A compound and its application

Abstract

The present invention relates to a compound and application thereof. The compound has a structure shown in Formula I. The compound provided by the present invention is a red phosphorescent host material containing diarylamine, which can effectively improve the hole transport performance of the host material. When applied to an OLED device, it can effectively improve the device efficiency and reduce the driving voltage. The compound is a good host material, especially a good red light host material.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to a compound and application thereof. Background Art

[0002] In recent years, organic light-emitting diodes (OLEDs) have developed rapidly and have occupied a place in the field of information display. This is mainly due to the fact that OLED devices can use the three primary colors of red, green and blue with high saturation to prepare full-color display devices, and do not require additional backlight sources to achieve colorful, light, thin and soft performance.

[0003] The thin layer structure containing a variety of organic functional materials plays an important role in OLED devices. Common organic functional materials include light-emitting layer materials, electron blocking layer materials, electron transport layer materials, hole blocking layer materials, hole transport layer materials, etc. After the power is turned on, electrons and holes are respectively injected and transported to the light-emitting layer, where they recombine to generate excitons and realize light emission. Therefore, the research on organic functional materials in OLED devices is a key research topic for those skilled in the art.

[0004] At present, researchers have developed a variety of organic functional materials for use in various specific device structures, which can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device attenuation.

[0005] Common fluorescent luminescent bodies mainly emit light by utilizing singlet excitons generated when holes and electrons recombine, and such luminescent bodies are still used in various OLED devices. In addition, phosphorescent luminescent bodies are also included, i.e., materials that can simultaneously utilize triplet excitons and singlet excitons to emit light, such as iridium complexes. What is most noteworthy is that thermally excited delayed fluorescence (TADF) technology can effectively utilize triplet excitons to achieve higher luminescence efficiency without using metal complexes by promoting the transformation of triplet excitons to singlet excitons. Thermally excited sensitized fluorescence (TASF) technology uses TADF materials to sensitize luminescent bodies through energy transfer to achieve higher luminescence efficiency. TADF materials have broad application prospects in the field of OLEDs.

[0006] Although a variety of organic functional layer materials have been developed, people nowadays have increasingly higher requirements for the performance of OLED devices, and existing organic functional materials are no longer suitable for new OLED devices with higher performance.

[0007] Therefore, it is urgent to develop more types of organic functional materials in this field so that when they are applied to OLED devices, they can improve the luminous efficiency, reduce the driving voltage, and extend the service life. Summary of the invention

[0008] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a compound which, when applied to an OLED device, can improve the luminous efficiency, reduce the driving voltage, and extend the service life.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] The present invention provides a compound having a structure shown in Formula I;

[0011]

[0012] In Formula I, A is selected from the structure shown in Formula (a) or Formula (b);

[0013] When A is a structure represented by formula (a), Ar1 is a substituted or unsubstituted C3-C30 heteroaryl group, wherein the heteroatom is N, O, S, P, or Si; when A is a structure represented by formula (b), Ar1 is a substituted or unsubstituted C3-C30 heteroaryl group, wherein the heteroatom is N, O, P, or Si, and when the heteroatom is N, Ar1 contains at least two N atoms;

[0014] The X1, X2, X3, and X4 are independently selected from N or CR, and R is selected from hydrogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, halogen, cyano, nitro, hydroxyl, silane, amino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C3-C30 heteroaryl, and when there are multiple Rs, adjacent Rs can be bonded to each other to form C6-C30 aryl or C4-C30 heteroaryl;

[0015] The L1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0016] In formula (a), Ar2, Ar3, and Ar4 are independently selected from a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;

[0017] L2 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0018] L3 is selected from a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group;

[0019] In formula (b), Ar5, Ar6, Ar7, and Ar8 are independently selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group;

[0020] L4 is selected from a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group;

[0021] When the above-mentioned groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, C3-C30 heteroaryl.

[0022] Preferably, in Formula I, Ar1 is a substituted or unsubstituted C3-C30 heteroaryl group, wherein the heteroatom is N.

[0023] More preferably, in Formula I, when A is a structure represented by Formula (a), Ar1 is selected from the following substituted or unsubstituted groups:

[0024]

[0025] When A is a structure represented by formula (b), Ar1 is selected from the following substituted or unsubstituted groups:

[0026]

[0027] When the above-mentioned groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, and C3-C30 heteroaryl.

[0028] Preferably, in Formula I, L1 is selected from a single bond, phenylene, biphenylene, terphenylene, naphthylene, furanylene, thienylene, pyridylene, pyrimidylene or triazinylene;

[0029] In formula (a), L2 is selected from a single bond, phenylene, biphenylene, terphenylene, naphthylene, furanylene or thienylene, and L3 is selected from phenylene, biphenylene, terphenylene, naphthylene, furanylene or thienylene;

[0030] In formula (b), L4 is selected from phenylene, biphenylene, terphenylene, naphthylene, furanylene or thienylene.

[0031] Preferably, in Formula I, X1, X2, X3, and X4 are independently selected from CR, and R is selected from one of hydrogen, C1-C5 chain alkyl, C3-C5 cycloalkyl, C1-C5 alkoxy, halogen, cyano, C6-C30 aryl, C6-C30 arylamino, C3-C30 heteroarylamino, and C3-C30 heteroaryl; preferably, R is hydrogen;

[0032] Alternatively, in Formula I, one of X1, X2, X3, and X4 is N, three of X1, X2, X3, and X4 are independently selected from CR, and R is selected from hydrogen, C1-C5 chain alkyl, C3-C5 cycloalkyl, C1-C5 alkoxy, halogen, cyano, C6-C30 aryl, C6-C30 arylamino, C3-C30 heteroarylamino, and C3-C30 heteroaryl; preferably, R is hydrogen.

[0033] More preferably, in formula (a), Ar2, Ar3, and Ar4 are independently selected from phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrene, chrysene, peryl, fluoranthene, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenylene, tetraphenylene, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothiophene One of phenyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzooxazolyl, naphthooxazolyl, anthrazolyl, phenanthrooxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, and quinoxalinyl;

[0034] In formula (b), Ar5, Ar6, Ar7, and Ar8 are independently selected from phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthene, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenyl, quaternary, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothiophene The invention can be selected from the group consisting of 1,2-dimethylaminobenzoic acid, ...

[0035] Most preferably, in formula (a), Ar2, Ar3, and Ar4 are independently selected from one of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, fluorenyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, and carbazolyl;

[0036] In formula (b), Ar5, Ar6, Ar7, and Ar8 are independently selected from one of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, fluorenyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, and carbazolyl.

[0037] The above-mentioned "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the present invention, they all have the same meaning, and the selection range of the substituents is as shown above and will not be repeated one by one.

[0038] In the present invention, the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms in the group generally does not include the number of carbon atoms in the substituent.

[0039] In the present invention, the expression of chemical elements includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1 H (protium or H), 2H (deuterium or D), etc.; Carbon (C) includes 12 C. 13 C, etc.

[0040] The C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, and more preferably a C1-C5 chain alkyl group, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, and tert-butyl groups.

[0041] The above-mentioned C3-C30 cycloalkyl group is preferably a C3-C20 cycloalkyl group, more preferably a C3-C10 cycloalkyl group, and further preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.

[0042] In the present invention, C6-C30 aromatic groups include C6-C30 monocyclic aromatic groups or C10-C30 condensed-ring aromatic groups, wherein monocyclic aromatic groups refer to aromatic rings existing in the form of a single ring without condensation, including but not limited to phenyl, biphenyl or terphenyl; condensed-ring aromatic groups refer to structures in which at least two aromatic rings are condensed, including but not limited to naphthyl, anthracenyl, phenanthrenyl, fluorenyl, etc.

[0043] In the present invention, C6-C30 arylamino represents a group formed by replacing hydrogen on an amino group with one or two C6-C30 aryl groups, wherein the connection point of the C6-C30 arylamino can be connected to the aryl group in the arylamino group, or can be connected to N in the arylamino group, and the exemplary carbon number and specific group of the C6-C30 aryl group in the C6-C30 arylamino group are the same as described above.

[0044] In the present invention, C3-C30 heteroaryl includes C3-C30 monocyclic heteroaryl or C6-C30 condensed heteroaryl, wherein the monocyclic heteroaryl refers to a heteroaromatic ring existing in the form of a single ring without condensation, including but not limited to furan, thiophene, pyridine, pyrimidine, triazine or a group formed by connecting at least two of them; condensed heteroaryl refers to a condensed aromatic group containing heteroatoms, including but not limited to a dibenzofuran group, a dibenzothiophene group or a carbazole group.

[0045] In the present invention, C3-C30 heteroarylamino represents a group formed by replacing the hydrogen on the amino group with one or two C3-C30 heteroaryl groups, wherein the connection point of the C3-C30 heteroarylamino can be connected to the heteroaryl in the heteroarylamino, and can also be connected to the N in the heteroarylamino, and the exemplary carbon number and specific group of the C3-C30 heteroaryl in the C3-C30 heteroarylamino are the same as described above.

[0046] The substituted or unsubstituted C6-C30 aryl group of the present invention is preferably a C6-C30 aryl group, and the aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthyl group is selected from the group consisting of 1-naphthyl, 2-naphthyl and 9-naphthyl.

[0047] The substituted or unsubstituted C3-C30 heteroaryl group of the present invention is preferably a C3-C30 heteroaryl group, and the heteroaryl group is preferably a furyl 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 carbazole group and derivatives thereof, wherein the carbazole group derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolecarbazole.

[0048] Preferably, the compound has any one of the structures described in P1 to P104 below:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] The second object of the present invention is to provide an application of the compound described in the first object, wherein the application is as a functional material in an organic electronic device, wherein the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or an electronic paper;

[0061] Preferably, the compound is used in an organic electroluminescent device, preferably a red organic electroluminescent device.

[0062] More preferably, the compound is used as a host material of the organic electroluminescent device, preferably as a red light host material.

[0063] The third object of the present invention is to provide an organic electroluminescent device, comprising a first electrode, a second electrode and a plurality of light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer contains at least one compound described in one of the objects.

[0064] Preferably, the light-emitting functional layer comprises a light-emitting layer, and the light-emitting layer contains at least one compound described in one of the purposes.

[0065] Preferably, the light-emitting layer comprises a main material and a doping material, and the main material comprises at least one compound described in one of the purposes.

[0066] In a specific embodiment, the light-emitting functional layer may further include a hole transport region and an electron transport region.

[0067] In one embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0068] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used 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 is used as a cathode, a metal or 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.

[0069] The light-emitting functional layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the light-emitting functional layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0070] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0071] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives, wherein the aromatic amine derivatives include compounds shown in HT-1 to HT-50 below; or any combination thereof.

[0072]

[0073]

[0074]

[0075] 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 use one or more compounds of HT-1 to HT-50 mentioned above, or one or more compounds of HI-1 to HI-3 described below; or one or more compounds of HT-1 to HT-50 can be doped with one or more compounds of HI-1 to HI-3 described below.

[0076]

[0077] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer can be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors can be arranged in a plane according to a pixel pattern, or they can be stacked together to form a color light-emitting layer. When 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 simultaneously emit different colors such as red, green, and blue.

[0078] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0079] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0080]

[0081] The electron transport region may be a single-layer 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 region may also be a multi-layer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0082] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0083]

[0084]

[0085]

[0086]

[0087] The device may further include an electron injection layer located between the electron transport layer and the cathode. Materials for the electron injection layer include, but are not limited to, one or more combinations of the following.

[0088] Liq, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Yb.

[0089] The cathode is a metal such as a magnesium-silver mixture, LiF / Al, ITO, a metal mixture, or an oxide.

[0090] The specific reasons for the excellent performance of the compounds of the present invention are not yet clear, but it is speculated that the reasons may be as follows:

[0091] The compound provided by the present invention is a carbazole derivative containing a diarylamine, and the substitution site is fixed at the 3-position of carbazole. On the one hand, the diarylamine group has good hole transport performance, which can effectively reduce the voltage of the device and improve the efficiency; on the other hand, because the 3-position of carbazole has high electrical richness, it is easy to have an electrophilic reaction. In the device, due to the complex electrochemical environment, if there is exposed active hydrogen at the 3-position of carbazole, it is easy to react, thereby affecting the life of the device. Therefore, the present invention adopts substitution at the 3-position of carbazole, so that compared with compounds substituted at other positions of carbazole, the compound of the present invention has a longer service life. The compound provided by the present invention can be used as a good luminescent host material, especially a good red light host material. DETAILED DESCRIPTION

[0092] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0093] The representative synthesis route of the compound of general formula I of the present invention is as follows:

[0094]

[0095] The above symbols have the same meanings as in Formula I.

[0096] Synthesis example 1:

[0097] Synthesis of compound P2

[0098]

[0099] 3-Bromocarbazole (100 mmol), 2-chloro-4-phenylquinazoline (110 mmol), cesium carbonate (150 mmol) and 200 mL of N,N-dimethylformamide were added to a reaction bottle, heated to 150°C for 4 h, and the reaction was complete under the monitoring of TLC. After cooling, the reaction was poured into water and filtered, and recrystallized from xylene to obtain P2-A.

[0100] N1-([1,1'-biphenyl]-4-yl-N1-(4-bromophenyl)-N4,N4-diphenyl-1,4-diphenylamine (100mmol), bipyraclostrobin (120mmol), potassium acetate (150mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (1.2mmol), and 200ml of dioxane were added to a reaction bottle and refluxed for 4h under nitrogen protection. After the reaction was complete, water and dichloromethane were added for extraction. The organic phase was concentrated and purified by column chromatography to obtain P2-B.

[0101] P2-A (50 mmol), P2-B (55 mmol), potassium carbonate (80 mmol), tetrakis(triphenylphosphine)palladium (0.5 mmol), water (30 mL), and 300 mL of dioxane were added to a reaction bottle, heated to 120°C for 6 h, and the reaction was complete after TLC monitoring. Water and dichloromethane were added for extraction, and the organic phase was separated and concentrated, and purified by column chromatography to obtain P2. Mass spectrum (M / Z): 858.4.

[0102] Synthesis example 2:

[0103] Synthesis of compound P10

[0104] The difference from Synthesis Example 1 is that N1-([1,1'-biphenyl]-4-yl-N1-(4-bromophenyl)-N4,N4-diphenyl-1,4-diphenylamine is replaced by an equal amount of N 1 -(4-Bromophenyl)-N 1 -(Dibenzofuran-2-yl)-N 4 ,N 4 -diphenyl-1,4-diphenylamine to obtain compound P10. Mass spectrum (M / Z): 872.3.

[0105] Synthesis example 3:

[0106] Synthesis of compound P26

[0107]

[0108] P2-A (50 mmol), N4, N4, N6-triphenyldibenzofuran-4, 6-diphenylamine (50 mmol), sodium tert-butoxide (80 mmol), tris (dibenzylideneacetone) dipalladium (0.05 mmol), 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl (0.1 mmol, S-Phos), toluene (200 ml) were added to a reaction bottle, heated to 120°C for 7 hours, and the reaction was complete under TLC monitoring. After cooling, water and dichloromethane were added for extraction, and the organic phase was concentrated and purified by column chromatography to obtain P26. Mass spectrum (M / Z): 796.3.

[0109] Synthesis example 4:

[0110] Synthesis of compound P54

[0111]

[0112] 3-Bromocarbazole (100 mmol), 2-chloro-3-phenylquinoxaline (110 mmol), cesium carbonate (150 mmol) and 200 mL of N,N-dimethylformamide were added to a reaction bottle, heated to 150°C for 4 h, and the reaction was complete under the monitoring of TLC. After cooling, the reaction was poured into water and filtered, and recrystallized from xylene to obtain P54-A.

[0113] P54-A (50 mmol), S1 (50 mmol), sodium tert-butoxide (80 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (0.1 mmol, S-Phos), toluene (200 ml) were added to a reaction bottle, heated to 120°C for 5 hours, and the reaction was complete after TLC monitoring. After cooling, water and dichloromethane were added for extraction, and the organic phase was concentrated and purified by column chromatography to obtain P54. Mass spectrum (M / Z): 858.4.

[0114] Synthesis example 5:

[0115] Synthesis of compound P59

[0116] The difference from Synthesis Example 4 is that S1 is replaced with an equal amount of N2,N2,N6-triphenyl-naphthalene-2,6-diphenylamine to obtain compound P59. Mass spectrum (M / Z): 756.3.

[0117] Synthesis example 6:

[0118] Synthesis of compound P69

[0119]

[0120] 3-Bromocarbazole (100 mmol), 2-(2-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (110 mmol), cesium carbonate (150 mmol) and 200 mL of N,N-dimethylformamide were added to a reaction bottle, heated to 150°C for 4 h, and the reaction was complete under the monitoring of TLC. After cooling, the reaction was poured into water and filtered, and recrystallized from xylene to obtain P69-A.

[0121] P69-A (50 mmol), N,N,N-triphenyl-1,4-phenylenediamine (50 mmol), sodium tert-butoxide (80 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (0.1 mmol, S-Phos), toluene (200 ml) were added to a reaction bottle, heated to 120°C for 5 hours, and the reaction was complete under TLC monitoring. After cooling, water and dichloromethane were added for extraction, and the organic phase was concentrated and purified by column chromatography to obtain P69. Mass spectrum (M / Z): 809.3.

[0122] Synthesis example 7:

[0123] Synthesis of compound P78

[0124] The difference from Synthesis Example 1 is that N1-([1,1'-biphenyl]-4-yl-N1-(4-bromophenyl)-N4,N4-diphenyl-1,4-diphenylamine is replaced with an equal amount of 5-bromo-N,N,N',N'-tetraphenyl-benzene-1,3-diamine to obtain compound P78. Mass spectrum (M / Z): 782.3.

[0125] Synthesis example 8:

[0126] Synthesis of compound P93

[0127]

[0128] 8-Bromo-5H-pyrido[3,2-B]indole (100 mmol), 2-chloro-4-phenylquinazoline (110 mmol), cesium carbonate (150 mmol) and 200 mL of N,N-dimethylformamide were added to a reaction bottle, heated to 150°C for 4 h, and the reaction was completed under the monitoring of TLC. After cooling, the reaction mixture was poured into water and filtered, and recrystallized from xylene to obtain P93-A.

[0129] S2 (100 mmol), bipyraclostrobin (120 mmol), potassium acetate (150 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (1.2 mmol), and 200 ml of dioxane were added to a reaction bottle and refluxed for 4 hours under nitrogen protection. After the reaction was complete, water and dichloromethane were added for extraction. The organic phase was concentrated and purified by column chromatography to obtain P93-B.

[0130] P93-A (50 mmol), P93-B (55 mmol), potassium carbonate (80 mmol), tetrakis(triphenylphosphine)palladium (0.5 mmol), water (30 mL), and 300 mL of dioxane were added to a reaction bottle, heated to 120°C for 6 h, and the reaction was complete after TLC monitoring. Water and dichloromethane were added for extraction, and the organic phase was separated and concentrated, and purified by column chromatography to obtain P93. Mass spectrum (M / Z): 935.4.

[0131] Synthesis example 9:

[0132] Synthesis of compound P101

[0133] The difference from Synthesis Example 4 is that 3-bromocarbazole is replaced with an equal amount of 8-bromo-5H-pyrido[4,3-B]indole to obtain compound P101. Mass spectrum (M / Z): 859.4.

[0134] The present invention exemplifies the specific synthesis methods of the above compounds. For the compounds for which the specific synthesis methods are not given in the following embodiments, they are also prepared by similar methods, and only the raw materials need to be replaced, which will not be described here. Alternatively, those skilled in the art can also prepare them by other methods in the prior art.

[0135] Examples 1-10, Comparative Examples 1-2

[0136] The above embodiment and comparative example respectively provide an organic electroluminescent device, and the specific preparation method is as follows:

[0137] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0138] Place the glass substrate with ITO anode in a vacuum chamber and evacuate to <1×10 -5Pa, on the above-mentioned anode layer film, 10nm of HT-4:HI-3 (97 / 3, w / w) mixture was vacuum-evaporated in sequence as a hole injection layer; 60nm of compound HT-4 was used as a hole transport layer; on the hole transport layer, compound HT-47 was vacuum-evaporated as the electron blocking layer material of the device, the evaporation rate was 0.1nm / s, and the total film thickness of the evaporation was 60nm; 40nm of the main material: RPD-8 (100:3, w / w) binary mixture was used as the light-emitting layer; 5nm of ET-17 was vacuum-evaporated on the light-emitting layer as the hole blocking layer of the device; 25nm of the compound ET-69:ET-57 (50 / 50, w / w) mixture was used as the electron transport layer; 1nm of LiF was used as the electron injection layer; 150nm of metal aluminum was used as the cathode.

[0139] The host in the light-emitting layer is the compounds listed in Table 1. The total evaporation rate of all organic layers and LiF is controlled at 0.1 nm / sec, and the evaporation rate of the metal electrode is controlled at 1 nm / sec.

[0140]

[0141] For details of the above compound C1, please refer to patent application KR1020130024521A, and for details of compound C2, please refer to patent application WO2012043996A2.

[0142] Performance Test:

[0143] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in the examples and comparative examples were measured. Specifically, the voltage was increased at a rate of 0.1 V per second, and the driving voltage and current efficiency of the organic electroluminescent devices were measured when the brightness reached 3000 cd / m 2 The voltage at this time is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the current efficiency of comparative example 1 is recorded as 1, the voltage is recorded as 1, and the rest are ratios with comparative example 1; the life test is based on the initial brightness of 10000cd / m 2 Under this condition, the brightness is reduced to 9800cd / m 2 The required time is that the life of C1 in Comparative Example 1 is set to 1, and the rest are ratios to Comparative Example 1.

[0144] The device performance test results of the various embodiments and comparative examples prepared above are shown in Table 1.

[0145] Table 1:

[0146]

[0147]

[0148] It can be seen from Table 1 that the compound provided by the present invention, as a light-emitting host material of a device, can improve the efficiency of the device, reduce the driving voltage, and increase the service life of the device.

[0149] The difference between the compound C1 in the prior art and the compound of the present invention in molecular structure is that the substitution sites on the carbazole group are different. The diarylamine structure in the compound C1 is connected to the 2-position of the parent core carbazole group. This molecular structure may cause the compound to be unstable under complex electrochemical environments, while the diarylamine structure in the compound of the present invention is connected to the 3-position of the parent core carbazole group, thereby avoiding the problem of affecting the device life if the exposed active hydrogen at the 3-position is prone to electrophilic reaction. It can be seen from the data in Table 1 above that the device life of Examples 1 to 10 prepared using the compounds of the present invention as the luminescent host material is greater than the device life of Comparative Example 1 prepared using C1 as the luminescent host material. The difference in molecular structure between the compound C2 in the prior art and the compound of the present invention is that a single nitrogen group is used in the C2 molecule to connect the N atom on the carbazole group as an electron-deficient group. From the data in Table 1 above, it can be seen that the effect of the device of Comparative Example 2 prepared by using C2 as the light-emitting main material is that the voltage is relatively higher than the voltage of the device of Examples 1 to 10 prepared by using the compound of the present invention as the light-emitting main material. At the same time, because the molecular structure of C2 leads to an imbalance in the transmission of electrons and holes in the device, the efficiency of the device of Comparative Example 2 is also deteriorated, which is significantly lower than the efficiency of the devices of Examples 1 to 10.

[0150] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound having a structure shown in Formula I: In Formula I, A is selected from the structure shown in Formula (a); When A is a structure represented by formula (a), Ar1 is the following substituted or unsubstituted group: When the above Ar1 has a substituent group, the substituent group is selected from C6 to C30 aryl groups; One of X1, X2, X3, and X4 is N, three of X1, X2, X3, and X4 are independently selected from CR, and R is selected from hydrogen; The L1 is selected from a single bond; In formula (a), Ar2, Ar3, and Ar4 are independently selected from one of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, and carbazolyl; The L2 is selected from a single bond, a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a furanylene group or a thienylene group; The L3 is selected from phenylene, biphenylene, terphenylene, naphthylene, furanylene or thienylene.

2. A compound having the structure shown below:

3. Use of the compound according to any one of claims 1 to 2 as a functional material in an organic electronic device, wherein the organic electronic device includes 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.

4. Use of the compound according to any one of claims 1 to 2 as a main material of a red light emitting layer in an organic electroluminescent device.

5. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, The light-emitting functional layer comprises a light-emitting layer, and the light-emitting layer contains the compound according to any one of claims 1-2.

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