Triphenylene compound, intermediate, composition and organic electroluminescent device

Abstract

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

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescent materials, and in particular relates to a triphenylene compound, an intermediate, a composition and an organic electroluminescent device. Background Art

[0002] The structure of an organic electroluminescent device specifically consists of an anode, a cathode, and an organic layer between them. To improve the efficiency and stability of organic electroluminescent elements, the organic material layer includes multiple layers made of different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, a light-emitting layer, an electron transport layer (ETL), and an electron injection layer (EIL). Currently, organic electroluminescence has become a mainstream display technology, and accordingly, various new OLED materials have also been developed.

[0003] In order to meet people's higher requirements for OLED devices, the field urgently needs to develop more types of materials to improve the performance of OLED devices in terms of current efficiency, lifespan, etc. Summary of the Invention

[0004] To address the shortcomings of the prior art, the present invention provides a triphenylene compound, intermediate, composition, and organic electroluminescent device. By designing the structure of the compound, the present invention makes it suitable as a host material for the phosphorescent light-emitting layer of an organic electroluminescent device, thereby enabling the device to have a lower driving voltage, higher current efficiency, and longer life.

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

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

[0007]

[0008] Wherein, in the compound of formula I and the compound of formula II, Ar is independently selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group;

[0009] In the compounds of formula I and formula II, A1, A2, and A3 are each independently selected from N or CR, and at least one is selected from N, and R is selected from any one of H, C6-C20 aryl, or C1-C12 alkyl;

[0010] In the compounds of formula I and formula II, R1, R2, and R3 are each independently selected from any one of H, C6-C40 aryl, C6-C30 heteroaryl, and C1-C12 alkyl;

[0011] The hydrogen atoms in the compounds of formula I and formula II can each independently be substituted by at least one of a deuterium atom (D), -F, -CN, a C6-C20 aryl group, a triphenylmethyl group, a triphenylsilyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0012] The present invention designs the structure of the compound so that it is suitable for use as a host material of a phosphorescent light-emitting layer of an organic electroluminescent device, thereby enabling the organic electroluminescent device to have a lower driving voltage, higher current efficiency and longer life.

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

[0016] C1-C12 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12. It should be noted that, in the present invention, "D" represents a deuterium atom, and the same applies hereinafter.

[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 arylene group is selected from phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrenyl, fluorenylene, benzofluorenylene, dibenzofluorenylene, naphthofluorenylene, pyrenylene, perylene, spirofluorenylene, triphenylene, fluoranthenylene, hydrogenated benzanthrylene, indenylene, benzoindenylene, dibenzoindenylene, naphthofluorenylene, tetraphenylmethane or any one or a combination of at least two of benzonaphthofluorenyl.

[0019] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of a carbazolyl group, a dibenzothiophenyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group or a dinaphthothiophenyl group.

[0020] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, fluorenyl, triphenylene or fluoranthenyl.

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

[0022] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl and adamantyl.

[0023] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and octyloxy.

[0024] As a preferred technical solution of the present invention, Ar 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 triphenylene group, a fluoranthenyl group, an indenofluorenyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group or a carbazolyl group.

[0025] As a preferred technical solution of the present invention, Ar is selected from at least one of a single bond, a phenylene group, a carbazolylene group, a naphthylene group, a 9,9-dimethylfluorenyl group, a dibenzothiophenylene group, a dibenzofuranyl group or a biphenylene group.

[0026] Preferably, the R is selected from any one of H, methyl or phenyl;

[0027] Preferably, R1 and R2 are each independently selected from any one of H, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9-dimethylfluorenyl, methyl, tert-butyl, methoxy, triphenylmethyl, and triphenylsilyl.

[0028] Preferably, R3 is selected from any one of phenyl, naphthyl, biphenyl, ethyl, and tert-butyl.

[0029] As a preferred technical solution of the present invention, one of A1, A2, and A3 is selected from N, and the other two are CR.

[0030] Preferably, two of A1, A2, and A3 are selected from N, and the other one is CR.

[0031] Preferably, A1, A2, and A3 are all selected from N.

[0032] It should be noted that R has the same definition as above.

[0033] As a preferred technical solution of the present invention, the hydrogen atoms in the compounds of Formula I and Formula II can each independently be substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, carbazolyl, triphenylmethyl, triphenylsilyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy.

[0034] As a preferred technical solution of the present invention, the triphenylene compound is selected from any one of the following substituted or unsubstituted compounds:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] The substitution means that the hydrogen atoms in the above-mentioned triphenylene compounds can be independently replaced by deuterium atoms. Preferably, the triphenylene compounds are selected from any one of the following compounds:

[0041]

[0042]

[0043] It should be noted that the present invention does not have any special restrictions on the preparation method of the above-mentioned triphenylene compounds, and the preparation methods commonly used in the art are applicable. For example, the preparation method of the compound of formula I provided by the present invention comprises the following steps:

[0044]

[0045] Wherein, X and Y are each independently selected from any one of fluorine, chlorine, bromine or iodine;

[0046] Ar, A1, A2, A3, R1, and R2 have the same meanings as above.

[0047] In a second aspect, the present invention provides an intermediate comprising a compound having a structure as shown in Formula M1:

[0048]

[0049] Wherein, X is selected from any one of fluorine, chlorine, bromine or iodine;

[0050] Ar, A1, A2, A3 have the same definitions as above;

[0051] The intermediate is used to prepare the triphenylene compound as described in the first aspect.

[0052] Preferably, the intermediate includes the following compounds:

[0053]

[0054] In a third aspect, the present invention provides a composition comprising a first component and a second component;

[0055] The first component includes the triphenylene compound as described in the first aspect;

[0056] The second component includes a compound having a structure shown in the following formula III:

[0057]

[0058] Among them, Ar 21 、Ar 22 Each is independently selected from C6-C30 aryl or C6-C20 heteroaryl;

[0059] Ar 23 Any one selected from a single bond, a phenylene group or a biphenylene group;

[0060] The hydrogen atoms in the compound of formula III may be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl or C1-C6 alkoxy.

[0061] Preferably, the Ar 21 、Ar 22 Each is independently selected from any one of phenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl and triphenylene.

[0062] Preferably, the hydrogen atoms in the compound of formula III may be substituted by at least one of -F, -CN, phenyl, biphenyl, naphthyl, triphenylene, methyl, and ethyl.

[0063] As a preferred technical solution of the present invention, the compound of formula III is selected from any one of the following substituted or unsubstituted compounds:

[0064]

[0065]

[0066] The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

[0067] Preferably, the compound of formula III is selected from any one of the following substituted or unsubstituted compounds H-1 to H-40, H-17o, and H-17m:

[0068]

[0069]

[0070] The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

[0071] It should be noted that there is no particular limitation on the preparation method of the compound of formula III in the present invention, and any commonly used preparation method in the art is applicable.

[0072] In a fourth aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0073] The organic thin film layer material includes the triphenylene compound described in the first aspect and / or the composition described in the third aspect.

[0074] 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 compound described in the first aspect and / or the composition described in the third aspect.

[0075] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0076] As a preferred technical solution of the present invention, the organic electroluminescent device is a green organic electroluminescent device.

[0077] The luminescent layer of the present invention includes a luminescent layer host material and a dopant material, wherein the dopant material is also called a dye or a phosphorescent luminescent material. The luminescent layer host material can be a single compound or a mixture of two or more compounds.

[0078] 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, a yellow phosphorescent light-emitting layer, and a blue phosphorescent light-emitting layer.

[0079] The volume percentage of the main material in the phosphorescent light-emitting 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%.

[0080] In the present invention, the doping material for the light-emitting layer may be a phosphorescent material, which is also called a triplet light-emitting material and refers to a substance that emits light from a triplet excited state. The specific choice of phosphorescent material in the present invention is not particularly limited, and any doping material for the light-emitting layer commonly used in the art is applicable, including but not limited to a compound having the structure shown in the following formula PD:

[0081]

[0082] wherein M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu, or Au;

[0083] Y1-Y4 are each independently selected from carbon or nitrogen;

[0084] 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;

[0085] Cy1 and Cy2 are each independently selected from any one of phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothiophenyl, isobenzothiophenyl, benzimidazolyl, benzoxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazinyl, dibenzothiophenyl, and N-heterocarbazolyl, wherein Cy1 and Cy2 may be optionally linked to each other via a single bond or an organic linking group;

[0086] 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;

[0087] R 91 and R 92Each is 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 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C6 C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkenyl, substituted or unsubstituted 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, 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 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.

[0088] a1 and a2 are each independently an integer selected from 1 to 5, for example, 1, 2, 3, 4 or 5;

[0089] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0090] a is selected from 1, 2 or 3;

[0091] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0092] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] 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.

[0100] The hole injection layer material includes a P-type dopant. The P-type dopant coexists with the hole injection layer material in the OLED device and is capable of oxidizing the hole injection layer material, thereby acting as an electron acceptor and promoting the migration of holes from the hole injection layer toward 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 even more preferably greater than 0.2eV.

[0101] The P-type dopant is present in the hole injection layer at 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. For example, compounds D-1 to D-13 disclosed in CN113728453A or compounds HI-1 to HI-9 described below may be used:

[0102]

[0103]

[0104] 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:

[0105]

[0106] 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 group, a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl group;

[0107] Ar 41 、Ar42 each independently 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;

[0108] 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, naphthyl, triphenylene, fluoranthenyl, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted group (the substituted substituent is phenyl), substituted or unsubstituted dibenzothienyl (the substituted substituent is phenyl), 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.

[0109] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) further includes a compound having a structure as shown in the following formula IA or a compound having a structure as shown in the following formula IB:

[0116]

[0117] wherein L is selected from any one of a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40) arylene group, a dibenzofuranyl group, or a dibenzothiophenyl group;

[0118] 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;

[0119] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0120] 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, dibenzofuran group, or dibenzothiophenyl group;

[0121] 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.

[0122] R, R1, and R2 are each independently selected from any one of a C1-C20 (e.g., C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20) alkyl group, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40) aryl group, a dibenzofuranyl group, or a dibenzothiophenyl group;

[0123] H in the compound of formula IB and the compound of formula IA may each independently be replaced by at least one of -F, -CN, -D (deuterium atom), C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0124] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0125] 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 fluoranthenyl.

[0126] Preferably, L, Ar1, and Ar2 are each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylene, spirofluorenyl, indenofluorenyl, and hydrogenated benzanthryl.

[0127] Preferably, the compound of formula IB is selected from the following structures:

[0128]

[0129] Wherein, L is phenylene;

[0130] Ar1, Ar2, and m have the same meanings as above.

[0131] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0132]

[0133]

[0134]

[0135]

[0136]

[0137] In the OLED device provided by the present invention, the hole layer material, in addition to the compound of formula HT-GH4, the compound of formula IB, and the compound of formula IA, may also include conventional hole materials in the art, without particular limitation. Exemplary examples include, but are 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 (the absolute value is smaller), and they are 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.

[0138] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0139]

[0140] Among them, Ar 601 ~Ar 609 Each independently selected from a substituted or unsubstituted C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted naphthobenzofuranyl group, a substituted or unsubstituted naphthobenzothiophenyl group, a substituted or unsubstituted dinaphthofuranyl group, or a substituted or unsubstituted dinaphthothiophenyl group;

[0141] 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;

[0142] R 701 、R 702 、R 703 is 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.

[0143] A hole-blocking layer (HBL) can confine holes and / or excitons within the emitting layer (EL) to improve device current efficiency and lifetime. Compared to the EL material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or higher triplet energy.

[0144] 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 limitation on the ETL material, and any metal complex or organic compound may be used as long as it can transport electrons. Generally, the electron transport layer material contains at least one of the following structural fragments: pyridine structure, pyrimidine structure, triazine structure, benzimidazole structure, benzoxazole structure, benzothiazole structure, N-naphthalene structure, N-heterophthalene structure, N-heterocarbazole structure, and N-heterodibenzothiophene structure.

[0145] In the present invention, there is no particular limitation on the materials of the electron transport layer, and examples thereof include but are not limited to:

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] In the present invention, the cathode material is a metal with a 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 (e.g., an alloy composed of an alkali metal or alkaline earth metal and silver, e.g., 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, may also be used. In this case, combinations of these metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag.

[0155] Alternatively, a thin intermediate layer of a material with a high dielectric constant may be introduced between the metal cathode and the organic semiconductor to form a multilayer structure. The material with a high dielectric constant may also be referred to as an electron injection material, and may be fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ).

[0156] Compared with the prior art, the present invention has the following beneficial effects:

[0157] The present invention designs the structure of the compound so that it is suitable for use as a host material of a phosphorescent light-emitting layer of an organic electroluminescent device, thereby enabling the organic electroluminescent device to have a lower driving voltage, higher current efficiency and longer life. DETAILED DESCRIPTION

[0158] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0159] Preparation Example 1

[0160] This preparation example provides intermediate P1-1, the synthesis method of which is as follows:

[0161]

[0162] Under nitrogen protection, 80 mL of dioxane was added to a 250 mL three-necked flask in sequence, followed by 4.2 g of the compound represented by M1-0, 3.9 g of the compound represented by M1-1, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium. The temperature was slowly raised to 40°C for reaction for 2 hours, then raised to 60°C for reaction for 4 hours, then raised to reflux for reaction for 2 hours, cooled to room temperature, and separated by adding water and dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, and after removing the desiccant, concentrated to dryness, and crystallized from a mixed solvent of toluene and chloroform to obtain 5.1 g of intermediate P1-1.

[0163] The obtained intermediate P1-1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 645.20.

[0164] Preparation Example 2-5

[0165] Preparation Examples 2-5 respectively provide an intermediate, the structural formula of the intermediate is shown in Table 1 below, and the corresponding intermediate is synthesized by raw material 1 and raw material 2. The synthesis method refers to the synthesis method in Preparation Example 1, and the obtained intermediates are respectively subjected to mass spectrometry detection, and the measured mass-to-charge ratio (m / z) is shown in Table 1 below.

[0166] Table 1

[0167]

[0168] Synthesis Example 1

[0169] This synthesis example provides compound P1 and its synthesis method, which is as follows:

[0170]

[0171] Under a nitrogen atmosphere, dry xylene (100 mL), intermediate P1-1 (6.5 g), carbazole (1.8 g), Pd(dba)2 (bis(dibenzylideneacetonepalladium, 0.1 g), 10% tri-tert-butylphosphine toluene solution (the mass of tri-tert-butylphosphine solution is 0.8 g) and sodium tert-butoxide (1.2 g) were added to a 250 mL three-necked flask. The mixture was heated to reflux temperature and reacted for 8 h. The mixture was cooled to room temperature and separated by water. The organic layer was then washed with water until neutral, dried over magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography with petroleum ether: ethyl acetate: dichloromethane = 20:1:0.5 (volume ratio) to give compound P1 (5.3 g).

[0172] Compound P1 was detected by mass spectrometry: the mass-to-charge ratio (m / z) was measured to be 776.29.

[0173] Synthesis Examples 2-6

[0174] Synthesis Examples 2-6 respectively provide a compound and a synthesis method thereof. The structural formula of the compound is shown in Table 2 below. The corresponding compound is synthesized by raw material 3 and raw material 4. The synthesis method refers to the synthesis method in Synthesis Example 1, and the obtained compounds are respectively subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) is measured as shown in Table 2 below.

[0175] Table 2

[0176]

[0177]

[0178] Synthesis Example 7

[0179] This synthesis example provides compound P20 and its synthesis method, which is as follows:

[0180]

[0181] Under nitrogen atmosphere, to a 500 mL three-necked flask were added intermediate P1-1 (6.5 g), 9-phenylcarbazole-3-boronic acid (3.0 g), 160 mL of isopropanol, triethylamine (2.2 g), 0.1 g of bis(1,5-cyclooctadiene)nickel (0), and 0.18 g of triphenylphosphine. The temperature was raised to 35° C. for reaction for 8 hours, and then raised to 50° C. for reaction for 4 hours. Water and ethyl acetate were added for separation. The organic layer was washed with water until neutral, dried over anhydrous magnesium sulfate, filtered to remove the desiccant, concentrated to dryness, and separated by silica gel column chromatography with petroleum ether:ethyl acetate:dichloromethane = 20:1:0.5 (volume ratio) to obtain compound P20 (5.8 g).

[0182] The obtained compound P20 was detected by mass spectrometry, and the m / z was 852.33.

[0183] Other compounds for which the specific synthesis methods are not listed can be synthesized by referring to the above examples in combination with common knowledge in the art.

[0184] The specific structures of some of the compounds used in the following application examples and comparative application examples of the present invention are as follows:

[0185]

[0186]

[0187]

[0188] Application Example 1

[0189] This application example provides a green organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer. The structure of the green organic electroluminescent device is:

[0190] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / host material: PGD-1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0191] The preparation method of the green organic electroluminescent device is as follows:

[0192] 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 to prepare OLED devices.

[0193] PGD-1 [5%] refers to the dye doping ratio, meaning the volume ratio of the host material to the dye PGD-1 is 95:5. HT-1:HI-2 [5%] refers to the ratio of the p-type dopant, meaning the volume ratio of the hole-transporting material HT-1 to the p-type dopant HI-2 is 95:5. HT-1 is a hole-transporting material; HT-1:HI-2 [5%] serves as the hole-injection layer, and EB-1 is the electron-blocking layer.

[0194] The main material of the light-emitting layer of the green organic electroluminescent device provided in this application example is compound P1.

[0195] Application Example 2-21, Comparative Application Example 1-4

[0196] Application Examples 2-21 and Comparative Application Examples 1-4 respectively provide a green organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is replaced with other compounds (see Table 3 below for details). Other preparation steps and conditions are the same as those of Application Example 1.

[0197] Performance Testing

[0198] The brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the current efficiency is the brightness of 1000cd / 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 is constant. The driving voltage, current efficiency and LT95 are relative values. The specific test results are shown in Table 3 below:

[0199] Table 3

[0200] Main material <![CDATA[Brightness / (cd / m 2 )]]> Driving voltage Current efficiency LT95 Application Example 1 P1 1000 1 1 1 Application Example 2 P1D 1000 1.02 1.03 1.28 Application Example 3 P2 1000 1.11 1.12 1.09 Application Example 4 P3 1000 0.89 1.09 1.27 Application Example 5 P4 1000 1.00 1.09 1.31 Application Example 6 P5 1000 1.07 1.02 1.53 Application Example 7 P6 1000 1.06 1.11 1.27 Application Example 8 P7 1000 1.09 1.38 1.31 Application Example 9 P8 1000 1.09 1.57 1.12 Application Example 10 P9 1000 0.92 1.03 1.89 Application Example 11 P10 1000 0.87 1.19 0.96 Application Example 12 P11 1000 0.79 1.58 1.98 Application Example 13 P12 1000 0.90 1.02 0.87 Application Example 14 P13 1000 0.97 1.21 1.12 Application Example 15 P14 1000 1.18 1.09 1.12 Application Example 16 P15 1000 1.16 1.23 2.08 Application Example 17 P16 1000 0.97 1.10 1.16 Application Example 18 P17 1000 0.98 1.62 1.12 Application Example 19 P18 1000 1.10 0.98 1.20 Application Example 20 P19 1000 1.02 0.91 1.29 Application Example 21 P21 1000 1.01 1.02 1.37 Comparative Application Example 1 D1 1000 1.28 0.78 0.82 Comparative Application Example 2 D2 1000 1.22 0.69 0.80 Comparative Application Example 3 D3 1000 1.30 0.89 0.71 Comparative Application Example 4 D4 1000 1.38 1.09 0.72

[0201] From the above, it can be seen that the present invention designs the structure of the compound to make it suitable as the host material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0202] From the comparison between Application Examples 1-21 and Comparative Application Examples 1-2, it can be seen that the present invention, by providing two biphenyl groups on the A1, A2, and A3 rings and using this compound as the main material of the organic electroluminescent device, can further reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and LT95 life of the organic electroluminescent device.

[0203] From the comparison of Application Examples 1-21 and Comparative Application Example 3, it can be seen that the present invention, by providing two biphenyl groups on the rings containing A1, A2, and A3, and providing the connection site of one of the biphenyl groups to the rings containing A1, A2, and A3 at the meta position, uses this compound as the main material of the organic electroluminescent device, which can further reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and LT95 life of the organic electroluminescent device.

[0204] From the comparison of Application Examples 1-21 and Comparative Application Example 4, it can be seen that if Ar in the compound of Formula I and the compound of Formula II is not selected from a single bond, the prepared device can reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and LT95 life of the organic electroluminescent device compared to D4.

[0205] Application Example 22, Comparative Application Example 5

[0206] Application Example 22 and Comparative Application Example 5 each provide a green organic electroluminescent device. The only difference from Application Example 1 is that the main material of the light-emitting layer is replaced with other compounds (see Table 4 below for details). The other preparation steps and conditions are the same as those of Application Example 1.

[0207] Performance Testing

[0208] The brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the current efficiency is the brightness of 1000cd / 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 is constant. The driving voltage, current efficiency and LT95 are relative values. The specific test results are shown in Table 4 below:

[0209] Table 4

[0210] Main material <![CDATA[Brightness / (cd / m 2 )]]> Voltage Current efficiency LT95 Application Example 22 P20 1000 1 1 1 Comparative Application Example 5 D5 1000 1.09 0.87 0.78

[0211] From the comparison between Application Example 22 and Comparative Application Example 5, it can be seen that the present invention, by arranging two specific biphenyl groups on the A1, A2, and A3 rings and using this compound as the main material of the organic electroluminescent device, can further reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and LT95 life of the organic electroluminescent device.

[0212] Application Example 23, Comparative Application Example 6

[0213] Application Example 23, Comparative Application Example 6

[0214] A green organic electroluminescent device is provided respectively. The only difference from Application Example 1 is that the main material of the light-emitting layer is two components, and the volume ratio of the two components is 1:1 (see Table 5 below for details). Other preparation steps and conditions are the same as those in Application Example 1.

[0215] Performance Testing

[0216] The brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent device provided above were tested, wherein the current efficiency is the brightness of 1000cd / 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 remains unchanged. The driving voltage, current efficiency and LT95 are relative values. The specific test results are shown in Table 5 below:

[0217] Table 5

[0218] Main material 1 Main material 2 <![CDATA[Brightness / (cd / m 2 )]]> Current efficiency LT95 Application Example 23 P1 H-26 1000 1 1 Comparative Application Example 6 D3 H-26 1000 0.76 0.81

[0219] From the above, it can be seen that the present invention designs the structure of the compound to make it suitable as one of the main materials of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0220] From the comparison between Application Example 23 and Comparative Application Example 6, it can be seen that the present invention, by providing two biphenyl groups on the rings containing A1, A2, and A3, and providing the connection site between one of the biphenyl groups and the rings containing A1, A2, and A3 at the meta position, uses this compound as one of the main materials of the organic electroluminescent device, which can further reduce the driving voltage of the organic electroluminescent device and improve the current efficiency and LT95 life of the organic electroluminescent device.

[0221] In summary, the present invention designs the structure of the compound to make it suitable as the host material of the phosphorescent light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0222] The applicant declares that the present invention uses the above-described embodiments to illustrate the detailed process flow of the present invention, but the present invention is not limited to the above-described detailed process flow, that is, it does not mean that the present invention must rely on the above-described detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for various raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A triphenylene compound, characterized in that The compound has the structure shown in the following formula I or formula II: Wherein, in the compound of formula I and the compound of formula II, Ar is independently selected from any one of a single bond, a C6-C40 arylene group or a C6-C30 heteroarylene group; In the compounds of formula I and formula II, A1, A2, and A3 are each independently selected from N or CR, and at least one is selected from N, and R is selected from any one of H, C6-C20 aryl, or C1-C12 alkyl; In the compounds of formula I and formula II, R1, R2, and R3 are each independently selected from any one of H, C6-C40 aryl, C6-C30 heteroaryl, and C1-C12 alkyl; The hydrogen atoms in the compounds of formula I and formula II may each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a triphenylmethyl group, a triphenylsilyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

2. The triphenylene compound according to claim 1, wherein The C6-C40 arylene group is selected from any one or a combination of at least two of phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrenyl, fluorenylene, benzofluorenylene, dibenzofluorenylene, naphthofluorenylene, pyrenylene, perylene, spirofluorenylene, triphenylene, fluoranthenylene, hydrobenzoanthrylene, indenofluorenylene, benzoindenofluorenylene, dibenzoindenofluorenylene, naphthofluorenylene, tetraphenylmethane or benzonaphthofluorenylene; Preferably, the C6-C30 heteroarylene group is selected from any one of a carbazolylene group, a dibenzothiophenylene group, a dibenzofuranyl group, a naphthobenzofuranyl group, a naphthobenzothiophenylene group, a dinaphthofuranyl group or a dinaphthothiophenylene group; Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, fluorenyl, triphenylene or fluoranthenyl; Preferably, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzothiophenyl, dibenzofuranyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl; Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl and adamantyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and octyloxy.

3. The triphenylene compound according to claim 1 or 2, characterized in that Ar 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 triphenylene group, a fluoranthenyl group, an indenofluorenyl group, a dibenzothienyl group, a naphthobenzofuranyl group, a naphthobenzothienyl group, or a carbazolyl group; As a preferred embodiment of the present invention, Ar is selected from at least one of a single bond, a phenylene group, a carbazolyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a dibenzothiophenyl group, a dibenzofuranyl group or a biphenylene group; Preferably, the R is selected from any one of H, methyl or phenyl; Preferably, R1 and R2 are each independently selected from any one of H, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9-dimethylfluorenyl, methyl, tert-butyl, methoxy, triphenylmethyl, and triphenylsilyl; Preferably, R3 is selected from any one of phenyl, naphthyl, biphenyl, ethyl, and tert-butyl.

4. The triphenylene compound according to any one of claims 1 to 3, characterized in that One of A1, A2, and A3 is selected from N, and the other two are CR; Preferably, two of A1, A2, and A3 are selected from N, and the other is CR; Preferably, A1, A2, and A3 are all selected from N.

5. The triphenylene compound according to any one of claims 1 to 4, characterized in that The hydrogen atoms in the compound of formula I and the compound of formula II can each independently be substituted by at least one of a deuterium atom, -F, -CN, a phenyl group, a naphthyl group, a biphenyl group, a carbazolyl group, a triphenylmethyl group, a triphenylsilyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

6. The triphenylene compound according to any one of claims 1 to 5, characterized in that The triphenylene compound is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the triphenylene compound can be independently replaced by deuterium atoms.

7. An intermediate, characterized in that The intermediate includes a compound having a structure as shown in Formula M1: Wherein, X is selected from any one of fluorine, chlorine, bromine or iodine; Ar, A1, A2, A3 have the same definitions as in claim 1; The intermediate is used to prepare the triphenylene compound according to any one of claims 1 to 6; Preferably, the intermediate includes the following compounds:

8. A composition, characterized in that The composition includes a first component and a second component; The first component comprises the triphenylene compound according to any one of claims 1 to 6; The second component includes a compound having a structure shown in the following formula III: Among them, Ar 21 、Ar 22 Each is independently selected from C6-C30 aryl or C6-C20 heteroaryl; Ar 23 Any one selected from a single bond, a phenylene group or a biphenylene group; The hydrogen atoms in the compound of formula III may be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl or C1-C6 alkoxy; Preferably, the Ar 21 、Ar 22 Each is independently selected from any one of phenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl and triphenylene; Preferably, the hydrogen atoms in the compound of formula III may be substituted by at least one of -F, -CN, phenyl, biphenyl, naphthyl, triphenylene, methyl, and ethyl.

9. The composition according to claim 8, characterized in that The compound of formula III is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the above compounds can each independently be replaced by a deuterium atom; Preferably, the compound of formula III is selected from any one of the following substituted or unsubstituted compounds H-1 to H-40, H-17o, and H-17m: The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

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 material comprises the triphenylene compound according to any one of claims 1 to 6 and / or the composition according to claim 8 or 9; Preferably, the organic thin film layer comprises a light-emitting layer, and a host material of the light-emitting layer comprises the compound according to any one of claims 1 to 6 and / or the composition according to claim 8 or 9.

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