An organic compound and application thereof, and an organic electroluminescence device comprising the same

Abstract

The present application relates to an organic compound, belongs to organic luminescent material technical field, and simultaneously relates to the application of the compound and an organic electroluminescent device containing the same.The organic compound has the structure shown in the following formula.When the compound is applied to an organic electroluminescent device, the working voltage of the device can be effectively reduced, and the efficiency of the device is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to an organic compound, belonging to the technical field of organic light-emitting materials, and simultaneously relates to the application of the compound and an organic electroluminescent device comprising the same. BACKGROUND

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them well suited for manufacturing on flexible substrates, allowing the design and production of aesthetically pleasing and cool optoelectronic products, with advantages unmatched by inorganic materials. Examples of such organic optoelectronic devices include organic light emitting diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, etc. Among them, OLEDs have developed particularly rapidly and have achieved commercial success in the field of information display. OLEDs can provide high saturation of red, green and blue colors, and full-color display devices made of them do not require additional backlights, with the advantages of colorful, thin, soft, etc.

[0003] The core of an OLED device is a thin film structure containing various functional organic materials. Commonly used functional organic materials include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light-emitting host materials and light-emitting guests (dyes), etc. When powered on, electrons and holes are injected and transported to the light-emitting region and recombine there, generating excitons and emitting light.

[0004] People have developed a variety of organic materials, combined with various unique device structures, which can improve carrier mobility, control carrier balance, break through electroluminescent efficiency, and delay device decay. For quantum mechanical reasons, common fluorescent emitters mainly utilize singlet excitons generated when electrons and holes combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet and singlet excitons, known as phosphorescent emitters, which can improve energy conversion efficiency by up to four times compared to traditional fluorescent emitters. The technology of thermally activated delayed fluorescence (TADF) promotes the transition of triplet excitons to singlet excitons, allowing efficient use of triplet excitons without using metal complexes to achieve high luminescent efficiency. The technology of thermally activated sensitized fluorescence (TASF) uses materials with TADF properties to sensitize emitters through energy transfer, also achieving high luminescent efficiency.

[0005] As OLED products gradually enter the market, people have increasingly high requirements for the performance of such products. The current OLED materials and device structures cannot completely solve the problems of OLED product efficiency, lifetime, cost, etc.

[0006] Therefore, there is an urgent need in the art to develop an organic electroluminescent material capable of improving the luminous efficiency of a device, reducing the driving voltage, and prolonging the service life. SUMMARY

[0007] One of the objectives of the present application is to provide a compound, in particular an organic electroluminescent material, especially an electron blocking layer material, which is applied to an organic electroluminescent device, capable of improving the luminous efficiency of the device, reducing the driving voltage, and can be used as a red light electron blocking layer material.

[0008] To achieve the above objective, the present application adopts the following technical solutions:

[0009] The present application provides a compound, which has a structure shown in Formula I;

[0010]

[0011] In Formula I:

[0012] L, L 1 and L 2 are each independently selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0013] Ar 1 is selected from one of a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group;

[0014] X is O or S;

[0015] X 1 ~X 11 are each independently selected from C, CR 1 or N, and the R 1 is selected from one of hydrogen, halogen, cyano, nitro, hydroxyl, a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cyclic alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 silyl group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group; 1 is independently connected to an aromatic ring or a heteroaromatic ring to form a ring or not to form a ring;

[0016] X 12 ~X 19 are each independently selected from C, CR 2 or N, and the R 2one selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and R 2 is independently linked to the aromatic ring or heteroaromatic ring to which it is attached to form a ring or not to form a ring;

[0017] When the above group has a substituent, the substituent is selected from one or a combination of at least two of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 thioalkoxy, C1-C20 silyl, cyano, nitro, hydroxyl, C6-C60 aryl, and C3-C60 heteroaryl.

[0018] In the present application, the "substituted or unsubstituted" group can be substituted with one substituent or can be substituted with a plurality of substituents, and when the substituents are a plurality, they can be selected from different substituents. When the same expression is used in the present application, it has the same meaning, and the selection range of the substituents is as described above and will not be described again.

[0019] In the present specification, the expression of Ca-Cb represents that the number of carbon atoms of the group is a to b, and unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0020] In the present specification, the expression of the ring structure with a dash through it represents that the connection site is at any position on the ring structure that can form a bond.

[0021] In the present specification, "each independently" means that when the subject has a plurality, they can be the same or different from each other.

[0022] In the present application, the expression of a chemical element, unless otherwise specified, generally includes the concept of its isotope, for example, the expression of "hydrogen (H)" includes the concept of its isotope 1 H (protium or H), 2 H (deuterium or D); and carbon (C) includes 12 C, 13 C, and the like, and will not be described again.

[0023] In the present application, the heteroatom in the heteroaryl group generally refers to an atom or atom group selected from N, O, S, P, Si, and Se, and preferably selected from N, O, and S.

[0024] In the present specification, as examples of halogen, fluorine, chlorine, bromine, iodine, and the like can be given.

[0025] In this invention, the substituted or unsubstituted C6-C30 aryl groups include monocyclic aryl groups and fused-ring aryl groups, with C6-C20 aryl groups being more preferred. A monocyclic aryl group refers to a molecule containing at least one phenyl group. When a molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, exemplarily such as phenyl, biphenyl, and terphenyl. Specifically, the biphenyl group includes 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, meta-terphenyl-4-yl, meta-terphenyl-3-yl, and meta-terphenyl-2-yl. A fused-ring aryl group refers to a molecule containing at least two aromatic rings, where the aromatic rings are not independent of each other but share two adjacent carbon atoms fused together. Examples include: naphthyl, anthracene, phenanthrene, indene, fluorenyl, fluoranthyl, triphenylene, pyrene, perylene, etc. Naphthyl, 2-naphthyl, and their derivative groups, etc. The naphthyl includes 1-naphthyl or 2-naphthyl; the anthraceneyl is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrene is selected from 1-pyrene, 2-pyrene, and 4-pyrene; the 2-tetraphenyl is selected from 1-2 ... The fluorene derivative group is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, 9,9'-spirodifluorenyl, and benzo[a]fluorenyl.

[0026] In this invention, the substituted or unsubstituted C3-C30 heteroaryl groups include monocyclic heteroaryl groups and fused-ring heteroaryl groups, more preferably C4-C20 heteroaryl groups, and more preferably C5-C12 heteroaryl groups. A monocyclic heteroaryl group refers to a molecule containing at least one heteroaryl group. When a molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and connected by a single bond. Examples of monocyclic heteroaryl groups include furanyl, thiophene, pyrrole, and pyridyl. A fused-ring heteroaryl group refers to a molecule containing at least one aromatic heterocycle and an aromatic ring (aromatic heterocycle or aromatic ring), and the two are not independent of each other but share a group consisting of two adjacent atoms fused together. Examples of fused-ring heteroaryl groups include: benzofuranyl, benzothiophenyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazoyl, acridineyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazoyl, azircarbazoyl, phenothiazinyl, phenothiazinyl, 9-phenylcarbazoyl, 9-naphthylcarbazoyl, dibenzocarbazoyl, indolocarbazoyl, etc.

[0027] Examples of the arylene group in the present application include divalent groups obtained by removing one hydrogen atom from the above-mentioned examples of the aryl group. Examples of the heteroarylene group in the present application include divalent groups obtained by removing one hydrogen atom from the above-mentioned examples of the heteroaryl group.

[0028] The chain alkyl group mentioned in the present application includes straight chain alkyl groups and branched chain alkyl groups unless otherwise specified. Specifically, the substituted or unsubstituted C1-C30 chain alkyl group is preferably a substituted or unsubstituted C1-C16 chain alkyl group, and more preferably a substituted or unsubstituted C1-C10 chain alkyl group. The substituted or unsubstituted C3-C30 cycloalkyl group is preferably a substituted or unsubstituted C3-C20 cycloalkyl group, and more preferably a substituted or unsubstituted C3-C10 cycloalkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, t-amyl, cyclohexyl, adamantyl, and the like.

[0029] Further, in formula I, the L is preferably a single bond; and / or, the L 1 is preferably a single bond; and / or, the L 2 is a single bond.

[0030] Further, in formula I, the N is attached to the position of X 12 ; or, the N is attached to the position of X 13 ; or, the N is attached to the position of X 14 ; or, the N is attached to the position of X 15 .

[0031] Further, in formula I, the X 1 to X 11 are each independently selected from CR 1 , the R 1 is independently selected from one of hydrogen, a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 silyl group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group, and the R 1 is independently bonded to or not bonded to the aromatic ring or the heteroaromatic ring; preferably, the X 1 to X 11 are each independently selected from CR 1 , the R 1 is hydrogen.

[0032] Further, in formula I, the X 12 to X 19 are each independently selected from C or CR 2 , the R 2independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cyclic alkyl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, said R 1 is independently linked to the aromatic or heteroaromatic ring to which it is attached to form a ring or is not linked to form a ring; preferably, X 12 ~ X 19 is independently selected from C or CR 2 , said R 2 is hydrogen.

[0033] When the above-mentioned substituted or unsubstituted groups have a substituent, the substituent is selected from one or a combination of at least two of deuterium, halogen, C1-C10 chain alkyl, C1-C10 alkoxy, C3-C10 cyclic alkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0034] Further, in formula I, said R 1 and R 2 are each independently selected from substituted or unsubstituted methyl, ethyl, n-propyl, i-propyl, n-butyl, n-hexyl, n-octyl, i-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, naphthyl, anthryl, phenanthryl, indenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, phenanthryl, indenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, naphthacenyl, tetracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirofluorenyl, and benzofluorenyl, furanyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, acridinyl, isobenzofuranyl, isobenzothienyl, acridinyl, pyridyl, benzocarbazolyl, azacarbazolyl, phenoxazinyl, phenazinyl;

[0035] When the above-mentioned substituted or unsubstituted groups have a substituent, the substituent is selected from one or a combination of at least two of deuterium, halogen, C1-C10 chain alkyl, C1-C10 alkoxy, C3-C10 cyclic alkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0036] Further, in formula I, said Ar 1 is selected from substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl, indenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, one of a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a 2-terphenyl group, a 3-terphenyl group, a 4-terphenyl group, a 9,9-dimethylfluorenyl group, a 9,9-diethylfluorenyl group, a 9,9-dipropylfluorenyl group, a 9,9-dibutylfluorenyl group, a 9,9-dipentylfluorenyl group, a 9,9-dihexylfluorenyl group, a 9,9-diphenylfluorenyl group, a 9,9-dinaphthylfluorenyl group, a spirofluorenyl group, and a benzofluorenyl group, a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an acridinyl group, an iso-benzofuranyl group, an iso-benzothienyl group, an acridinyl group, a pyridyl group, a benzocarbazolyl group, an azacarbazolyl group, a phenothiazinyl group, a phenoxazinyl group;

[0037] When the above-mentioned each group with or without substitution has a substituent, the substituent is preferably selected from one or a combination of at least two of deuterium, a halogen, a C1-C10 chain alkyl group, a C1-C10 alkoxy group, a C3-C10 cycloalkyl group, a C6-C30 aryl group, and a C3-C30 heteroaryl group.

[0038] Preferably, the Ar 1 is selected from the following structural groups with or without substitution, wherein the dotted line represents a bond:

[0039]

[0040] When the above-mentioned each structural group has a substituent, the substituent is selected from one or a combination of at least two of deuterium, a halogen, a C1-C10 chain alkyl group, a C1-C10 alkoxy group, a C3-C10 cycloalkyl group, a C6-C30 aryl group, and a C3-C30 heteroaryl group.

[0041] Further, in Formula I, the L 2 is connected to the position of X 12 .

[0042] Alternatively, the L 2 is connected to the position of X 13 .

[0043] Alternatively, the L 2 is connected to the position of X 14 .

[0044] Alternatively, the L 2 N is connected to the position of X 15 .

[0045] The present application provides a new organic electroluminescent material, the present application utilizes the coordination of diphenyl heterocyclic derivative and 2-position amino-substituted triolefin, which can obtain more optimal space structure, better thin film stacking form of electron blocking material, and the use of the electron material to the organic light emitting device can further improve the luminous efficiency of the device, and compared with the prior art compound, the effect of improving voltage and improving luminous efficiency is obvious.

[0046] In addition, the preparation process of the compound of the present application is simple and easy to operate, the raw materials are easy to obtain, and is suitable for mass production.

[0047] Further, the compound of the present application is preferably the following specific compounds, but the present application is not limited to the following specific compounds P1-P120:

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] The second object of the present application is to provide the use of the compound of the first object in an organic electroluminescent device, preferably as an electron blocking layer material of the organic electroluminescent device.

[0057] The compound of the present application as an electron blocking layer material of an organic electroluminescent device can effectively improve the luminous efficiency and reduce the driving voltage, and is especially suitable as a red light electron blocking layer material.

[0058] The third object of the present application is to provide an organic electroluminescent device, which comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode, and the organic layer contains the compound of the first object.

[0059] Preferably, the organic layer comprises an electron blocking layer, and the electron blocking layer contains the compound of the first object.

[0060] The compound of the present application can be applied not only to an organic electroluminescent device, but also to other types of organic electronic devices, including organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners, or electronic paper.

[0061] Specifically, another aspect of the present application provides an organic electroluminescent device, comprising a substrate, and an anode layer, a plurality of light-emitting functional layers, and a cathode layer formed in this order on the substrate; the light-emitting functional layers comprising at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer, and an electron transport layer, wherein the electron blocking layer contains at least one of the above-mentioned compounds.

[0062] An OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material layer can be further divided into a plurality of regions. For example, the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.

[0063] In a specific embodiment, a substrate can be used under the first electrode or over the second electrode. The substrate is a glass or a polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) can be provided on the substrate for display.

[0064] The first electrode can be formed by sputtering or depositing a material used for the first electrode on the substrate. When the first electrode serves as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof can be used. When the first electrode serves as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof can be used.

[0065] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used for the organic material layer can be an organic small molecule, an organic macromolecule, and a polymer, and a combination thereof.

[0066] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single layer structure of a hole transport layer (HTL), including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region can also be a multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL), and the electron blocking layer employs the compound of Formula I of the present application.

[0067] The material of the hole transport layer can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant-containing polymers such as polyphenylene vinylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphor sulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives, wherein the aromatic amine derivatives include compounds as shown in HT-1 to HT-51 below; or any combination thereof.

[0068]

[0069]

[0070]

[0071]

[0072] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can employ one or more compounds of HT-1 to HT-51 above, or one or more compounds of HI-1 to HI-3 below; or employ one or more compounds of HT-1 to HT-51 doped with one or more compounds of HI-1 to HI-3 below.

[0073]

[0074] The light-emitting layer includes light-emitting dyes (i.e., dopants) that can emit different wavelengths of light spectrum, and can also include host materials (Host). The light-emitting layer can be a single-color light-emitting layer that emits a single color such as red, green, blue, etc. Multiple single-color light-emitting layers of different colors can be arranged in a planar pattern according to a pixel pattern, or can be stacked together to form a color light-emitting layer. When the light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single-color light-emitting layer that can emit different colors such as red, green, blue, etc. at the same time.

[0075] Depending on the different technologies, the light-emitting layer material can employ different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, thermally activated delayed fluorescence light-emitting materials, etc. In an OLED device, a single light-emitting technology can be employed, or a combination of multiple different light-emitting technologies can be employed. These different light-emitting materials classified by technology can emit the same color of light, or can emit different colors of light.

[0076] In an aspect of the application, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, a combination of one or more of the following BFH-1 to BFH-17 listed below.

[0077]

[0078] In an aspect of the application, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of the following BFD-1 to BFD-24 listed below.

[0079]

[0080]

[0081] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The host material of the light-emitting layer is selected from, but not limited to, a combination of one or more of PH-1 to PH-85.

[0082]

[0083]

[0084]

[0085]

[0086] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of the following GPD-1 to GPD-47 listed below.

[0087]

[0088]

[0089] wherein D is deuterium.

[0090] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of the following RPD-1 to RPD-28 listed below.

[0091]

[0092] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of the following YPD-1 to YPD-11 listed below.

[0093]

[0094] The OLED organic material layer can also include an electron transport zone between the light-emitting layer and the cathode. The electron transport zone can be a single-layer structure electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport zone can also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0095] In one aspect of the present application, the electron transport layer material can be selected from, but not limited to, a combination of one or more of the following listed ET-1 to ET-73.

[0096]

[0097]

[0098]

[0099]

[0100] The device can also include an electron injection layer between the electron transport layer and the cathode, and the electron injection layer material includes, but is not limited to, a combination of one or more of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Yb, Li, or Ca.

[0101] Compared with the prior art, the present application has the following beneficial effects:

[0102] The present application provides a new type of organic electroluminescent material, the present application utilizes the coordination of diphenylfluorene derivative or silicon heterocyclic compound with 2-position amino-substituted triolefin, through reasonable structure adjustment, a more optimal spatial structure and better thin film stacking morphology of electron blocking material can be obtained, the use of the electron material in an organic light-emitting device can further improve the luminous efficiency of the device, and the effect of improving the voltage and improving the luminous efficiency is obvious compared with the prior art compound.

[0103] In addition, the preparation process of the compound of the present application is simple and easy to operate, the raw materials are easy to obtain, and is suitable for mass production. DETAILED DESCRIPTION

[0104] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0105] The representative synthesis path of the compound of formula I of the present application is as follows:

[0106]

[0107] wherein, Ar 1 , L, L 1 , X, X 1 -X 19 all have the same meaning as the symbols in formula I; Pd2(dba)3 represents tris(dibenzylacetone)dipalladium(0), IPr.HCl represents 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium tert-butoxide, (t-Bu)3P represents tri-tert-butylphosphine. The preparation of the compound of formula I of the present application includes the above-mentioned method, but is not limited to the above-mentioned method, and the compound of formula I synthesized by other methods by those skilled in the art also belongs to the protection scope of the present application.

[0108] More specifically, the present application is exemplarily provided with a specific synthesis method of a representative compound as follows: the solvents and reagents used in the following synthesis examples can be purchased or customized from the domestic chemical product market. In addition, those skilled in the art can also synthesize by known methods.

[0109] Synthesis Example 1: Synthesis of compound P4

[0110]

[0111] In a 1000 mL single-necked flask, 13.5 g of M1, 7.8 g of bromobenzene, 0.5 g of tris(dibenzylacetone)dipalladium (i.e. Pd2(dba)3), 0.5 g of IPr.HCl, 500 mL of toluene, 14.5 g of sodium tert-butoxide (NaOBu-t) were added, vacuumed and replaced with nitrogen for 3 times, and the reaction was heated to 90°C for 5 h. After the reaction was completed, the reaction was stopped. After cooling to room temperature, the reaction liquid was separated, the organic phase was filtered through a silica gel column twice, the organic phase was concentrated, methanol was added, refluxed and stirred for 1 h, and then filtered to obtain a light yellow powder M1-1, which was then recrystallized with ethyl acetate to obtain a pure product.

[0112] In a 1000 mL three-necked flask, 17.3 g of M1-1, 12.3 g of 1-bromodibenzofuran, 0.5 g of tris(dibenzylacetone)dipalladium (i.e. Pd2(dba)3), 0.5 mL of tri-tert-butylphosphine ((t-Bu)3P), 500 mL of toluene, 14.5 g of sodium tert-butoxide (NaOBu-t) were added, vacuumed and replaced with nitrogen for 3 times, and the reaction was heated to 110°C for 5 h. After the reaction was completed, the reaction was stopped. After cooling to room temperature, the reaction liquid was separated, the organic phase was filtered through a silica gel column twice, the organic phase was concentrated, methanol was added, refluxed and stirred for 1 h, and then filtered to obtain a light yellow powder P4, which was then recrystallized with ethyl acetate three times to obtain a pure product. M / Z theoretical value: 511; M / Z actual value: 512, determined by ZAB-HS type mass spectrometer (manufactured by Micromass Company, UK).

[0113] Synthesis Example 2: Synthesis of compound P6

[0114]

[0115] Compound Ml-2 was also synthesized by the method of synthesis of compound Ml-1, except that bromobenzene was replaced by 3-bromodibenzofuran; compound P6 was also synthesized by the method of synthesis of compound P4, except that 1-bromodibenzofuran was replaced by 4-bromobiphenyl and intermediate Ml-1 was replaced by Ml-2. M / Z calcd 587; M / Z found 588 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0116] Synthesis Example 3: Synthesis of compound P12

[0117]

[0118] Compound Ml-3 was also synthesized by the method of synthesis of compound Ml-1, except that bromobenzene was replaced by 1-bromodibenzofuran; compound P12 was also synthesized by the method of synthesis of compound P4, except that 1-bromodibenzofuran was replaced by 2-bromobiphenyl and intermediate Ml-1 was replaced by Ml-3. M / Z calcd 587; M / Z found 588 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0119] Synthesis Example 4: Synthesis of compound P22

[0120]

[0121] Compound Ml-2 was also synthesized by the method of synthesis of compound Ml-1, except that bromobenzene was replaced by 3-bromodibenzofuran; compound P6 was also synthesized by the method of synthesis of compound P4, except that 1-bromodibenzofuran was replaced by Al and intermediate Ml-1 was replaced by Ml-2. M / Z calcd 663; M / Z found 664 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0122] Synthesis Example 5: Synthesis of compound P24

[0123]

[0124] Compound Ml-3 was also synthesized by the method of synthesis of compound Ml-1, except that bromobenzene was replaced by 1-bromodibenzofuran; compound P24 was also synthesized by the method of synthesis of compound P4, except that 1-bromodibenzofuran was replaced by A2 and intermediate Ml-1 was replaced by Ml-3. M / Z calcd 663; M / Z found 664 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0125] Synthesis of compound P30

[0126]

[0127] Compound M1-2 was also synthesized by the method for synthesizing compound M1-1 except that bromobenzene was replaced by 3-bromodibenzofuran; compound P30 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by A3 and intermediate M1-1 was replaced by M1-2. M / Z calcd 739; M / Z found 740 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0128] Synthesis of compound P42

[0129]

[0130] Compound M1-2 was also synthesized by the method for synthesizing compound M1-1 except that bromobenzene was replaced by 3-bromodibenzofuran; compound P42 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by A4 and intermediate M1-1 was replaced by M1-2. M / Z calcd 663; M / Z found 664 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0131] Synthesis of compound P86

[0132]

[0133] Compound M1-4 was also synthesized by the method for synthesizing compound M1-1 except that bromobenzene was replaced by 3-bromodibenzothiophene; compound P86 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by A2 and intermediate M1-1 was replaced by M1-4. M / Z calcd 679; M / Z found 680 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0134] Synthesis of compound P105

[0135]

[0136] Compound M1-5 was also synthesized by the method for synthesizing compound M1-1 except that bromobenzene was replaced by 4-bromodibenzothiophene; compound P6 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by A4 and intermediate M1-1 was replaced by M1-5. M / Z calcd 679; M / Z found 680 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0137] Synthesis Example 10: Synthesis of compound P2

[0138]

[0139] Compound Ml-2 was also synthesized by the method for synthesizing compound Ml-1 except that bromobenzene was replaced by 3-bromodibenzofuran; and compound P2 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by bromobenzene and intermediate Ml-1 was replaced by Ml-2. M / Z calcd 511; M / Z found 512 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0140] Synthesis Example 11: Synthesis of compound P7

[0141]

[0142] Compound Ml-4 was also synthesized by the method for synthesizing compound Ml-1 except that bromobenzene was replaced by 2-bromodibenzofuran; and compound P7 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by 4-bromobiphenyl and intermediate Ml-1 was replaced by Ml-4. M / Z calcd 587; M / Z found 588 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0143] Synthesis Example 12: Synthesis of compound P114

[0144]

[0145] Compound M2-1 was also synthesized by the method for synthesizing compound Ml-1 except that Ml was replaced by M2 and bromobenzene was replaced by Al; and compound P114 was also synthesized by the method for synthesizing compound P4 except that 1-bromodibenzofuran was replaced by A2 and intermediate Ml-1 was replaced by M2-1. M / Z calcd 829; M / Z found 830 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0146] Synthesis Example 13: Synthesis of compound P117

[0147]

[0148] Compound M3-1 was also synthesized by the synthetic method of compound M1-1, except that M1 was replaced by M3 and bromobenzene was replaced by 3-bromodibenzofuran; compound P117 was also synthesized by the synthetic method of compound P4, except that 1-bromodibenzofuran was replaced by bromobenzene and intermediate M1-1 was replaced by M3-1. M / Z calcd for C42H24N2O2: 567; M / Z found: 568 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0149] Synthesis Example 14: Synthesis of compound P116

[0150]

[0151] Compound M1-2 was also synthesized by the synthetic method of compound M1-1; compound P116 was also synthesized by the synthetic method of compound P4, except that 1-bromodibenzofuran was replaced by 3-bromodibenzothiophene and intermediate M1-1 was replaced by M1-2. M / Z calcd for C42H24N2O2: 567; M / Z found: 568 by ZAB-HS mass spectrometer (manufactured by Micromass, England).

[0152] Example 1

[0153] The organic electroluminescent device was prepared in the following manner in this example:

[0154] The ITO transparent conductive layer-coated glass plate was subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, subjected to ultrasonic oil removal in an acetone: ethanol mixed solvent, baked in a clean environment until water was completely removed, washed with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0155] The glass substrate with the anode was placed in a vacuum chamber, vacuumed to less than 1 x 10 -5 Pa, and a mixture of HT-4: HI-3 (97 / 3, w / w) was vacuum-deposited as a hole injection layer on the anode layer film at a deposition rate of 0.1 nm / s and a total film thickness of 10 nm;

[0156] HT-4 was vacuum-deposited as a hole transport layer of the device on the hole injection layer at a deposition rate of 0.1 nm / s and a total film thickness of 60 nm;

[0157] P2 was vacuum-deposited as an electron blocking layer of the device on the hole transport layer at a deposition rate of 0.1 nm / s and a total film thickness of 35 nm;

[0158] The light-emitting layer of the device was vacuum evaporated on the hole transport layer, and the light-emitting layer included a host material and a dye material, and a 40 nm ternary mixture of compounds PH-61:PH-3:GPD-12 (100:100:20, w / w / w) was evaporated as the light-emitting layer by a multi-source co-evaporation method; the evaporation rate was 0.1 nm / s;

[0159] The electron transport layer material ET-69:ET-57 (50 / 50, w / w) mixture of the device was vacuum evaporated on the light-emitting layer, and the evaporation rate was 0.1 nm / s, and the total film thickness was 25 nm;

[0160] LiF with a thickness of 0.5 nm was vacuum evaporated on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm was used as the cathode of the device.

[0161] The processes for preparing the organic electroluminescent devices of Examples 2-14 and Comparative Examples 1-3 were the same as those of Example 1, except that the electron blocking layer material compound P2 was replaced by the compounds shown in Table 1, respectively.

[0162] The structures of the electron blocking layer materials of Comparative Examples 1-3 are shown below:

[0163]

[0164] The synthesis of Comparative Compounds R-1, R-2, and R-3 was performed according to the methods described in patent documents CN1479561A, CN107108499A, and CN102282695A, respectively, and the descriptions thereof are omitted here.

[0165] Performance test:

[0166] The current efficiency of the organic electroluminescent device prepared by the above process was measured as follows. Specifically, the voltage was increased at a rate of 0.1 V / s, and the current efficiency was measured when the luminance of the organic electroluminescent device reached 10000 cd / m 2 The test results are shown in Table 1.

[0167] Table 1:

[0168]

[0169]

[0170] As can be seen from the data in Table 1, when the compound of the present application is used as the electron blocking layer material of the organic electroluminescent device, the luminance of the device reaches 10000 cd / m 2At this time, the voltage is as low as 4.1, and the current efficiency is as high as 58.2 d / A or above, which can effectively reduce the voltage of the device and improve the current efficiency, and is a good electron blocking layer material.

[0171] Compared with the prior art, the electron blocking material with the space structure and the film accumulation morphology being better can be obtained by using the triolefin complex of the diphenyl heterocyclic derivative substituted with the amino group at the 2-position, the luminous efficiency of the organic light-emitting device can be further improved by using the electron material, and the effect of improving the voltage and the luminous efficiency is obvious compared with the prior art compound.

[0172] The detailed method of the present application is illustrated by the above embodiments, but the present application is not limited to the above detailed method, that is, it does not mean that the present application must rely on the above detailed method to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. An organic compound having a structure represented by Formula I: In Formula I: L, L 1 and L 2 each independently is selected from a single bond or phenylene; Ar 1 one selected from the group consisting of phenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, furanyl, thienyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, isobenzothienyl; X is O or S; X 1 ~X 11 are independently from each other selected from CR 1 , said R 1 is selected from hydrogen, C1-C20 chain alkyl; X 12 ~ X 19 are independently from each other selected from C or CR 2 , said R 2 is selected from hydrogen, C1-C20 chain alkyl.

2. The organic compound according to claim 1, wherein L is a single bond in Formula I. and / or, said L 1 is a single bond; and / or, the L 2 is a single bond.

3. The organic compound according to claim 1, wherein X 1 ~ X 11 is independently selected from CR 1 , said R 1 is hydrogen.

4. The organic compound according to claim 1, X 12 ~ X 19 independently selected from C or CR 2 , said R 2 is hydrogen.

5. The organic compound according to claim 1, in the formula I, the R 1 and R 2 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-hexyl, n-octyl, i-butyl, t-butyl.

6. The organic compound of claim 1, said Ar 1 is selected from the following structural groups, wherein the dotted line represents a bond of attachment:

7. The organic compound according to claim 1, in the formula I, the L 2 attached at the position of X 12 ; or, the L 2 attached at the position of X 13 . Alternatively, the L 2 connected at the position of X 14 ; Alternatively, the L 2 N is attached at the position of X 15 .

8. The organic compound according to claim 1, having a structure represented by the following formula:

9. Use of the organic compound according to any one of claims 1 to 8 as a functional material in an organic electronic device, including an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an information tag, an electronic artificial skin sheet, a sheet-type scanner, or an electronic paper. The organic compound is used as an electron blocking layer material in an organic electroluminescent device.

10. An organic electroluminescent device comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first and second electrodes, the light-emitting functional layers comprising an electron blocking layer and at least one of a hole injecting layer, a hole transporting layer, a light-emitting layer, and an electron transporting layer, the electron blocking layer containing the organic compound according to any one of claims 1 to 8.

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