Triphenylene compound, intermediate and organic electroluminescent device

Abstract

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

Description

Technical Field

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

[0002] Electroluminescence, also known as electroluminescence or EL for short, is a light-emitting phenomenon in which a solid directly converts electrical energy into light energy by generating an electric field through a voltage applied to two electrodes. Among these, electroluminescence from organic materials is an injection-type composite light emission. Based on their function and structure in organic electroluminescent (OLED) devices, organic electroluminescent materials can be further classified into hole injection layer (HIL), hole transport layer (HTL), emissive layer (EML), electron transport layer (ETL), and electron injection layer (EIL), among others.

[0003] Currently, organic light-emitting diodes (OLEDs) have become the mainstream display technology, and correspondingly, various new OLED materials have been developed. However, their various properties still need improvement, especially in terms of efficiency, lifespan, and voltage. To meet the higher requirements for OLED devices, there is an urgent need in this field to develop more types and higher-performance blue light host materials. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a triphenylene oxide compound, an intermediate, and an organic electroluminescent device. In this invention, the structure of the triphenylene oxide compound is designed to be suitable as the main material for the light-emitting layer of an organic electroluminescent device, resulting in an organic electroluminescent device with lower driving voltage, higher current efficiency, and longer lifespan.

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

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

[0007]

[0008] Where ring A has the structure shown in formula I-1, ring A is fused with the two adjacent benzene rings, and the dashed lines represent the fusion sites;

[0009] Ar1 and Ar2 are selected from -H or -D, and the other is selected from C6-C40 aryl or C6-C30 heteroaryl.

[0010] R1 is selected from any one of C6-C40 aryl or C6-C30 heteroaryl;

[0011] In compounds of formula I, each hydrogen atom can be independently substituted by at least one of -D, -CN, -F, C6-C20 aryl, C1-C12 alkyl, or C1-C12 alkoxy.

[0012] In this invention, the structure of triphenylene compounds is designed such that the two substituents of triphenylene are in the ortho-substitution position. These two substituents are in an approximately parallel state, resulting in a more regular spatial structure, better charge transport performance, and greater suitability as the main material for the light-emitting layer of organic electroluminescent devices.

[0013] In this invention, the structure of triphenylene compounds is designed to make them suitable as the main material for the light-emitting layer of organic electroluminescent devices, thereby enabling the organic electroluminescent devices to have lower driving voltage, higher current efficiency, and longer lifespan.

[0014] In this invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0015] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28, or C30, etc.

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

[0017] C1-C12 can be C1, C2, C4, C6, C8, C10, or C12, etc.

[0018] It should be noted that in this invention, "-D" represents a deuterium atom, and the same applies below.

[0019] 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.

[0020] As a preferred embodiment of the present invention, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, anthracene, phenanthrene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthreneyl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthylfluorenyl.

[0021] Preferably, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, or dinaphthothiophenyl.

[0022] Preferably, the C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, triphenylene, or fluoranthracene.

[0023] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or decyl.

[0024] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy.

[0025] As a preferred embodiment of the present invention, the triphenylene compounds have any one of the structures shown in Formula I-1 to Formula I-6:

[0026]

[0027] Among them, R1, Ar1, and Ar2 have the same definitions as above.

[0028] As a preferred embodiment of the present invention, Ar1 is selected from C6-C40 aryl or C6-C30 heteroaryl, and Ar2 is selected from -H or -D.

[0029] Preferably, the Ar2 is selected from C6-C40 aryl or C6-C30 heteroaryl, and the Ar1 is selected from -H or -D.

[0030] As a preferred embodiment of the present invention, Ar1 is selected from -H or -D, and Ar2 is selected from any one or a combination of at least two of carbazolyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, and dibenzothiophene.

[0031] Preferably, the Ar2 is selected from -H or -D, and the Ar1 is selected from any one or a combination of at least two of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl or carbazoleyl.

[0032] As a preferred embodiment of the present invention, R1 is selected from any one of phenyl, naphthyl, biphenyl, carbazole, dibenzofuranyl or dibenzothiophene, preferably phenyl.

[0033] As a preferred embodiment of the present invention, each hydrogen atom in the compound of Formula I may be independently substituted by at least one of -D, -CN, -F, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, tert-butyl, hexyl, methoxy, ethoxy, or propoxy.

[0034] Preferably, each hydrogen atom in the compound of formula I can be independently substituted by at least one of -D, -CN, -F, phenyl, naphthyl, biphenyl, tert-butyl, ethyl, methoxy, or propoxy.

[0035] As a preferred embodiment of the present invention, the triphenylene compounds are selected from the following substituted or unsubstituted compounds:

[0036]

[0037]

[0038]

[0039] The substitution refers to the independent substitution of each hydrogen atom in the aforementioned triphenylene compounds by a deuterium atom. Preferably, the triphenylene compounds are selected from any one of the following compounds:

[0040]

[0041]

[0042] Secondly, the present invention provides an intermediate having a structure as shown in formula MA:

[0043]

[0044] Ring A has the same definition as above;

[0045] Either X1 or X2 is selected from any one of -F, -Cl, -Br or I, and the other is selected from -H or -D; the intermediate is used to prepare triphenylene compounds as described in the first aspect.

[0046] Preferably, X2 is selected from one of F, Cl, Br, and I, and X1 is selected from -H or -D.

[0047] Preferably, X1 is selected from one of F, Cl, Br, and I, and X2 is selected from -H or -D.

[0048] As a preferred embodiment of the present invention, the intermediate comprises the following compounds:

[0049]

[0050]

[0051] In this invention, there are no special limitations on the synthesis method of the intermediate; commonly used synthesis methods in the art are applicable, including but not limited to:

[0052]

[0053] Ring A has the same definition as above;

[0054] One of X1 and X2 is selected from any one of -F, -Cl, -Br or I, and the other is selected from -H or -D;

[0055] X3 is selected from any one of -F, -Cl, -Br, or I.

[0056] It should be noted that the present invention does not impose any special limitations on the synthesis method of the above-mentioned triphenylene compounds, and commonly used synthesis methods in the art are applicable.

[0057] 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;

[0058] The organic thin film layer includes triphenylene compounds as described in the first aspect.

[0059] As a preferred embodiment of the present invention, the organic thin film layer includes a light-emitting layer;

[0060] The main material of the light-emitting layer includes triphenylene compounds as described in the first aspect.

[0061] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0062] As a preferred embodiment of the present invention, the organic electroluminescent device is a green organic electroluminescent device.

[0063] 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.

[0064] The light-emitting layer includes a phosphorescent light-emitting layer, which includes a green phosphorescent light-emitting layer, a red phosphorescent light-emitting layer, a yellow phosphorescent light-emitting layer, and a blue phosphorescent light-emitting layer.

[0065] The volume percentage of the main material in the phosphorescent luminescent layer is 60% to 99.9% (e.g., it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 99.9%), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0066] 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.

[0067]

[0068] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0069] Y1-Y4 are each independently selected from carbon or nitrogen;

[0070] 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.

[0071] 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;

[0072] 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.

[0073] 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, etc.) 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, etc.) alkenyl, substituted or unsubstituted C2-C60 (e.g., can be C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55, or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (e.g., can be C1, C5, C10, C15, C20, C40, C50, C55, C60, etc.) alkyne, substituted or unsubstituted C1-C60 (e.g., can be C1, C5, C10, C15, C20, C50, C10, C15, C20, C1 ... 25. alkoxy, substituted or unsubstituted C2-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, or C10), heterocyclic alkyl, 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 (… For example, it can be any one of the following: aryloxy group (C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.), substituted or unsubstituted C6-C60 (e.g., it can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.), substituted or unsubstituted monovalent non-aromatic fused polycyclic group, or substituted or unsubstituted monovalent non-aromatic fused heterocyclic group.

[0074] a1 and a2 are each independent integers selected from 1 to 5, for example, they can be 1, 2, 3, 4 or 5;

[0075] b is an integer selected from 0 to 4, for example, it can be 0, 1, 2, 3 or 4;

[0076] a is selected from 1, 2, or 3;

[0077] L1 can be a monovalent organic ligand, a divalent organic ligand, or a trivalent organic ligand.

[0078] Preferably, the PD compound is selected from any one of the following compounds:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] In this invention, the organic thin film layer includes a hole layer, which comprises a hole injection layer, a hole transport layer, and an electron blocking layer.

[0086] 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 -0.2V, preferably greater than -0.1eV, more preferably greater than 0eV, more preferably greater than 0.1eV, and more preferably greater than 0.2eV.

[0087] The P-type dopant exists in the hole injection layer at a volume percentage of 1% to 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 described below can be used.

[0088]

[0089]

[0090] In this invention, 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:

[0091]

[0092] Among them, L 41 Selected from single-bonded, C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, and C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0093] Ar 41 Ar42 Each is independently selected from C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl and C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0094] X is selected from CR 41 R 42 Or NR 43 , where R 41 R 42 R 43 Each is independently selected from any one of 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.

[0095] The HT-GH4 compound is selected from any one of the following compounds:

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] In this invention, the hole layer material (including a hole injection layer, a hole transport layer, and an electron blocking layer) further includes a compound having a structure as shown in Formula IA or a compound having a structure as shown in Formula IB:

[0102]

[0103] Wherein, 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 group;

[0104] m is selected from an integer between 0 and 4 (for example, it can be 0, 1, 2, 3 or 4), and n is selected from 0 or 1;

[0105] Ar is selected from any one of triphenylene, fluorene anthracene, dibenzofuranyl or dibenzothiophene;

[0106] 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.);

[0107] Ar1 and Ar, Ar2 and Ar, and Ar1 and Ar2 can be independently connected or bridged by single bonds, O, S, CR1R2, NR.

[0108] R, R1, and R2 are each independently selected from any one of the following: C1-C20 (e.g., C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20), alkyl, C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40), aryl, dibenzofuranyl, or dibenzothiopheneyl.

[0109] In compounds of formula IB and formula IA, the H 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.

[0110] Preferably, the Ar is fluoreneanthracene, where m+n>1.

[0111] 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, and fluoranthyl.

[0112] Preferably, 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.

[0113] Preferably, the compound of formula IB is selected from the following structures:

[0114]

[0115] Wherein, L represents phenylene;

[0116] Ar1, Ar2, and m have the same protection range as described above.

[0117] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0118]

[0119]

[0120]

[0121] In the OLED device provided by this invention, the hole layer material, in addition to the compounds described in formula HT-GH4, formula IB, and formula IA, may also include conventional hole materials in the art, without particular limitation. Exemplarily, it includes, but is not limited to, triarylamine compounds or triphenylene compounds. Preferably, triarylamine compounds or triphenylene compounds containing three or more nitrogen atoms are used because they have a higher HOMO (lower absolute value) and are more suitable as hole injection layer materials. Triarylamine compounds or triphenylene compounds containing two or one nitrogen atom can be used as hole transport layer materials. Some compounds or triphenylene compounds containing one nitrogen atom, if they have a high LUMO, can also be used as electron blocking layer materials.

[0122] The triarylamine compound or triphenylene oxide compound is used as the hole layer material, and the hole layer material includes the following structure:

[0123]

[0124] Among them, Ar 601 ~Ar 609Each 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 dibenzothiophene, substituted or unsubstituted naphthobenzofuranyl, substituted or unsubstituted naphthobenzothiophene, substituted or unsubstituted dinaphthofuranyl, substituted or unsubstituted dinaphthothiophene.

[0125] 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;

[0126] 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.

[0127] 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.

[0128] 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.

[0129] In this invention, no special restrictions are placed on the electron transport layer material, which includes, but is not limited to, the following:

[0130]

[0131]

[0132] 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, etc.)), 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.

[0133] 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).

[0134] Compared with the prior art, the present invention has the following beneficial effects:

[0135] This invention designs the structure of triphenylene compounds to make them suitable as the main material for the light-emitting layer of organic electroluminescent devices, thereby enabling the organic electroluminescent devices to have lower driving voltage, higher current efficiency, and longer lifespan. Detailed Implementation

[0136] 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.

[0137] Preparation Example 1

[0138] This preparation example provides intermediate P1-1, which is synthesized as follows:

[0139]

[0140] Under a nitrogen atmosphere, dry toluene (100 mL), intermediate M1 (3.8 g), intermediate M1-1 (3.3 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.1 g), a 10% (w / w) solution of tri-tert-butylphosphine in toluene (w / w) and sodium tert-butoxide (1.2 g) were added to a three-necked flask. The mixture was heated to reflux for 4 h, cooled to room temperature, and water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and crystallized three times from toluene to obtain intermediate P1-1 (4.1 g).

[0141] Mass spectrometry analysis of intermediate P1-1 showed a mass-to-charge ratio (m / z) of 636.12.

[0142] Preparation Examples 2-6

[0143] Preparation Examples 2-6 each provide an intermediate. The synthesis method of the intermediate can refer to the synthesis method of intermediate P1-1 provided in Preparation Example 1. The corresponding starting materials are used to prepare the corresponding compounds, as shown in Table 1 below.

[0144] The obtained intermediates were subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) data are shown in Table 1 below.

[0145] Table 1

[0146]

[0147]

[0148] Preparation Example 7

[0149] This preparation example provides intermediate P7-1, which is synthesized as follows:

[0150]

[0151] Under a nitrogen atmosphere, dry toluene (100 mL), intermediate M1 (3.8 g), intermediate M1-1 (3.3 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.1 g), a 10% (w / w) solution of tri-tert-butylphosphine in toluene (w / w) and sodium tert-butoxide (1.2 g) were added to a three-necked flask. The mixture was heated to reflux for 4 h, cooled to room temperature, and water was added to dissolve the mixture. The organic layer was then 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 petroleum ether to obtain intermediate P7-1 (1.6 g).

[0152] Mass spectrometry analysis of intermediate P7-1 revealed a mass-to-charge ratio (m / z) of 636.12.

[0153] To verify the structure of intermediate P7-1, the following experiment was conducted:

[0154]

[0155] Under nitrogen atmosphere, 0.1 g of intermediate P7-1 was added to 20 mL of dry tetrahydrofuran. Under controlled nitrogen atmosphere, an equimolar amount of butyllithium solution was slowly added dropwise at -78℃ to -70℃. After the addition was complete, the temperature was maintained at -78℃ to -70℃ for 20 min. 0.5 mL of ethanol was added, and the temperature was slowly raised to room temperature. Dichloromethane and water were added. After the organic layer was concentrated, the mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain intermediate P7-1D.

[0156] Mass spectrometry analysis of intermediate P7-1 showed a mass-to-charge ratio (m / z) of 558.21.

[0157] The intermediate P7-1D was analyzed by NMR, and the data are as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ 9.37 (d, 1H), δ 9.00 (m, 1H), 8.56 (m, 2H), δ 8.30 (m, 1H), δ 8.27 (d, 1H), δ 8.16 (m, 1H), δ 7.73 (m, 2H), δ 7.65~7.47 (m, 12H), 7.18~7.10 (m, 4H), δ 7.06 (d, 1H).

[0158] Example 1

[0159] This embodiment provides compound P1D, whose synthesis method is as follows:

[0160]

[0161] Under a nitrogen atmosphere, dry toluene (90 mL), intermediate P1-1 (6.4 g), deuterated carbazole (1.8 g), Pd(dba)2 (bis(dibenzylacetone)palladium, 0.1 g), a 10% (w / w) solution of tri-tert-butylphosphine in toluene (w / w) and sodium tert-butoxide (1.2 g) were added to a three-necked flask. The mixture was heated to reflux for 6 h, cooled to room temperature, and water was added to dissolve the mixture. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and crystallized from toluene to obtain compound P1D (5.8 g).

[0162] Mass spectrometry analysis of compound P1D showed a mass-to-charge ratio (m / z) of 731.32.

[0163] Examples 2-7

[0164] Examples 2-7 each provide a compound. The synthesis method of the compound can refer to the synthesis method of compound P1 provided in Example 1. The corresponding raw materials are used to react and prepare the corresponding compound, as shown in Table 2 below.

[0165] The obtained compounds were analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) data are shown in Table 2 below.

[0166] Table 2

[0167]

[0168]

[0169] Example 8

[0170] This embodiment provides compound P15, whose synthesis method is as follows:

[0171]

[0172] Under a nitrogen atmosphere, 80 mL of dioxane was added to a three-necked flask, followed by 6.4 g of intermediate P1-1, 1.3 g of phenylboronic acid, 2.12 g of sodium carbonate, and 0.23 g of tetrakis(triphenylphosphine)palladium. The mixture was slowly heated to reflux and reacted for 6 h. After cooling to room temperature, water and toluene were added to separate the layers. The organic layer was washed with water and dried with magnesium sulfate. After removing the desiccant, the mixture was concentrated to dryness and separated by silica gel column chromatography. The elution was performed with petroleum ether to obtain compound P15 (5.6 g).

[0173] The obtained compound P15 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 634.24.

[0174] Example 9

[0175] This embodiment provides compound 7, whose synthesis method is as follows:

[0176]

[0177] Following the synthesis of compound P15, compound P7 was prepared.

[0178] The obtained compound P7 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was found to be 634.24.

[0179] For other compounds whose specific synthesis methods are not listed, they can be synthesized by referring to the above examples and combining them with common knowledge in the field.

[0180] The specific structures of some of the compositions used in the following application examples and comparative application examples are as follows:

[0181]

[0182] Application Example 1

[0183] This application example provides a green organic electroluminescent device, using the compound P1D provided by this invention as the host material of the light-emitting layer. The structure of the green organic electroluminescent device is as follows:

[0184] ITO / HT-1: HI-2[5%](70nm) / HT-1(35nm) / Main material: GD1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0185] The fabrication method of the green organic electroluminescent device is as follows:

[0186] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto a cleaned ITO substrate to fabricate OLED devices.

[0187] Wherein, GD1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the host material to the dye GD1 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 the hole transport material; HT-1:HI-2[5%] is the material used to form the hole injection layer.

[0188] Application Example 2-13

[0189] Application Examples 2-13 provide an organic electroluminescent device, which differs from Application Example 1 only in that the host material compound P1D of the light-emitting layer is replaced with other compounds (see Table 3 below). The other preparation steps and conditions are the same as in Application Example 1.

[0190] Comparative application examples 1-2

[0191] Comparative Application Examples 1-2 provide an organic electroluminescent device. The only difference from Application Example 1 is that the host material compound P1D of the light-emitting layer is replaced with other compounds (see Table 3 below). The other preparation steps and conditions are the same as in Application Example 1.

[0192] Performance testing

[0193] The luminance, driving voltage, current efficiency, and LT95 of the organic electroluminescent devices provided above were tested. The current efficiency is measured when the luminance is 1000 cd / m². 2 The corresponding value, LT95, refers to maintaining an initial device current density of 10 mA / cm². 2The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, while remaining constant, is given. Voltage, current efficiency, and LT95 are relative values. Specific test results are shown in Table 3 below.

[0194] Table 3

[0195] Main materials dye <![CDATA[Brightness / (cd / m 2 )]]> Drive voltage Current efficiency LT95 Application Example 1 P1D GD1 1000 1.02 1.07 1.68 Application Example 2 P11 GD1 1000 1 1 1.31 Application Example 3 P12 GD1 1000 0.96 1.01 1.09 Application Example 4 P13 GD1 1000 0.95 1.03 1.11 Application Example 5 P14 GD1 1000 1.10 0.90 1.08 Application Example 6 P15 GD1 1000 1.12 1.18 1.17 Application Example 7 P2 GD1 1000 1.03 1.06 0.90 Application Example 8 P3 GD1 1000 1.04 1.31 1.06 Application Example 9 P4 GD1 1000 1.21 1.65 1.00 Application Example 10 P5 GD1 1000 1.04 1.02 0.91 Application Example 11 P6 GD1 1000 0.81 1.09 1.12 Application Example 12 P7 GD1 1000 0.56 1.01 1.01 Application Example 13 P72 GD1 1000 0.61 0.92 1.06 Comparative Application Example 1 GHD1 GD1 1000 1.27 0.79 0.46 Comparative Application Example 2 GHD2 GD1 1000 1.31 0.67 0.71

[0196] As can be seen from the above, this invention designs the structure of triphenylene compounds so that the indole-carbazole group attached to the triphenylene and another group (Ar1, Ar2) not selected from H or D are connected in the ortho position. In this way, the two groups are in a relatively parallel position, resulting in a more flat molecular structure, higher charge mobility, and better film-forming properties. This makes it suitable as the main material for the light-emitting layer of organic electroluminescent devices, enabling the organic electroluminescent devices to have lower driving voltage, higher current efficiency, and longer lifespan.

[0197] A comparison of Application Examples 1-11 and 12-13 shows that when Ar2 in the triphenylene compound is selected from H, the organic electroluminescent device prepared by using this triphenylene compound as the main material of the invention layer has a lower driving voltage.

[0198] As can be seen from Application Examples 8-9, when the triphenylene compounds have the structures of formulas I-3 and I-4, the prepared organic electroluminescent devices have high current efficiency.

[0199] As can be seen from the above, this invention designs the structure of triphenylene compounds to make them suitable as the main material for the light-emitting layer of organic electroluminescent devices, thereby enabling organic electroluminescent devices to have lower driving voltage, higher current efficiency, and longer lifespan.

[0200] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A triphenylene derivative compound, characterized in that, The triphenylene compounds have the structure shown in Formula I: Where ring A has the structure shown in formula I-1, ring A is fused with the two adjacent benzene rings, and the dashed lines represent the fusion sites; Ar1 and Ar2 are selected from -H or -D, and the other is selected from C6-C40 aryl or C6-C30 heteroaryl. R1 is selected from any one of C6-C40 aryl or C6-C30 heteroaryl; In compounds of formula I, each hydrogen atom can be independently substituted by at least one of -D, -CN, -F, C6-C20 aryl, C1-C12 alkyl, or C1-C12 alkoxy.

2. The triphenylene derivative compound according to claim 1, characterized in that, The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, naphthylphenyl, anthracene, phenanthrene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthreneyl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthylfluorenyl. Preferably, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, or dinaphthothiophenyl; Preferably, the C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, triphenylene, or fluoranthracene. 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, pentoxy, or hexoxy.

3. The triphenylene derivative compound according to claim 1 or 2, characterized in that, The triphenylene compounds have any one of the structures shown in Formulas I-1 to I-6: R1, Ar1, and Ar2 have the same definitions as in claim 1.

4. The triphenylene derivative compound according to any one of claims 1-3, characterized in that, The Ar1 is selected from C6-C40 aryl or C6-C30 heteroaryl, and the Ar2 is selected from -H or -D; Preferably, Ar2 is selected from C6-C40 aryl or C6-C30 heteroaryl, and Ar1 is selected from -H or -D; Preferably, Ar1 is selected from -H or -D, and Ar2 is selected from any one or a combination of at least two of carbazolyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, and dibenzothiopheneyl. Preferably, the Ar2 is selected from -H or -D, and the Ar1 is selected from any one or a combination of at least two of phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl or carbazoleyl.

5. The triphenylene derivative compound according to any one of claims 1-4, characterized in that, R1 is selected from any one of phenyl, naphthyl, biphenyl, carbazole, dibenzofuranyl or dibenzothiophenyl, preferably phenyl; Preferably, each hydrogen atom in the compound of formula I can be independently substituted by at least one of -D, -CN, -F, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, tert-butyl, hexyl, methoxy, ethoxy, or propoxy. Preferably, each hydrogen atom in the compound of formula I can be independently substituted by at least one of -D, -CN, -F, phenyl, naphthyl, biphenyl, tert-butyl, ethyl, methoxy, or propoxy.

6. The triphenylene derivative compound according to any one of claims 1-5, characterized in that, The triphenylene compounds are selected from the following substituted or unsubstituted compounds: The substitution refers to the fact that each hydrogen atom in the aforementioned triphenylene compounds can be independently replaced by a deuterium atom.

7. An intermediate, characterized in that, The intermediate has the structure shown in equation MA: Wherein, ring A has the same definition as in claim 1; One of X1 and X2 is selected from any one of -F, -Cl, -Br or I, and the other is selected from -H or -D; The intermediate is used to prepare the triphenylene compounds as described in any one of claims 1-6.

8. The intermediate according to claim 7, characterized in that, X2 is selected from one of F, Cl, Br, and I, and X1 is selected from -H or -D; Preferably, X1 is selected from one of F, Cl, Br, and I, and X2 is selected from -H or -D; Preferably, the intermediate comprises the following compounds:

9. 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 organic thin film layer comprises a triphenylene compound as described in any one of claims 1-6; As a preferred embodiment of the present invention, the organic thin film layer includes a light-emitting layer; The main material of the light-emitting layer includes the triphenylene compounds as described in any one of claims 1-6; Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

10. The organic electroluminescent device according to claim 9, characterized in that, The organic electroluminescent device is a green organic electroluminescent device.

Images