A triazine compound, intermediates and organic electroluminescent device

Abstract

This invention provides a triazine compound, an intermediate, and an organic electroluminescent device, relating to the field of organic electroluminescent materials technology. By designing the structure of the compound, this invention yields a triazine compound with excellent performance. Using this carbazole compound as the host material for the light-emitting layer, the resulting organic electroluminescent device exhibits high current efficiency, long lifetime, and low driving voltage.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a triazine compound, an intermediate, and an organic electroluminescent device. Background Technology

[0002] Compared to other flat panel displays, such as liquid crystal displays (LCDs), plasma display panels (PDPs), and field emission displays (FEDs), organic light-emitting devices (OLEDs) have a simpler structure, various processing advantages, higher brightness, excellent viewing angle characteristics, faster response speed, and lower driving voltage. Therefore, they have been fully developed for use as light sources for flat panel displays (e.g., wall-mounted TVs) or as backlight units for displays, lighting fixtures, advertising boards, etc.

[0003] The structure of an organic light-emitting diode (OLED) consists of an anode, a cathode, and an organic layer between them. To improve the efficiency and stability of OLEDs, the organic layer comprises multiple functional layers made of different materials. To meet the increasingly demanding requirements for OLED devices, there is an urgent need to develop a wider variety of materials to improve the performance of OLED devices in terms of current efficiency, lifetime, and other aspects. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a triazine compound, an intermediate, and an organic electroluminescent device, wherein the carbazole compound is used as the main material of the light-emitting layer, and the resulting organic electroluminescent device exhibits high current efficiency, long lifespan, and low driving voltage.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a triazine compound having the structure shown in Formula I:

[0007]

[0008] Formula I;

[0009] Ar1 is selected from any one of C6~C20 aryl and C3~C20 heteroaryl;

[0010] L2 is selected from any one of the C6~C20 arylene groups;

[0011] Ar2, Ar3, and Ar4 are each independently selected from any one of the C6 to C20 aryl groups;

[0012] Y is selected from C or Si;

[0013] In Formula I compounds, each hydrogen atom can be independently replaced by a deuterium atom, -F, cyano group, C1-C12 straight-chain or branched alkyl group, C3-C12 cycloalkyl group, C1-C12 straight-chain or branched alkoxy group, C3-C12 cycloalkoxy group, (Triphenylsilyl) At least one of (triphenylmethyl), C6-C20 aryl, and C3-C20 heteroaryl is substituted, with the dashed line indicating the linking site.

[0014] This invention designs the structure of compounds to obtain triazine compounds with excellent performance. Using triazine compounds as the main material of the light-emitting layer, the organic electroluminescent devices prepared have high current efficiency, long lifespan and low driving voltage.

[0015] In this invention, C1~C12 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.

[0016] C3~C12 can be C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.

[0017] C6~C20 can be C6, C8, C10, C12, C18 or C20.

[0018] C3~C20 can be C3, C4, C5, C7, C8, C9, C12, C18 or C20.

[0019] In this invention, "-D" represents a deuterium atom. Unless otherwise specified, H and hydrogen in this invention both represent "protium".

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0021] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, terphenyl, 9,9-dimethylfluorenyl, triphenylene, anthracene, phenanthrene, or fluoranthyl.

[0022] Preferably, the C3~C20 heteroaryl group is selected from any one of triazinyl, carbazole, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, and naphthobenzothiophenyl.

[0023] Preferably, the C6-C20 arylene group is selected from any one of phenylene, naphthylene, biphenylene, terphenylene, 9,9-dimethylfluorene, trimethyleneene, anthracene, phenanthrene, and fluoranthracene.

[0024] Preferably, the C1-C12 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-undecyl.

[0025] Preferably, the C3-C12 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0026] Preferably, the C1-C12 straight-chain or branched alkoxy groups are selected from any one of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, and n-hexoxy.

[0027] Preferably, the C3~C12 cycloalkoxy group is selected from any one of cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexyloxy.

[0028] Preferably, Ar1 is selected from any one of phenyl, naphthyl, biphenyl, terphenyl, carbazolyl, N-phenylcarbazolyl, dibenzofuranyl, dibenzothiazolyl, and 9,9-dimethylfluorenyl.

[0029] Preferably, Ar1 is selected from carbazole or N-phenylcarbazole. In this invention, when Ar1 is selected from the above-mentioned groups, the triazine compound, as the host material of the light-emitting layer, can significantly improve the current efficiency of the device.

[0030] Preferably, the L2 is selected from phenylene.

[0031] Preferably, Ar2, Ar3, and Ar4 are all selected from phenyl groups.

[0032] Preferably, the triazine compound is selected from any one of the following substituted or unsubstituted compounds:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] ;

[0043] The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom.

[0044] Preferably, the triazine compound is selected from any one of the following compounds:

[0045] , , , , , , , , , .

[0046] In this invention, there are no special restrictions on the preparation method of the above-mentioned triazine compounds, and commonly used preparation methods in the art are applicable.

[0047] Secondly, the present invention provides an intermediate having a structure as shown in formula MA:

[0048]

[0049] In the formula MA, X2 is selected from -F, -Cl, -Br or -I;

[0050] Y, L2, Ar2, Ar3, and Ar4 have the same defined range as in Equation I;

[0051] In compounds of formula MA, each hydrogen atom can be independently replaced by a deuterium atom, -F, cyano group, C1-C12 straight-chain or branched alkyl group, C3-C12 cycloalkyl group, C1-C12 straight-chain or branched alkoxy group, or C3-C12 cycloalkoxy group. , At least one of the following substitutions: C6-C20 aryl and C3-C20 heteroaryl; the dashed line indicates the linking site.

[0052] The intermediate is used to prepare triazine compounds as described in the first aspect.

[0053] Preferably, the intermediate comprises the following compounds:

[0054] , .

[0055] The preparation of compounds represented by formula MA and their application in the preparation of compounds of formula I are illustrated below with examples:

[0056]

[0057] Among them, X1 and X2 are each independently selected from any one of -F, -Cl, -Br or -I;

[0058] Y, L2, Ar1, Ar2, Ar3, and Ar4 have the same definitions as above;

[0059] The hydrogen atoms in each of the above-mentioned raw materials and intermediate compounds can be independently replaced by -F, cyano, C1-C12 straight-chain or branched alkyl, C3-C12 cycloalkyl, C1-C12 straight-chain or branched alkoxy, C3-C12 cycloalkoxy, , At least one of the following substitutions: C6-C20 aryl and C3-C20 heteroaryl; the dashed line indicates the linking site.

[0060] Thirdly, 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; the material of the organic thin film layer comprises a triazine compound as described in the first aspect.

[0061] Preferably, the organic thin film layer includes a light-emitting layer, and the light-emitting layer includes the triazine compound.

[0062] In this invention, the light-emitting layer comprises a host material and a dopant material, wherein the dopant material is also called a dye or a phosphorescent material. The host material of the light-emitting layer can be a single compound or a mixture of two or more compounds.

[0063] Preferably, the light-emitting layer includes a phosphorescent light-emitting layer, which comprises a host material and a dopant material, wherein the host material includes the aforementioned triazine compound.

[0064] Preferably, the volume percentage of the main material in the phosphorescent light-emitting layer is 60% to 99.9% (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 99.9%), more preferably 70% to 99.5%, and even more preferably 85% to 95%.

[0065] In this invention, the phosphorescent emitting layer includes a green phosphorescent emitting layer, a red phosphorescent emitting layer, a yellow phosphorescent emitting layer, and a blue phosphorescent emitting layer. Preferably, the phosphorescent emitting layer is a blue phosphorescent emitting layer.

[0066] Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

[0067] In this invention, the doping material of the light-emitting layer can be a phosphorescent material, also known as a triplet luminescent material, which refers to the light emitted by a substance from a triplet excited state. The specific selection of phosphorescent materials in this invention is not particularly limited; commonly used doping materials for the light-emitting layer in this field are applicable, including but not limited to: compounds having a structure as shown in formula PD.

[0068]

[0069] PD;

[0070] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0071] Y1-Y4 are each independently selected from carbon or nitrogen;

[0072] Y1 and Y2 can be connected by a single key or a double key, and Y3 and Y4 can be connected by a single key or a double key.

[0073] Cy1 and Cy2 are each independently selected from any one of phenyl, naphthyl, fluorenyl, spirofluorenyl, indyl, pyrroleyl, thiopheneyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, benzoquinolinyl, quinoxalinyl, quinazolinyl, carbazoleyl, benzimidazolyl, benzofuranyl, benzothiopheneyl, isobenzothiopheneyl, benzimidazolyl, benzozolyl, triazolyl, tetrazolyl, diazolyl, triazinyl, dibenzofuranyl, dibenzothiopheneyl, N-hexacarbazolyl, N-hexadibenzofuranyl, wherein Cy1 and Cy2 may optionally be linked to each other via a single bond or an organic linking group;

[0074] Any two or more ligands of M can be connected by single or double bonds, or by O or S bridging, or by any chemical group or chemical structure to form a structure that conforms to chemical principles.

[0075] R 91 and R 92Each group is independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidine, hydrazine, hydrazone, carboxylic acid group, carboxylate group, sulfonic acid group, sulfonate group, phosphate group, phosphate group, -SF5, substituted or unsubstituted C1-C60 (e.g., can be C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60) alkyl, substituted or unsubstituted C2-C6 0 (e.g., can be C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60) alkenyl, substituted or unsubstituted C2-C60 (e.g., can be C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60) alkynyl, substituted or unsubstituted C1-C60 (e.g., can be C1, C5, C10, C15, C20, C60, C70, C80, C9 ... 25. alkoxy, substituted or unsubstituted C2-C10 (e.g., can be C2, C3, C4, C5, C6, C7, C8, C9, or C10) heterocyclic alkyl, substituted or unsubstituted C6-C60 (e.g., can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54, or C60) aryl, substituted or unsubstituted C6-C60 (e.g., C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54, or C60) aryl, substituted or unsubstituted C6-C60 (e.g., C30, C35, C40, C45, C50, C55, or C60) alkyl ... For example, it can be any one of the following: (C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54, or C60) aryloxy group, substituted or unsubstituted C6-C60 (e.g., it can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54, or C60) arylthio group, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, or substituted or unsubstituted monovalent non-aromatic fused heterocyclic group; R 91 and R 92 In this context, the substituent is preferably at least one of -D, -F, C1-C6 alkyl, and C6-C12 aryl;

[0076] a1 and a2 are each independent integers selected from 1 to 5, for example, they can be 1, 2, 3, 4 or 5;

[0077] b is an integer selected from 0 to 4, for example, it can be 0, 1, 2, 3 or 4;

[0078] a is selected from 1, 2, or 3;

[0079] L1 can be a monovalent organic ligand, a divalent organic ligand, or a trivalent organic ligand.

[0080] Preferably, the PD compound is selected from any one of the following compounds:

[0081] .

[0082] Preferably, the organic thin film layer includes a hole layer, which includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0083] The hole injection layer material includes a P-type dopant. A P-type dopant is a material that coexists with the hole injection layer material in the OLED device, oxidizing the hole injection layer material and thus acting as an electron acceptor to promote the movement of holes from the hole injection layer to the anode. In this 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 -0.2 eV, preferably greater than -0.1 eV, more preferably greater than 0 eV, more preferably greater than 0.1 eV, and more preferably greater than 0.2 eV.

[0084] The P-type dopant exists in the hole injection layer at a volume percentage of 1%-10% (e.g., 1%, 2%, 4%, 6%, 8%, or 10%). In this invention, no particular limitation is made on the type of P-type dopant; exemplarily, compounds D-1 to D-13 disclosed in CN113728453A, or compounds HI-1 to HI-9 as shown below, can be used.

[0085] .

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

[0087] ;

[0088] In formula HT-GH4, L 41 Selected from single-bonded, C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40) aryl, and C6-C20 (e.g., C6, C8, C10, C12, C16, or C20) heteroaryl;

[0089] In formula HT-GH4, Ar 41 Ar 42 Each is independently selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40) aryl and C6-C20 (e.g., C6, C8, C10, C12, C16, or C20) heteroaryl;

[0090] In formula HT-GH4, X is selected from CR 41 R 42 Or NR 43 , where R 41 R 42 R 43 Each is independently selected from substituted or unsubstituted phenyl groups (the substituents are selected from C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkoxy, dibenzofuranyl, naphthyl, triphenylene, fluoranyl, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted dibenzofuranyl (the substituent is phenyl), substituted or unsubstituted dibenzothiophenyl (the substituent is phenyl), dibenzofuran-substituted thiophenyl, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl, R 41 R 42 They can be connected into a ring using a single key.

[0091] In this invention, the hole layer material (including the hole injection layer, the hole transport layer, and the electron blocking layer) may further include a compound having the structure shown in Formula IA or a compound having the structure shown in Formula IB:

[0092] Formula ⅠA;

[0093] Formula IB;

[0094] In Formula IA and Formula IB, L is selected from any one of C6-C40 (e.g., it can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) arylene, dibenzofuranyl or dibenzothiophene.

[0095] In Equations IA and IB, m is selected from integers between 0 and 4 (for example, it can be 0, 1, 2, 3 or 4), and n is selected from 0 or 1;

[0096] In Formula IA and Formula 1B, Ar is selected from any one of phenylenetriene, fluorenetrienylene, dibenzofuranylene, or dibenzothiopheneylene.

[0097] In Formula IA and Formula 1B, Ar1 and Ar2 are each independently selected from any one of aryl, dibenzofuranyl, or dibenzothiophene groups containing C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.);

[0098] In Equations IA and IB, Ar1 and Ar, Ar2 and Ar, and Ar1 and Ar2 can be independently connected or bridged by single bonds, O, S, CR1R2, and NR.

[0099] In Formula IA and Formula 1B, R, R1, and R2 are each independently selected from any one of C1-C20 (e.g., C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20), C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40), dibenzofuranyl, or dibenzothiopheneyl.

[0100] In compounds of formula IB and formula IA, the hydrogen atoms can be independently replaced by at least one of -F, -CN, -D (deuterium atom), C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthracene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, triphenylene, fluoranyl, pyrene, perylene, spirofluorenyl, indo[a]fluorenyl, or hydrogenated benzo[a]anthryl.

[0101] Preferably, in Formula IA and Formula IB, Ar is fluoreneanthracene, and m+n>1.

[0102] Preferably, the H in the compounds of formula IB and formula IA can be replaced by at least one of -F, -CN, -D, C1-C3 alkyl (e.g., methyl, ethyl, or propyl), C1-C3 alkoxy (e.g., methoxy, ethoxy, or propoxy), phenyl, biphenyl, triphenylene, or fluoranthyl.

[0103] Preferably, in Formula IA and Formula IAB, L, Ar1, and Ar2 are each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, triphenylene, fluoranyl, pyrene, perylene, spirofluorenyl, indo[a]fluorenyl, or hydrogenated benzo[a]anthryl.

[0104] Preferably, the compound of formula IB is selected from any one of the following compounds:

[0105] .

[0106] In the OLED device provided by this invention, the hole layer material may include, in addition to the compounds described in Formula HT-GH4, Formula IB, and Formula IA, conventional hole materials in the art, without particular limitation. Exemplarily, it includes, but is not limited to, triarylamine compounds or carbazole compounds. Triarylamine compounds or carbazole compounds containing three or more nitrogen atoms are preferred because they have a higher HOMO (lower absolute value) and are more suitable as hole injection layer materials. Triarylamine compounds or carbazole compounds containing two or one nitrogen atom can be used as hole transport layer materials. Some compounds or carbazole compounds containing one nitrogen atom, if they have a high LUMO, can also be used as electron blocking layer materials.

[0107] The triaryl amine compound or carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0108] ;

[0109] Among them, Ar 601 ~Ar 609 Each is independently selected from any one of the following: substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted naphthobenzofuranyl, substituted or unsubstituted naphthobenzothiopheneyl, substituted or unsubstituted dinaphthofuranyl, and substituted or unsubstituted dinaphthothiopheneyl; Ar 601 ~Ar 609 In this context, the substituent is preferably at least one of -D, -F, C1-C6 alkyl, and C6-C12 aryl;

[0110] And Ar 601 ~Ar 609 Ar atoms that are adjacent to or connected to the same N atom 601 ~Ar 609 It can be connected via a single key or via O, S, CR 701 R 702 NR 703 bridging;

[0111] R 701 R 702 R 703 Selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl, C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl, and R 701 R 702 It can be connected with a single button.

[0112] Hole blocking layers (HBLs) can confine holes and / or excitons within the emissive layer to improve device current efficiency and lifetime. Compared to emissive layer materials closest to the HBL interface, HBL materials exhibit lower HOMO (larger absolute values) and / or higher triplet energies.

[0113] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped, and doping can be used to enhance conductivity. In this invention, there are no particular limitations on the ETL material; any metal complex or organic compound can be used, as long as it can transport electrons. Generally, electron transport layer materials contain at least one of the following structural segments: pyridine, pyrimidine, triazine, benzimidazole, benzoxazole, benzothiazole, N-naphthalene, N-phenanthion, N-carbazole, N-dibenzofuran, and N-dibenzothiophene.

[0114] In this invention, no special restrictions are placed on the electron transport layer material, which includes, but is not limited to, the following:

[0115] .

[0116] In this invention, the cathode material is a metal with low work function (e.g., alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm), a metal alloy composed of multiple metals (an alloy composed of alkali metals or alkaline earth metals 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 function can also be used, such as Ag or Al. In this case, combinations of the metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag.

[0117] Alternatively, a thin interlayer of material with a high dielectric constant can be introduced 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 can be an alkali metal or alkaline earth metal fluoride, as well as the corresponding oxide or carbonate (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ).

[0118] Fourthly, the present invention provides a display device comprising the organic electroluminescent device as described in the third aspect.

[0119] Compared with the prior art, the present invention has the following beneficial effects:

[0120] This invention designs the structure of compounds to obtain triazine compounds with excellent performance. Using triazine compounds as the main material of the light-emitting layer, the organic electroluminescent devices prepared have high current efficiency, long lifespan and low driving voltage. Detailed Implementation

[0121] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0122] Preparation Example 1: Synthesis of Intermediate M1

[0123]

[0124] Add 10g of raw material M0, 100ml of glacial acetic acid, 10ml of 10% sulfuric acid, and 0.1g of PdCl2 to a high-pressure reactor. Seal and heat to 100℃ for 24 hours. After the reaction is completed, cool down and pour the obtained reaction product into water. Filter and wash the obtained solid until neutral. Then separate by silica gel column chromatography with dichloromethane as the eluent to obtain intermediate M1 (3.9g).

[0125] The obtained intermediate M1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 643.23.

[0126] The MRI scan was performed, and the data is as follows: 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ 8.26 (s, 2H), δ 8.24–8.20 (m, 2H), 8.11 (s, 2H), δ 7.90–7.85 (m, 4H), δ 7.82 (s, 1H), δ 7.66–7.50 (m, 8H), δ 7.37–7.31 (m, 2H), δ 7.25–7.21 (m, 8H).

[0127] Preparation Example 2

[0128] This preparation provides intermediate 1-1 and its synthesis method, which is as follows:

[0129]

[0130] Under nitrogen protection, dry methyltetrahydrofuran (120 mL), intermediate M1 (6.1 g), intermediate 1-0 (4.7 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.0575 g), a 10% (w / w) toluene solution of tri-tert-butylphosphine (0.4 g by mass), and sodium tert-butoxide (1.5 g) were added to a three-necked flask. The mixture was heated to 40 °C and reacted for 24 hours. After cooling to room temperature, water and chloroform were added to separate the layers. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and crystallized with a mixed solvent of toluene and chloroform to obtain intermediate 1-1 (3.6 g).

[0131] The obtained intermediate 1-1 was subjected to mass spectrometry analysis, and the mass-to-charge ratio (m / z) was measured to be 1090.33.

[0132] Preparation Example 3

[0133] This preparation provides intermediate 2-1 and its synthetic method, which is as follows:

[0134]

[0135] Following the preparation of intermediate 1-1, intermediate 2-1 was obtained.

[0136] The obtained intermediate 2-1 was subjected to mass spectrometry analysis, and the mass-to-charge ratio (m / z) was measured to be 1090.33.

[0137] Example 1

[0138] This embodiment provides compound 1 and its synthesis method, which is as follows:

[0139]

[0140] Under nitrogen protection, toluene (200 mL), ethanol (70 mL), water (30 mL), intermediate 1-1 (8.0 g), phenylboronic acid (1.1 g), sodium carbonate (2.0 g), and tetraphenylphosphine palladium (0.20 g) were added to a three-necked flask, and the mixture was slowly heated to room temperature. flow The reaction was carried out for 6 h, then cooled to room temperature. Water and toluene were added and the mixture was separated. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and crystallized with toluene to obtain compound 1 (5.8 g).

[0141] The obtained compound 1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 1132.40.

[0142] Example 2

[0143] This embodiment provides compound 2 and its synthesis method, which is as follows:

[0144]

[0145] Compound 2 was obtained by referring to the preparation of compound 1.

[0146] The obtained compound 2 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 1132.40.

[0147] Example 3

[0148] This embodiment provides compound 3 and its synthesis method, which is as follows:

[0149]

[0150] The preparation of intermediate 1-1 was the same, except that the reaction at 40°C for 24 hours was changed to a reflux reaction for 6 hours.

[0151] The obtained compound 3 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 1116.42.

[0152] Example 4

[0153] This embodiment provides compound 8 and its synthesis method, which is as follows:

[0154]

[0155] Under nitrogen protection, dry methyltetrahydrofuran (190 mL), intermediate 1-1 (10.0 g), carbazole (1.7 g), Pd(dba)2 (bis(dibenzylacetone palladium, 0.0575 g), a 10% (w / w) toluene solution of tri-tert-butylphosphine (0.4 g by mass), and sodium tert-butoxide (1.5 g) were added to a three-necked flask. The mixture was heated to reflux for 6 hours, cooled to room temperature, and separated by adding water and chloroform. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and crystallized with a mixed solvent of toluene and chloroform to obtain compound 8 (5.6 g).

[0156] The obtained compound 8 was subjected to mass spectrometry, and the mass-to-charge ratio (m / z) was measured to be 1221.42.

[0157] Other compounds not listed can be synthesized by referring to the above examples and combining them with common knowledge in the art.

[0158] The specific structures of some of the compounds used in the following application examples and comparative application examples are as follows:

[0159] , , , , , , , , , , , , , , , , , , .

[0160] Application Example 1

[0161] This application example provides a blue organic electroluminescent device, using compound 1 provided by the present invention as the host material of the light-emitting layer. The structure of the blue organic electroluminescent device is as follows:

[0162] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / Main material: PBD-1[5%](35nm) / ETL-1(25 nm) / LiF(0.5nm) / Al(150 nm).

[0163] The fabrication method of the blue organic electroluminescent device is as follows:

[0164] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa, the above materials are sequentially vacuum-deposited onto the cleaned ITO substrate to prepare OLED devices.

[0165] Among them, the main material: PBD-1[5%] (35nm) is the light-emitting layer. The main material: PBD-1[5%] refers to the doping ratio of the dye in the light-emitting layer, that is, the volume ratio of the main material to the dye PBD-1 in the light-emitting layer is 95:5, and the film thickness of the light-emitting layer is 35nm; in this application example, the main material of the light-emitting layer is compound 1.

[0166] HT-1:HI-2[5%] (80nm) is the hole injection layer. HT-1:HI-2[5%] refers to the proportion of P-type dopant in the hole injection layer. That is, the volume ratio of hole injection material HT-1 and P-type dopant HI-2 in the hole injection layer is 95:5, and the thickness of the hole injection layer is 80nm.

[0167] HT-1 (30nm) is a hole transport layer with a film thickness of 30nm;

[0168] EB-1 (20nm) is an electron blocking layer with a film thickness of 20nm;

[0169] ETL-1 (25nm) is an electron transport layer with a film thickness of 25nm;

[0170] The LiF layer (0.5nm) is used for electron injection, and its thickness is 0.5nm.

[0171] ITO refers to the anode, and Al (150nm) refers to the cathode.

[0172] Application Examples 2 to 6

[0173] Application Examples 2 through 6 provide a blue organic electroluminescent device. The only difference from Application Example 1 is that the host material compound 1 of the light-emitting layer is replaced with other compounds (see Table 1 below). The other preparation steps and conditions are the same as in Application Example 1.

[0174] Comparative Application Example 1

[0175] Comparative Application Example 1 provides a blue organic electroluminescent device. The only difference between this and Application Example 1 is that the host material compound 1 of the light-emitting layer is replaced with other compounds (see Table 1 below). The other preparation steps and conditions are the same as in Application Example 1.

[0176] Performance testing

[0177] The luminance, driving voltage, current efficiency, and LT95 of the organic electroluminescent devices provided above were tested. The current efficiency was measured at a luminance of 1000 cd / m². 2 The corresponding value, LT95, refers to maintaining an initial device current density of 10 mA / cm². 2 The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, while remaining constant, is given. The drive voltage, current efficiency, and LT95 are relative values ​​(based on Application Example 1). Specific test results are shown in Table 1 below:

[0178] Table 1

[0179]

[0180] As described above, this invention, through the design of the compound structure, yields triazine compounds with excellent performance. Using these triazine compounds as the host material for the light-emitting layer, the resulting organic electroluminescent devices exhibit high current efficiency, long lifetime, and low driving voltage. In particular, when Ar1 is selected from carbazole or N-phenylcarbazole groups, the triazine compound, as the host material for the light-emitting layer, can significantly improve the current efficiency of the device.

[0181] Application Example 7

[0182] Application Example 7 provides a blue organic electroluminescent device, which differs from Application Example 1 only in that the dye in the light-emitting layer is replaced by PBD-2 instead of PBD-1. The other preparation steps and conditions are the same as in Application Example 1.

[0183] Application Examples 8-11

[0184] Application Examples 8-11 provide a blue organic electroluminescent device. The only difference from Application Example 1 is that the host material compound 1 of the light-emitting layer is replaced with other compounds (see Table 2 below), and the dye of the light-emitting layer is replaced with PBD-2 instead of PBD-1. The other preparation steps and conditions are the same as in Application Example 1.

[0185] Performance testing

[0186] The luminance, driving voltage, current efficiency, and LT95 of the organic electroluminescent devices provided above were tested. The current efficiency was measured at a luminance of 1000 cd / m². 2 The corresponding value, LT95, refers to maintaining an initial device current density of 10 mA / cm². 2 The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, while remaining constant, is given. The drive voltage, current efficiency, and LT95 are relative values ​​(based on Application Example 7). Specific test results are shown in Table 2 below:

[0187] Table 2

[0188]

[0189] As can be seen from the above, this invention has obtained triazine compounds with excellent performance by designing the structure of the compounds. The organic electroluminescent devices prepared by using triazine compounds as the main material of the light-emitting layer have high current efficiency, long lifespan and low driving voltage.

[0190] The present invention has been illustrated with the above embodiments to describe the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the 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, characterized in that, The triazine compound has the structure shown in Formula I: Formula I; Ar1 is selected from any one of C6~C20 aryl and C3~C20 heteroaryl; L2 is selected from any one of the C6~C20 arylene groups; Ar2, Ar3, and Ar4 are each independently selected from any one of the C6 to C20 aryl groups; Y is selected from C or Si; In Formula I compounds, each hydrogen atom can be independently replaced by a deuterium atom, -F, cyano group, C1-C12 straight-chain or branched alkyl group, C3-C12 cycloalkyl group, C1-C12 straight-chain or branched alkoxy group, C3-C12 cycloalkoxy group, , At least one of the following substitutions: C6-C20 aryl and C3-C20 heteroaryl; the dashed line indicates the linking site.

2. The triazine compound according to claim 1, characterized in that, The C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, terphenyl, 9,9-dimethylfluorenyl, triphenylene, anthracene, phenanthrene, or fluoranthyl. Preferably, the C3~C20 heteroaryl group is selected from any one of triazinyl, carbazole, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, and naphthobenzothiophenyl. Preferably, the C6-C20 arylene group is selected from any one of phenylene, naphthylene, biphenylene, terphenylene, 9,9-dimethylfluorene, trimethyleneene, anthracene, phenanthrene, and fluoranthracene. Preferably, the C1-C12 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-undecyl. Preferably, the C3-C12 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; Preferably, the C1-C12 straight-chain or branched alkoxy groups are selected from any one of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, and n-hexoxy. Preferably, the C3~C12 cycloalkoxy group is selected from any one of cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexyloxy.

3. The triazine compound according to claim 1, characterized in that, The Ar1 is selected from any one of phenyl, naphthyl, biphenyl, terphenyl, carbazolyl, N-phenylcarbazolyl, dibenzofuranyl, dibenzothiazolyl, and 9,9-dimethylfluorenyl. Preferably, Ar1 is selected from carbazolyl or N-phenylcarbazolyl.

4. The triazine compound according to claim 1, characterized in that, The L2 is selected from phenylene; Preferably, Ar2, Ar3, and Ar4 are all selected from phenyl groups.

5. The triazine compound according to claim 1, characterized in that, The triazine compounds are selected from any one of the following substituted or unsubstituted compounds: ； The substitution refers to the replacement of at least one hydrogen atom in the above compound with a deuterium atom; Preferably, the triazine compound is selected from any one of the following compounds: 、 、 、 、 、 、 、 、 、 。 6. An intermediate, characterized in that, The intermediate has a structure as shown in formula MA: In the formula MA, X2 is selected from -F, -Cl, -Br or -I; Y, L2, Ar2, Ar3, and Ar4 have the same defined range as in Equation I; In compounds of formula MA, each hydrogen atom can be independently replaced by a deuterium atom, -F, cyano group, C1-C12 straight-chain or branched alkyl group, C3-C12 cycloalkyl group, C1-C12 straight-chain or branched alkoxy group, C3-C12 cycloalkyl group, etc. , At least one of the following substitutions: C6-C20 aryl and C3-C20 heteroaryl; the dashed line indicates the linking site. The intermediate is used to prepare the triazine compound as described in any one of claims 1 to 5; Preferably, the intermediate comprises the following compounds: 、 。 7. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode; the material of the organic thin film layer includes triazine compounds as described in any one of claims 1 to 5.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic thin film layer includes a light-emitting layer, and the light-emitting layer includes the triazine compound.

9. The organic electroluminescent device according to claim 8, characterized in that, The light-emitting layer includes a phosphorescent light-emitting layer, which comprises a host material and a dopant material, wherein the host material includes the aforementioned triazine compound.

10. The organic electroluminescent device according to claim 9, characterized in that, The phosphorescent luminescent layer is a blue phosphorescent luminescent layer; Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

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