thin film layer 104 is any one of a Hole Transport Layer (HTL), a Hole Injection Layer (HIL), or an Electron Blocking Layer (EBL), or a combination of at least 2, and the second organic thin film layer 105 includes an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL) and/or an Electron Injection Layer (EIL); a cap layer (CPL) is also optionally provided on the cathode 102 (on the side remote from 105).
The OLED device can be prepared by 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. Among them, known film forming methods such as vapor deposition, sputtering, spin coating, dipping, ion plating, and the like can be used for forming the organic thin layer.
It is a fourth object of the present invention to provide a display panel comprising an OLED device as described in the third object.
The following examples of organic compounds according to the invention are given by way of example:
example 1
An organic compound M5 having the structure:
the preparation method of the organic compound M5 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M5-1 (12 mmol), M5-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/absolute ethanol (EtOH)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then a palladium catalyst Pd (PPh 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M5-3.
(2)
In a 250mL round bottom flask, the intermediate M5-3 (12 mmol), the reactant M5-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad, extracted with methylene chloride, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the objective product M5.
The structure of the organic compound M5: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 45 H 28 N 2 Calculated 596.2 and tested 596.4.
Elemental analysis test value (%): and C90.58,H 4.73,N 4.69.
Example 2
An organic compound M12 having the structure:
the preparation method of the organic compound M12 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M12-1 (12 mmol), M12-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M12-3.
(2)
In a 250mL round bottom flask, the intermediate M12-3 (12 mmol), the reactant M12-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad, extracted with methylene chloride, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the objective product M12.
The structure of the organic compound M12: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 48 H 29 N 3 Calculated 647.2 and tested 647.4.
Elemental analysis test value (%): and C89.00,H 4.51,N 6.49.
Example 3
An organic compound M16 having the structure:
/>
the preparation method of the organic compound M16 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M16-1 (12 mmol), M16-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M16-3.
(2)
In a 250mL round bottom flask, the intermediate M16-3 (12 mmol), the reactant M16-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad, extracted with methylene chloride, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the objective product M16.
The structure of the organic compound M16: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 45 H 28 N 2 Calculated 596.3 and tested 596.5.
Elemental analysis test value (%): and C90.58,H 4.73,N 4.69.
Example 4
An organic compound M20 having the structure:
the preparation method of the organic compound M20 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M20-1 (12 mmol), M20-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M20-3.
(2)
In a 250mL round bottom flask, the intermediate M20-3 (12 mmol), the reactant M5-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude was purified by silica gel column chromatographyThe product gives the target product M20.
The structure of the organic compound M20: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 46 H 27 N 3 Calculated 621.2 and tested 621.3.
Elemental analysis test value (%): and C88.86,H 4.38,N 6.76.
Example 5
An organic compound M32 having the structure:
the preparation method of the organic compound M32 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M32-1 (12 mmol), M32-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M32-3.
(2)
In a 250mL round bottom flask, the intermediate M32-3 (12 mmol), the reactant M32-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixtureIn the resultant solution, the intermediate obtained by carrying out the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the objective product M32.
Structure of the organic compound M32: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 50 H 31 N 5 Calculated 701.3 and tested 701.4.
Elemental analysis test value (%): and C85.57,H 4.45,N 9.98.
Example 6
An organic compound M36 having the structure:
the preparation method of the organic compound M36 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M36-1 (12 mmol), M36-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite while extracting with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give intermediate M36-3.
(2)
Firing at 250mL round bottomIn a bottle, the intermediate M36-3 (12 mmol), the reactant M36-4 (12 mmol) and Na obtained in step (1) were added 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad, extracted with methylene chloride, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the final product M36.
The structure of the organic compound M36: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 37 H 21 N 3 O calculated 523.2 and tested 523.4.
Elemental analysis test values: and C84.88,H 4.04,N 8.03,O 3.06.
Example 7
An organic compound M44 having the structure:
the preparation method of the organic compound M44 comprises the following steps:
(1)
in a 250mL round bottom flask, reactants M44-1 (12 mmol), M44-2 (12 mmol) and Na 2 CO 3 (80 mmol) added to toluene/EtOH (absolute ethanol)/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a pad of celite, extracted with methylene chloride at the same time, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporatedAfter the reaction, the crude product was purified by silica gel column chromatography to give intermediate M44-3.
(2)
In a 250mL round bottom flask, the intermediate M44-3 (12 mmol), the reactant M44-4 (12 mmol) and Na obtained in step (1) were reacted 2 CO 3 (80 mmol) added to toluene/EtOH/H respectively 2 O (75/25/50, mL) in a solvent to form a mixed solution, and then Pd (PPh) 3 ) 4 (0.48 mmol) was added to the above mixed solution, and the intermediate obtained by conducting the reflux reaction under nitrogen atmosphere for 20 hours was cooled to room temperature, added to water, then filtered through a celite pad, extracted with methylene chloride, then washed with water, and dried with anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the objective product M44.
The structure of the organic compound M44: MALDI-TOF MS (m/z) was obtained by matrix assisted laser desorption ionization time-of-flight mass spectrometry: c (C) 50 H 31 N 5 Calculated 701.2 and tested 701.4.
Elemental analysis test values: and C85.57,H 4.45,N 9.98.
Simulation calculation of the compound:
by applying the Density Functional Theory (DFT), the organic compound and the comparison compound provided by the invention are optimized and calculated under the calculation level of B3LYP/6-31G (d) through a Guassian 09 program package (Guassian Inc.), the energy level and the distribution condition of the HOMO and the LUMO of the front line orbitals of the molecules are obtained, and meanwhile, the singlet energy level E of the compound molecules is calculated based on the simulation of the time-dependent density functional theory (TDDFT) S And triplet energy level E T The specific calculation results are shown in table 1.
Comparative compound 1:comparative compound 2: />
TABLE 1
Organic compound HOMO(eV) LUMO(eV) E S (eV) E T (eV) M W
M5 -5.38 -1.80 3.23 2.45 596
M12 -5.25 -1.93 3.28 2.49 647
M16 -5.18 -1.78 3.36 2.52 596
M20 -5.51 -1.98 3.15 2.40 621
M32 -5.46 -2.01 3.24 2.46 701
M36 -5.67 -2.01 3.19 2.42 523
M44 -5.48 -2.02 3.28 2.47 701
Comparative Compound 1 -5.49 -1.77 3.54 2.81 496
Comparative Compound 2 -5.57 -1.88 3.62 2.76 651
As can be seen from the data in Table 1, the organic compound provided by the invention has a proper LUMO energy level of between-1.75 and-2.05 eV, is beneficial to electron injection and transmission, effectively improves the luminous efficiency and service life of the device, and reduces the driving voltage of the device. Compared with the comparison compound 1 and the comparison compound 2 which do not contain the benzocarbazole structural unit, the organic compound has relatively smaller triplet energy level, so that part of superfluous high-energy excitons of the light-emitting layer can be transited to one side of electron transmission, the generation of non-radiative heat caused by aggregation and collision of the excitons in the light-emitting layer is reduced, and the service life of the device is prolonged.
The following examples of applications of the organic compounds of the present invention in OLED devices are listed:
application example 1
An OLED device comprising the following structure, in order: a substrate, an Indium Tin Oxide (ITO) anode 15nm, a hole injection layer 10nm, a first hole transport layer 100nm, a second hole transport layer 20nm, a light emitting layer 30nm, a hole blocking layer 5nm, an electron transport layer 30nm, and a cathode 90nm (magnesium-silver electrode, magnesium-silver mass ratio 1:9).
The OLED device was prepared as follows:
(1) Cutting a glass substrate with an ITO anode into a size of 50mm multiplied by 0.7mm, respectively carrying out ultrasonic treatment in isopropanol and deionized water for 30min, and then exposing to ozone for cleaning for 10min; mounting the obtained glass substrate with the ITO anode having a thickness of 15nm on a vacuum deposition apparatus;
(2) At a vacuum degree of 2X 10 -6 Vacuum evaporating a compound a with the thickness of 10nm on the ITO anode layer under Pa to form a hole injection layer;
(3) Vacuum evaporating a compound b on the hole injection layer to form a first hole transport layer with the thickness of 100nm;
(4) Vacuum evaporating a compound c on the first hole transport layer to form a second hole transport layer with the thickness of 20nm;
(5) Vacuum co-evaporating a compound d (host material) and a compound e (doping material, doping mass ratio is 3%) on the second hole transport layer as a light emitting layer, wherein the thickness is 30nm;
(6) Vacuum evaporating a compound f on the light-emitting layer to serve as a hole blocking layer, wherein the thickness of the hole blocking layer is 5nm;
(7) Vacuum co-evaporating the organic compound M5 (example 1) and the doping compound g (doping ratio is 4:6) serving as an electron transport layer on the hole blocking layer, wherein the thickness is 30nm;
(8) And vacuum evaporating a magnesium-silver electrode on the electron transport layer, wherein the mass ratio of magnesium to silver is 1:9, and the thickness of the magnesium-silver electrode serving as a cathode is 90nm.
The structure of the compound used in the OLED device is as follows:
application example 2
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M12; the other preparation steps were identical.
Application example 3
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M16; the other preparation steps were identical.
Application example 4
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M20; the other preparation steps were identical.
Application example 5
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M32; the other preparation steps were identical.
Application example 6
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M36; the other preparation steps were identical.
Application example 7
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) is replaced with an equivalent amount of the organic compound M44; the other preparation steps were identical.
Comparative example 1
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) was replaced with an equivalent amount of the comparative compound 1 [ ]) Replacement; the other preparation steps were identical.
Comparative example 2
An OLED device differing from application example 1 only in that the organic compound M5 in step (7) was replaced with an equivalent amount of the comparative compound 2 [ ]) Replacement; the other preparation steps were identical.
Performance evaluation of OLED device:
testing the currents of the OLED device under different voltages by using a Keithley 2365A digital nano-volt meter, and dividing the currents by the light emitting areas to obtain the current densities of the OLED device under different voltages; testing the brightness and radiant energy density of the OLED device under different voltages by using a Konicaminolta CS-2000 spectroradiometer; according to the current density and brightness of the OLED device under different voltages, the OLED device with the same current density (10 mA/cm 2 ) Operating voltage (op.v) and current efficiency (cd/a); by measuring the brightness of OLED devicesLifetime LT obtained for 95% of initial brightness 95 (at 50 mA/cm) 2 Under test conditions; the performance data are shown in table 2.
TABLE 2
OLED device Electron transport layer material Op.V(V) Current efficiency (cd/A) Life LT 95 (h)
Application example 1 M5 3.42 65.2 142
Application example 2 M12 3.45 65.8 144
Application example 3 M16 3.40 64.2 145
Application example 4 M20 3.42 64.8 144
Application example 5 M32 3.42 65.4 143
Application example 6 M36 3.45 65.0 145
Application example 7 M44 3.40 64.9 140
Comparative example 1 Comparative Compound 1 3.56 61.5 125
Comparative example 2 Comparative Compound 2 3.50 62.4 130
As can be obtained from the data in table 2, the organic compound provided by the invention has lower working voltage, higher current efficiency and longer device life as an electron transport material, and compared with the comparative compound 1 and the comparative compound 2, the working voltage, the current efficiency and the device life of the device are respectively improved by about 3.5%, 5% and 11%; and the current efficiency and the service life of the device are improved simultaneously, and the material provided by the invention has more proper LUMO energy level and lower triplet state energy level, so that the material has more excellent electron transmission characteristics.
The applicant states that the organic compound, electroluminescent material, OLED device and display panel of the present invention are illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be carried out by relying on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (13)

1. An organic compound, characterized in that the organic compound has a structure as shown in formula I:
wherein X is selected from S or N-R N ；
R N Any one selected from C6-C20 aryl;
L 1 、L 2 、L 3 、L 4 each independently selected from any one of C6-C20 arylene groups;
Ar 1 、Ar 2 each independently selected from Any one of C6-C30 aryl substituted by cyano; and Ar is Ar 1 、Ar 2 Comprises at least one cyano-substituted C6-C30 aryl group;
R A any one of deuterium, halogen, cyano, C1-C10 straight-chain or branched-chain alkyl and C6-C18 aryl;
s 2 s is an integer selected from 0 to 3 3 S is selected from an integer of 0 to 2 5 An integer selected from 0 to 5;
the cyano-substituted C6-C30 aryl is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group;
L 5 any one selected from single bond, phenylene, naphthylene or biphenylene;
Ar 3 any one selected from cyano and C6-C18 aryl;
n is 1;
a. b, c, d, e, f are each independently selected from integers from 0 to 3, and a and f are not simultaneously 0;
a+b+c+d+e+f≥2。
2. the organic compound according to claim 1, wherein the organic compound has a structure as shown in formula II:
therein, X, L 1 、L 2 、L 3 、L 4 、Ar 1 、Ar 2 Each of a, b, c, d, e, f independently has the same defined range as in formula I.
3. The organic compound according to claim 1, wherein theR N Any one selected from phenyl, biphenyl, naphthyl, anthryl or phenanthryl.
4. The organic compound according to claim 1, wherein L 1 、L 2 、L 3 、L 4 Each independently selected from any one of phenylene, biphenylene, naphthylene, or terphenylene.
5. The organic compound according to claim 1, wherein the cyano-substituted C6-C30 aryl is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
6. The organic compound according to claim 1, wherein Ar 1 、Ar 2 Each independently selected from cyano-substituted C6-C30 aryl or any one of the following groups:
wherein the dotted line represents the attachment site of the group.
7. An organic compound, wherein the organic compound is selected from any one of the following compounds M1 to M60:
8. an electroluminescent material, characterized in that it comprises an organic compound according to any one of claims 1 to 7.
9. An OLED device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode, wherein the material of the organic thin film layer comprises the electroluminescent material of claim 8.
10. The OLED device of claim 9, wherein the organic thin film layer includes an electron transport layer, and wherein the material of the electron transport layer includes the electroluminescent material of claim 8.
11. The OLED device of claim 9, wherein the organic thin film layer includes a light-emitting layer, and wherein the material of the light-emitting layer includes the electroluminescent material of claim 8.
12. The OLED device of claim 9, wherein the organic thin film layer includes a hole blocking layer, and wherein the material of the hole blocking layer includes the electroluminescent material of claim 8.
13. A display panel comprising an OLED device as claimed in any one of claims 9 to 12.
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