Triazine compound containing carbazolyl, intermediate and organic electroluminescent device

Abstract

The invention provides a triazine compound containing carbazolyl, an intermediate and an organic electroluminescent device. The triazine compound containing carbazolyl has a structure as shown in a formula I in the specification. The structure of the triazine compound containing carbazolyl is designed, so that the triazine compound is suitable for being used as a main body material of a luminescent layer of the organic electroluminescent device, and the organic electroluminescent device has relatively high current efficiency, relatively long service life and relatively low driving voltage.

Description

Technical Field

[0001] The invention belongs to the technical field of electroluminescent materials, and in particular relates to a triazine compound containing a carbazole group, an intermediate and an organic electroluminescent device. Background Art

[0002] Electroluminescence, also known as electric field luminescence, or EL for short, is a luminescence phenomenon in which a solid directly converts electrical energy into light energy under the action of an electric field generated by a voltage applied to two electrodes. Among them, the electroluminescence of organic materials belongs to injection-type composite luminescence. Organic electroluminescent materials can be divided into hole injection layer (HIL), hole transport layer (HTL), light-emitting layer (EML), electron transport layer (ETL), electron injection layer (EIL) and other materials according to their functions and device structures in organic electroluminescent (OLED) devices.

[0003] Currently, organic electroluminescence (OLED) has become the mainstream display technology, and accordingly, various new OLED materials have also been developed. However, its various performances need to be improved, especially in terms of efficiency, life, voltage, etc. In order to meet people's higher requirements for OLED devices, the field urgently needs to develop more types of blue light host materials with higher performance. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a triazine compound containing carbazole groups, an intermediate and an organic electroluminescent device. In the present invention, the structure of the triazine compound containing carbazole groups is designed so that it is suitable for use as a host material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency, longer life and lower driving voltage.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a triazine compound containing a carbazole group, wherein the triazine compound has a structure shown in the following formula I:

[0007]

[0008] Wherein, Ar1 is selected from any one of C6-C40 aryl or C6-C30 heteroaryl;

[0009] Ar2 is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group;

[0010] The hydrogen atoms in the compound of formula I may be independently substituted by at least one of a deuterium atom (D), -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0011] In the present invention, the structure of the triazine compound is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency, longer life and lower driving voltage.

[0012] It should be noted that, in the present invention, "D" represents a deuterium atom, and unless otherwise indicated in the present invention, H and hydrogen therein all represent "protium", and the same shall apply hereinafter.

[0013] In the present invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0014] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0015] C1-C12 can be C1, C2, C4, C6, C8, C10 or C12, etc.

[0016] C6-C20 can be C6, C8, C10, C12, C16 or C20, etc.

[0017] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0018] As a preferred technical solution of the present invention, the C6-C40 aromatic group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthanofluorenyl, pyrene, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthanofluorenyl or benzonaphthofluorenyl.

[0019] Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, naphthylphenylene, anthracene, phenanthrenyl, fluorenylene, benzofluorenylene, dibenzofluorenylene, naphthofluorenylene, pyrenylene, perylene, spirofluorenylene, triphenylene, fluoranthenylene, hydrogenated benzanthrylene, indenofluorenylene, benzoindenofluorenylene, dibenzoindenofluorenylene, naphthofluorenylene or benzonaphthofluorenylene.

[0020] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthiobenzofuranyl, naphthiobenzothiophenyl, dinaphthofuranyl and dinaphthothiophenyl.

[0021] Preferably, the C6-C30 heteroarylene group is selected from any one of dibenzofuranylene, dibenzothiophenylene, naphthobenzofuranylene, naphthobenzothiophenylene, dinaphthofuranylene, dinaphthothiophenylene or carbazolylene.

[0022] As a preferred technical solution of the present invention, the C6-C20 aromatic group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene and fluoranthene.

[0023] As a preferred technical solution of the present invention, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or decyl.

[0024] As a preferred technical solution of the present invention, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy.

[0025] As a preferred technical solution of the present invention, Ar1 is selected from at least one of phenyl, carbazolyl, biphenyl, fluorenyl, naphthyl, triphenylene, fluoranthene, indenofluorenyl, dibenzofuranyl, dibenzothienyl, naphthiobenzofuranyl or naphthiobenzothienyl, preferably at least one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl.

[0026] As a preferred technical solution of the present invention, Ar2 is selected from any one of a single bond, a phenylene group, a carbazolyl group, a biphenylene group, a fluorenyl group, a naphthyl group, a dibenzofuranyl group, and a dibenzothiophenyl group, and is preferably any one of a single bond, a phenylene group, and a biphenylene group.

[0027] As a preferred technical solution of the present invention, the hydrogen atoms in the compound of formula I can be independently replaced by at least one of a deuterium atom, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy.

[0028] Preferably, the hydrogen atoms in the compound of formula I may be independently substituted by at least one of a deuterium atom, -F, -CN, a methyl group, a tert-butyl group, a methoxy group, a phenyl group or a naphthyl group.

[0029] As a preferred technical solution of the present invention, the triazine compound containing a carbazole group has a structure shown in the following formula II-1 and formula II-2:

[0030]

[0031] wherein Ar1 has the same definition as above;

[0032] The hydrogen atoms in the compound of formula II-1 and the compound of formula II-2 can each independently be substituted by at least one of a deuterium atom, a methyl group, a tert-butyl group, a methoxy group, and a phenyl group.

[0033] As a preferred technical solution of the present invention, the triazine compound containing a carbazole group is selected from any one of the following substituted or unsubstituted compounds:

[0034]

[0035]

[0036]

[0037] The substitution means that the hydrogen atoms in the triazine compound containing carbazole groups can be independently replaced by deuterium atoms. Preferably, the triazine compound containing carbazole groups is selected from any one of the following compounds:

[0038]

[0039]

[0040] It should be noted that the present invention has no special restrictions on the preparation method of the above-mentioned triazine compounds containing carbazole groups, and the commonly used preparation methods in the art are applicable. The synthesis method of the triazine compounds containing carbazole groups of the present invention is illustrated by way of example:

[0041] Exemplarily: when Ar2 is not selected from a single bond, the synthesis method comprises the following steps:

[0042]

[0043] Wherein, X1, X2, and X3 are each independently selected from any one of -F, -Cl, -Br, and -I, and those skilled in the art can reasonably select the specific types of X1, X2, and X3 according to common knowledge to generate the target compound;

[0044] Ar1 and Ar2 have the same meanings as above;

[0045] The hydrogen atoms in the above compound M0, compound M1, compound MB, compound MA and compound of formula I can each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0046] In a second aspect, the present invention further provides an intermediate, wherein the intermediate comprises the following compound:

[0047]

[0048] Wherein, X1 and X2 are each independently selected from any one of -F, -Cl, -Br, and -I;

[0049] Ar1 and Ar2 have the same meanings as above;

[0050] The hydrogen atoms in the above MB intermediate, MA intermediate and compound of formula I can each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group;

[0051] The intermediates do not include the following compounds:

[0052]

[0053] The intermediate is used to prepare the triazine compound containing carbazole group as described in the first aspect.

[0054] Preferably, the intermediate includes the following compounds:

[0055]

[0056]

[0057] In a third aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0058] The organic thin film layer includes the triazine compound containing a carbazole group as described in the first aspect.

[0059] As a preferred technical solution of the present invention, the organic thin film layer includes a light-emitting layer, and the main material of the light-emitting layer includes the triazine compound containing a carbazole group as described in the first aspect.

[0060] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0061] As a preferred technical solution of the present invention, the organic electroluminescent device is a blue light organic electroluminescent device.

[0062] The luminescent layer in the present invention includes a luminescent layer main material and a doping material, wherein the doping material is also called a dye or a phosphorescent luminescent material. The luminescent layer main material can be a single compound or a mixture of two or more compounds.

[0063] The light-emitting layer includes a phosphorescent light-emitting layer, and the phosphorescent light-emitting layer includes a green phosphorescent light-emitting layer, a red phosphorescent light-emitting layer, and a yellow phosphorescent light-emitting layer.

[0064] The volume percentage of the main material in the phosphorescent layer is 60% to 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99.9%, etc.), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0065] In the present invention, the doping material of the light-emitting layer may be a phosphorescent material, which is also called a triplet light-emitting material, and refers to the light emitted from a triplet excited state. The specific selection of the phosphorescent material in the present invention is not particularly limited, and the doping materials of the light-emitting layer commonly used in the art are applicable, including but not limited to: a compound having a structure shown in Formula PD:

[0066]

[0067] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0068] Y1-Y4 are each independently selected from carbon or nitrogen;

[0069] Y1 and Y2 can be connected by a single bond or a double bond, and Y3 and Y4 can be connected by a single bond or a double bond;

[0070] Cy1 and Cy2 are each independently selected from phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothienyl, benzimidazolyl, benzoxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazine, dibenzofuranyl, dibenzothienyl, N-heterocarbazolyl, N-heterodibenzofuranyl, wherein Cy1 and Cy2 may be optionally linked to each other via a single bond or an organic linking group;

[0071] Any two ligands of M, or more than two ligands, may be connected by a single bond or a double bond, or may be bridged by O or S, or may be connected by any chemical group or chemical structure to form a structural form that conforms to chemical principles;

[0072] R 91 and R 92each independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphoric acid, phosphate, -SF5, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C6 C2-C60 (for example, C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) C2-C10 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) heterocycloalkyl, substituted or unsubstituted C6-C60 (for example, C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryl, substituted or unsubstituted C6-C60 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) For example, it can be any one of C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryloxy, substituted or unsubstituted C6-C60 (for example, it can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) arylthio, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

[0073] a1 and a2 are each independently an integer selected from 1-5, for example, 1, 2, 3, 4 or 5;

[0074] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0075] a is selected from 1, 2 or 3;

[0076] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0077] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0078]

[0079]

[0080]

[0081]

[0082] In the present invention, the organic thin film layer includes a hole layer, and the hole layer includes a hole injection layer, a hole transport layer and an electron blocking layer.

[0083] The hole injection layer material includes a P-type dopant. The P-type dopant refers to a dopant that coexists with the hole injection layer material in the OLED device and can oxidize the hole injection layer material, thereby acting as an electron acceptor and promoting the movement of holes in the hole injection layer to the anode. In the present invention, the difference between the absolute value of the LUMO of the P-type dopant and the absolute value of the HOMO of the hole layer material is greater than -0.2V, preferably greater than -0.1eV, more preferably greater than 0eV, more preferably greater than 0.1eV, and more preferably greater than 0.2eV.

[0084] The P-type dopant is present in the hole injection layer in a volume percentage of 1% to 10% (e.g., 1%, 2%, 4%, 6%, 8% or 10%). In the present invention, there is no particular limitation on the type of the P-type dopant, and illustratively, the compounds D-1 to D-13 disclosed in CN113728453A or the compounds HI-1 to HI-9 described below can be selected:

[0085]

[0086] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) has a structure shown in the following formula HT-GH4:

[0087]

[0088] Among them, L 41 is selected from a single bond, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, or a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0089] Ar 41 ,Ar 42 Each is independently selected from C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, C6-C20 (for example, C6, C8, C10, C12, C16 or C20, etc.) heteroaryl;

[0090] X is selected from CR 41 R 42 or NR 43 , where R 41 , R 42 , R 43 Each independently selected from substituted or unsubstituted phenyl (the substituted substituent is selected from C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy, dibenzofuranyl), naphthyl, triphenylene, fluoranthene, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted dibenzofuranyl (the substituted substituent is phenyl), substituted or unsubstituted dibenzothiophene (the substituted substituent is phenyl), dibenzofuran-substituted thienyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, any one of R 41 , R 42 They can be linked to form rings via single bonds.

[0091] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0092]

[0093]

[0094] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) also includes a compound having a structure shown in the following formula IA or a compound having a structure shown in the following formula IB:

[0095]

[0096] Wherein, L is selected from any one of C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) arylene, dibenzofuranyl or dibenzothiophenylene;

[0097] m is selected from an integer between 0 and 4 (for example, 0, 1, 2, 3 or 4), and n is selected from 0 or 1;

[0098] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0099] Ar1 and Ar2 are each independently selected from any one of a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl group, a dibenzofuranyl group or a dibenzothiophenyl group;

[0100] Ar1 and Ar, Ar2 and Ar, and Ar1 and Ar2 can each independently be connected or bridged by a single bond, O, S, CR1R2, or NR.

[0101] R, R1, and R2 are each independently selected from any one of C1-C20 (for example, C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20, etc.) alkyl, C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, dibenzofuranyl, or dibenzothiophenyl;

[0102] H in the compound of formula IB and the compound of formula IA can each independently be replaced by at least one of -F, -CN, -D (deuterium atom), C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0103] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0104] Preferably, H in the compound of formula IB and the compound of formula IA can be replaced by at least one of -F, -CN, -D, C1-C3 alkyl (for example, methyl, ethyl or propyl), C1-C3 alkoxy (for example, methoxy, ethoxy or propoxy), phenyl, biphenyl, triphenylene, and fluoranthene.

[0105] Preferably, L, Ar1, Ar2 are each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrene, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0106] Preferably, the compound of formula IB is selected from the following structures:

[0107]

[0108] Wherein, L is phenylene;

[0109] Ar1, Ar2, and m have the same protection scope as described above.

[0110] Preferably, the compound of formula IB is selected from any one of the following compounds:

[0111]

[0112] In the OLED device provided by the present invention, the hole layer material may include conventional hole materials in the art in addition to the compound described in formula HT-GH4, the compound of formula IB, and the compound of formula IA, without special restrictions. Exemplary includes but is not limited to: triarylamine compounds or carbazole compounds. Triarylamine compounds or carbazole compounds containing more than 3 N atoms are preferred, because the HOMO of triarylamine compounds or carbazole compounds containing more than 3 N atoms is higher (smaller absolute value), and is more suitable for use as hole injection layer materials. Triarylamine compounds or carbazole compounds containing 2 or 1 N atoms can be used as hole transport layer materials. Some compounds or carbazole compounds containing 1 N atom, if they have a higher LUMO, can also be used as electron blocking layer materials.

[0113] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0114]

[0115] Among them, Ar 601 ~Ar 609 Each independently selected from any one of substituted or unsubstituted C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted naphthobenzofuranyl, substituted or unsubstituted naphthobenzothiophenyl, substituted or unsubstituted dinaphthofuranyl, substituted or unsubstituted dinaphthothiophenyl;

[0116] And Ar 601 ~Ar 609 Ar atoms adjacent to or connected to the same N atom 601 ~Ar 609 , can be connected by single key or through O, S, CR 701 R 702 NR 703 bridging;

[0117] R 701 , R 702 , R 703is selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aromatic groups, C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl groups, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl groups, and R 701 , R 702 Can connect via one-touch.

[0118] The hole blocking layer (HBL) can confine holes and / or excitons within the EL to improve the current efficiency and lifetime of the device. Compared with the EL material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or higher triplet energy.

[0119] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped, and doping may be used to enhance conductivity. In the present invention, there is no particular restriction on the ETL material, and any metal complex or organic compound may be used as long as it can transport electrons. The general electron transport layer material contains the following structural fragments: at least one of a pyridine structure, a pyrimidine structure, a triazine structure, a benzimidazole structure, a benzoxazole structure, a benzothiazole structure, an N-naphthalene structure, an N-coffee structure, an N-carbazole structure, an N-dibenzofuran structure, and an N-dibenzothiophene structure.

[0120] In the present invention, there is no special restriction on the electron transport layer material, which exemplarily includes but is not limited to:

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] In the present invention, the material of the cathode is a metal with a low work function (e.g., alkaline earth metal, alkali metal, main group metal or lanthanide element (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (alloy composed of alkali metal or alkaline earth metal and silver, such as an alloy composed of magnesium and silver) or a multilayer structure. If the cathode material is a multilayer structure, in addition to the metals mentioned above, other metals with relatively high work functions, such as Ag or Al, can also be used. In this case, a combination of the metals is usually used, such as Ca / Ag, Mg / Ag or Ba / Ag.

[0127] It is also possible to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor to form a multilayer structure; the material with a high dielectric constant can also be called an electron injection material, and fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ) can be selected.

[0128] Compared with the prior art, the present invention has the following beneficial effects:

[0129] In the present invention, the structure of the triazine compound containing carbazole is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency, longer life and lower driving voltage. DETAILED DESCRIPTION

[0130] 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.

[0131] Preparation Example 1 Synthesis of Intermediate P1-2

[0132] This preparation example provides an intermediate P1-2 and a synthesis method thereof, the synthesis method is as follows:

[0133]

[0134] In a nitrogen atmosphere, 60 mL of DMF was added to a three-necked flask, and then 0.01 mol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 0.01 mol of 2-chlorophenylboric acid, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to 40°C for reaction for 2 hours, then raised to 60°C for reaction for 1 hour, then raised to 80°C for reaction for 2 hours, cooled to room temperature, and separated by adding water and toluene. The organic layer was washed with water, dried over magnesium sulfate, and after removing the desiccant, concentrated to dryness, and separated by silica gel column chromatography, eluted with petroleum ether: dichloromethane = 10:1 (volume ratio), to obtain 1.7 g of intermediate P1-2.

[0135] The obtained intermediate P1-2 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 301.02.

[0136] Preparation Example 2-5

[0137] Preparation Examples 2-5 respectively provide an intermediate and a synthesis method thereof. The synthesis method of the intermediate refers to the preparation method of intermediate P1-2, and o-chlorophenylboronic acid and the corresponding triazine compound are reacted to prepare the corresponding intermediate, and the mass spectrum of the prepared intermediate is measured to record m / z. Details are shown in Table 1 below.

[0138] Table 1

[0139]

[0140] Preparation Example 6 Synthesis of Intermediate P1-1

[0141] This preparation example provides an intermediate P1-1 and a synthesis method thereof, the synthesis method is as follows:

[0142]

[0143] In a nitrogen atmosphere, 60 mL of toluene, 40 mL of ethanol, and 20 mL of water were added to a three-necked flask, and then 0.01 mol of intermediate P1-2, 0.01 mol of intermediate P1-2a, 2.12 g (0.02 mol) of sodium carbonate, and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to reflux for reaction for 4 hours, and the temperature was lowered to room temperature. Water was added to separate the organic layer, and the organic layer was washed with water, dried with magnesium sulfate, and after removing the desiccant, it was concentrated to dryness and separated by silica gel column chromatography. Petroleum ether: dichloromethane = 10:1 (volume ratio) was used as the eluent to obtain 5.1 g of intermediate P1-1.

[0144] The obtained intermediate P1-1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 599.16.

[0145] Preparation Example 7-11

[0146] Preparation Examples 7-11 respectively provide an intermediate and its synthesis method. The synthesis method of the intermediate refers to the preparation method of intermediate P1-1. Raw material 1 and raw material 2 are reacted to prepare the corresponding intermediate, and the mass spectrum of the prepared intermediate is measured and m / z is recorded. Details are shown in Table 2 below.

[0147] Table 2

[0148]

[0149]

[0150] Synthesis Example 1 Synthesis of Compound P1

[0151] This synthesis example provides compound P1 and its synthesis method, and the synthesis method is as follows:

[0152]

[0153] In a nitrogen atmosphere, 100 mL of dry xylene, 6 g of intermediate P1-1, 1.7 g of carbazole, Pd(dba)2 (bis(dibenzylideneacetonepalladium, 0.0575 g, 0.0001 mol), 10% tri-tert-butylphosphine toluene solution (the mass of tri-tert-butylphosphine solution is 0.4 g, and the amount of tri-tert-butylphosphine is 0.0002 mol) and sodium tert-butoxide (1.44 g, 0.015 mol) were added to a three-necked flask, heated to reflux, reacted for 8 hours, cooled to room temperature, divided by adding water, and then the organic layer was washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, and eluted with a solvent of petroleum ether: dichloromethane = 10:1 (volume ratio) to obtain compound P1 (4.7 g).

[0154] The mass spectrometry detection of compound P1: the mass-to-charge ratio (m / z) was measured to be 730.26.

[0155] Synthesis Example 2-7

[0156] Synthesis Examples 2-7 respectively provide a compound and a synthesis method thereof. The synthesis method refers to the preparation method of compound P1, and raw material 1 and raw material 2 are reacted to prepare the corresponding compound, and the mass spectrum of the prepared compound is measured to record m / z. Details are shown in Table 3 below.

[0157] Table 3

[0158]

[0159]

[0160] Synthesis Example 8 Synthesis of Compound P9

[0161] This synthesis example provides compound P9 and its synthesis method, and the synthesis method is as follows:

[0162]

[0163] In a nitrogen atmosphere, 0.01 mol of P9-1 intermediate and 300 mL of tetrahydrofuran were added to a three-necked flask, and then the temperature was lowered to -78°C, and a n-hexane solution containing 0.011 mol of butyl lithium was slowly added, and then -78°C to -60°C was maintained for 30 min, 0.012 mol of P9-2 intermediate, 0.0001 mol of Pd(dba)2, and 0.0001 mol of anhydrous nickel chloride were added, and the temperature was slowly raised to room temperature for reaction for 2 hours, and then the temperature was raised to reflux for reaction for 2 hours, the temperature was lowered, water and toluene were added for separation, the organic layer was washed with water until neutral, dried over anhydrous magnesium sulfate, the desiccant was filtered out, and the mixture was concentrated to dryness. The mixture was separated by silica gel column chromatography and eluted with petroleum ether: dichloromethane = 10:1 (volume ratio) to obtain compound P9 (3.0 g).

[0164] The obtained compound P9 was detected by mass spectrometry, and the m / z was 654.22.

[0165] Other compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0166] The specific structures of some compositions used in the following application examples and comparative application examples are as follows:

[0167]

[0168]

[0169] Wherein, the synthesis method of compound H2 is as follows:

[0170]

[0171] The specific synthesis steps of compound H2 refer to the preparation method of intermediate P1-1 to prepare compound H2.

[0172] The obtained compound H2 was detected by mass spectrometry, and the m / z was 730.26.

[0173] Application Example 1

[0174] This application example provides a blue light organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer, and the structure of the blue light organic electroluminescent device is:

[0175] ITO / HT-1: HI-2 [5%] (80nm) / HT-1 (30nm) / host material: PBD-1 [5%] (35nm) / ETL-1 (25nm) / LiF (0.5nm) / Al (150nm).

[0176] The preparation method of the blue light organic electroluminescent device is as follows:

[0177] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa was vacuum evaporated onto the cleaned ITO substrate in sequence to prepare an OLED device.

[0178] Among them, PBD-1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the main material to the dye PBD-1 is 95:5; HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole material HT-1 and the P-type dopant HI-2 is 95:5. HT-1 is a hole transport material; HT-1:HI-2[5%] is used as a hole injection layer.

[0179] The main material of the light-emitting layer of the blue light organic electroluminescent device provided in this application example is compound P1.

[0180] Application Example 2-12

[0181] Application Examples 2-12 each provide a blue light organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced with other compounds (see Table 4 for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0182] Comparative Application Example 1-2

[0183] Comparative Application Examples 1-2 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced by other compounds (see Table 4 for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0184] Performance Testing

[0185] The brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the voltage and current efficiency were the brightness of 1000 cd / m 2 The corresponding value, LT95, refers to maintaining the initial current density of the device at 10mA / cm 2 The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, where the driving voltage, current efficiency and LT95 are relative values. The specific test results are shown in Table 4:

[0186] Table 4

[0187] Main material <![CDATA[Luminance / (cd / m 2 )]]> Driving voltage Current efficiency LT95 Application Example 1 P1 1000 0.96 1.08 1.09 Application Example 2 P2 1000 0.92 1.02 1.07 Application Example 3 P3 1000 1.01 1.09 1.18 Application Example 4 P4 1000 0.97 1.18 1.07 Application Example 5 P5 1000 0.86 1.02 1.01 Application Example 6 P6 1000 0.91 1.09 0.97 Application Example 7 P7 1000 0.92 1.37 1.16 Application Example 8 P8 1000 0.91 1.02 1.29 Application Example 9 P9 1000 0.76 / / Application Example 10 P10 1000 0.90 1.00 1.19 Application Example 11 P11 1000 0.98 1.09 1.02 Application Example 12 P12 1000 0.98 1.09 1.39 Comparative application example 1 H1 1000 1 1 1 Comparative Application Example 2 H2 1000 1.02 0.87 1.02

[0188] The “ / ” indicates that this data does not exist.

[0189] In the present invention, the structure of the triazine compound containing carbazole is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency, longer life and lower driving voltage.

[0190] From the comparison between Application Example 1 and Application Example 8, it can be seen that when the triazine compound containing a carbazole group conforms to the structure shown in Formula II-2, the driving voltage of the organic electroluminescent device prepared by using this triazine compound containing a carbazole group is reduced, the life span is improved, but the current efficiency is slightly poor; when the triazine compound containing a carbazole group conforms to the structure shown in Formula II-1, the voltage of the organic electroluminescent device prepared by using this triazine compound containing a carbazole group is higher, the life span is lower, but the current efficiency is better.

[0191] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow 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 triazine compound containing a carbazole group, characterized in that: The triazine compound has a structure as shown in the following formula I: Wherein, Ar1 is selected from any one of C6-C40 aryl or C6-C30 heteroaryl; Ar2 is selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group; The hydrogen atoms in the compound of formula I may be independently substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

2. The triazine compound containing a carbazole group according to claim 1, characterized in that: The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthofluorenyl or benzonaphthofluorenyl; Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, naphthylenephenyl, anthrylene, phenanthrylene, fluorenylene, benzofluorenylene, dibenzofluorenylene, naphthofluorenylene, pyrenylene, perylene, spirofluorenylene, triphenylene, fluoranthenylene, hydrogenated benzanthrylene, indenofluorenylene, benzoindenofluorenylene, dibenzoindenofluorenylene, naphthofluorenylene or benzonaphthofluorenylene; Preferably, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl and dinaphthothiophenyl; Preferably, the C6-C30 heteroarylene group is selected from any one of dibenzofuranylene, dibenzothiophenylene, naphthobenzofuranylene, naphthobenzothiophenylene, dinaphthofuranylene, dinaphthothiophenylene or carbazolylene; As a preferred technical solution of the present invention, the C6-C20 aromatic group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene and fluoranthene. Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or decyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy.

3. The triazine compound containing a carbazole group according to claim 1 or 2, characterized in that: The Ar1 is selected from at least one of phenyl, carbazolyl, biphenyl, fluorenyl, naphthyl, triphenylene, fluoranthene, indenofluorenyl, dibenzofuranyl, dibenzothienyl, naphthiobenzofuranyl or naphthiobenzothienyl, preferably at least one of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl.

4. The triazine compound containing a carbazole group according to any one of claims 1 to 3, characterized in that: The Ar2 is selected from any one of a single bond, a phenylene group, a carbazolylene group, a biphenylene group, a fluorenyl group, a naphthyl group, a dibenzofuranyl group, and a dibenzothiophenylene group, and is preferably any one of a single bond, a phenylene group, and a biphenylene group.

5. The triazine compound containing a carbazole group according to any one of claims 1 to 4, characterized in that: The hydrogen atoms in the compound of formula I may each independently be substituted by at least one of a deuterium atom, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy; Preferably, the hydrogen atoms in the compound of formula I may be independently substituted by at least one of a deuterium atom, -F, -CN, a methyl group, a tert-butyl group, a methoxy group, a phenyl group or a naphthyl group.

6. The triazine compound containing a carbazole group according to any one of claims 1 to 5, characterized in that: The triazine compound containing a carbazole group has a structure shown in the following formula II-1 and formula II-2: wherein Ar1 has the same definition as in claim 1; The hydrogen atoms in the compound of formula II-1 and the compound of formula II-2 can each independently be substituted by at least one of a deuterium atom, a methyl group, a tert-butyl group, a methoxy group, and a phenyl group.

7. The triazine compound containing a carbazole group according to any one of claims 1 to 6, characterized in that: The triazine compound containing a carbazole group is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the triazine compound containing a carbazole group can be independently substituted by deuterium atoms.

8. An intermediate, characterized in that The intermediates include the following compounds: Wherein, X1 and X2 are each independently selected from any one of -F, -Cl, -Br, and -I; Ar1 and Ar2 have the same definitions as in claim 1; The hydrogen atoms in the above MB intermediate, MA intermediate and compound of formula I can each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group; The intermediates do not include the following compounds: The intermediate is used to prepare the triazine compound containing a carbazole group as claimed in any one of claims 1 to 7.

9. The intermediate according to claim 8, characterized in that The intermediates include the following compounds:

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode; The organic thin film layer comprises a triazine compound containing a carbazole group as claimed in any one of claims 1 to 7; Preferably, the organic thin film layer comprises a light-emitting layer, and the main material of the light-emitting layer comprises the triazine compound containing a carbazole group as claimed in any one of claims 1 to 7; Preferably, the light-emitting layer is a phosphorescent light-emitting layer; Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

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