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 triphenylene compound is designed, so that the triphenylene 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 low driving voltage, relatively high current efficiency and relatively long service life.

Description

Technical Field

[0001] The 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] In response to the shortcomings of the prior art, the present invention provides a triphenylene compound, intermediate, composition, and organic electroluminescent device. The present invention designs the structure of the triphenylene compound to make it suitable as a host material for the 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.

[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 one of ring A and ring B is selected from a benzene ring, and the other is selected from a naphthalene ring;

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

[0010] Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl;

[0011] A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, C6-C20 aryl or C1-C12 alkyl;

[0012] R1, R2, and R3 are each independently selected from any one of H, C6-C40 aryl, C6-C30 heteroaryl, and C1-C12 alkyl;

[0013] 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.

[0014] The present invention designs the structure of the triphenylene compound so that it is suitable as the main 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.

[0015] In the present invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0016] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0017] C6-C20 can be C6, C8, C10, C12, C16 or C20, etc.

[0018] 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.

[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. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0020] 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.

[0021] 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 naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolyl group.

[0022] As a preferred technical solution of the present invention, the C6-C40 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthacenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzoanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthacenyl, tetraphenylmethane or benzonaphthofluorenyl.

[0023] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzothiophenyl, dibenzofuranyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl, or a combination of at least two thereof.

[0024] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, fluorenyl, triphenylene or fluoranthenyl.

[0025] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, octyl and adamantyl.

[0026] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and octyloxy.

[0027] As a preferred technical solution of the present invention, 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 dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group or a carbazolylene group.

[0028] As a preferred embodiment 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, and a biphenylene group.

[0029] As a preferred technical solution of the present invention, Ar1 and Ar2 are each independently selected from any one or a combination of at least two of H, phenyl, carbazolyl, biphenyl, 9,9-dimethylfluorenyl, naphthyl, triphenylene, fluoranthenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl.

[0030] As a preferred technical solution of the present invention, Ar1 and Ar2 are each independently selected from at least one of H, phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthenyl.

[0031] Preferably, one of A1, A2, and A3 is selected from N, and two of them are CR.

[0032] Preferably, two of A1, A2, and A3 are selected from N, and one is CR.

[0033] Preferably, A1, A2, and A3 are all selected from N.

[0034] Preferably, the R is selected from any one of H, phenyl or biphenyl.

[0035] Preferably, R1, R2, and R3 are each independently selected from any one of H, phenyl, biphenyl, naphthyl, and dibenzofuranyl.

[0036] As a preferred technical solution of the present invention, 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 -D, -F, -CN, phenyl, naphthyl, biphenyl, triphenylmethyl, triphenylsilyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy.

[0037] Preferably, 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 -D, -F, -CN, phenyl, naphthyl, methyl, ethyl, tert-butylmethoxy, ethoxy, and propoxy.

[0038] As a preferred technical solution of the present invention, the triphenylene compound has a structure shown in Formula I.

[0039] As a preferred technical solution of the present invention, the triphenylene compound is selected from any one of the following substituted or unsubstituted compounds:

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] The substitution means that the hydrogen atoms in the above compounds can be independently replaced by deuterium atoms. Preferably, the triphenylene compound is selected from any one of the following compounds:

[0047]

[0048]

[0049] 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. The preparation method of the compound of formula I provided by the present invention is illustrated by way of example:

[0050]

[0051] Wherein, Y is selected from any one of fluorine, chlorine, bromine and iodine;

[0052] Ar, Ar1, Ar2, A1, A2, A3, R1, and R2 have the same meanings as above.

[0053] In a second aspect, the present invention provides an intermediate, comprising a compound having a structure shown in the following formula M1:

[0054]

[0055] Ar, Ar1, Ar2, A1, A2, and A3 have the same definitions as above; the hydrogen atoms in the compound of formula M may each independently be replaced by a deuterium atom; the intermediate does not include the following compounds:

[0056]

[0057] The intermediate is used to prepare the triphenylene compound as described in the first aspect. Preferably, the intermediate includes the following compounds:

[0058]

[0059] In a third aspect, the present invention provides a composition comprising a first component and a second component;

[0060] The first component includes the triphenylene compound as described in the first aspect;

[0061] The second component includes a compound having a structure shown in the following formula III:

[0062]

[0063] Among them, Ar 21 、Ar 22 Each is independently selected from C6-C30 aryl or C6-C20 heteroaryl;

[0064] Ar 23 Any one selected from a single bond, a phenylene group or a biphenylene group;

[0065] The hydrogen atoms in the compound represented by formula III may be substituted by at least one of -F, -CN, C6-C20 aryl, C1-C6 alkyl or C1-C6 alkoxy;

[0066] Preferably, the Ar 21 、Ar 22 Each is independently selected from any one of phenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl and triphenylene.

[0067] 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.

[0068] 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:

[0069]

[0070]

[0071] The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

[0072] Preferably, the compound represented by formula III is selected from any one of the following substituted or unsubstituted compounds H-1 to H-40, H-17o, and H-17m:

[0073]

[0074]

[0075] The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

[0076] It should be noted that there is no special limitation on the preparation method of the above-mentioned compounds in the present invention, and all commonly used preparation methods in the art are applicable.

[0077] 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;

[0078] The organic thin film layer material includes the triphenylene compound described in the first aspect and / or the composition described in the third aspect.

[0079] 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.

[0080] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0081] As a preferred technical solution of the present invention, the organic electroluminescent device is a red organic electroluminescent device.

[0082] 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.

[0083] 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.

[0084] 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%.

[0085] 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:

[0086]

[0087] wherein M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu, or Au;

[0088] Y1-Y4 are each independently selected from carbon or nitrogen;

[0089] 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;

[0090] 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;

[0091] 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;

[0092] R 91 and R 92 Each 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.

[0093] a1 and a2 are each independently an integer selected from 1 to 5, for example, 1, 2, 3, 4 or 5;

[0094] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0095] a is selected from 1, 2 or 3;

[0096] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0097] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] 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.

[0105] 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.

[0106] 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:

[0107]

[0108] 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:

[0109]

[0110] Among them, L 41is selected from a single bond, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, or a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0111] Ar 41 、Ar 42 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;

[0112] X is selected from CR 41 R 42 or NR 43 , where R 41 、R 42 、R 43 are each independently selected from any one of 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, R 41 、R 42 They can be linked to form rings via single bonds.

[0113] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0114]

[0115]

[0116] 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:

[0117]

[0118]

[0119] 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;

[0120] 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;

[0121] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0122] 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;

[0123] 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.

[0124] 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;

[0125] 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.

[0126] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0127] 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.

[0128] 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.

[0129] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0130]

[0131]

[0132]

[0133]

[0134] 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.

[0135] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0136]

[0137] 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;

[0138] And Ar 601 ~Ar 609 Ar atoms adjacent to or connected to the same N atom601 ~Ar 609 , can be connected by single key or through O, S, CR 701 R 702 NR 703 bridging;

[0139] 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.

[0140] 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.

[0141] 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.

[0142] In the present invention, there is no particular limitation on the electron transport layer materials, which exemplarily include but are not limited to:

[0143]

[0144]

[0145]

[0146] 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.

[0147] 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).

[0148] Compared with the prior art, the present invention has the following beneficial effects:

[0149] The present invention designs the structure of the triphenylene compound so that it is suitable as the main 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. DETAILED DESCRIPTION

[0150] 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.

[0151] Synthesis Example 1

[0152] This synthesis example provides compound P1 and its synthesis method, the synthesis method is as follows:

[0153]

[0154] (1) Synthesis of intermediate P1-1

[0155] Under nitrogen protection, 80 mL of dioxane was added to a 250 mL three-necked flask in sequence, followed by 2.7 g of intermediate M1-0, 3.9 g of intermediate 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, added with water and dichloromethane for separation, the organic layer was washed with water, dried with magnesium sulfate, the desiccant was removed, and concentrated to dryness. The mixture was crystallized with a mixed solvent of toluene and chloroform to obtain 3.6 g of intermediate P1-1.

[0156] The obtained intermediate P1-1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 493.13.

[0157] (2) Synthesis of compound P1

[0158] Under a nitrogen atmosphere, 100 mL of dry xylene, 5.0 g of intermediate P1-1, 2.2 g of 7H-benzo[c]carbazole, 0.1 g of Pd(dba)2 (bis(dibenzylideneacetonepalladium), 10% by mass of tri-tert-butylphosphine toluene solution (the mass of tri-tert-butylphosphine solution is 0.8 g), and 1.2 g of sodium tert-butoxide 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 obtain 4.7 g of compound P1.

[0159] Compound P1 was detected by mass spectrometry: the mass-to-charge ratio (m / z) was measured to be 674.25.

[0160] Synthesis Example 2-23

[0161] Synthesis Examples 2-23 respectively provide a compound, the specific structure of the compound is shown in Table 1, and the synthesis method of the compound refers to the synthesis method in Synthesis Example 1. The intermediate is first synthesized using raw material 1 (chloride or bromide) and M1-1, the mass spectrum of the intermediate is measured, and the mass-to-charge ratio (m / z) is recorded. Then, the intermediate is reacted with raw material 2 to prepare the compound, and the obtained compound is subjected to mass spectrometry detection. The measured mass-to-charge ratio (m / z) is shown in Table 1 below.

[0162] Table 1

[0163]

[0164]

[0165]

[0166]

[0167] Other compounds for which specific synthesis methods are not listed can be synthesized by referring to the above examples in combination with common knowledge in the art. 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:

[0168]

[0169] Application Example 1

[0170] This application example provides a red organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer. The structure of the red organic electroluminescent device is:

[0171] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / host material: PRD-1[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0172] The preparation method of the red organic electroluminescent device is as follows:

[0173] 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.

[0174] PRD-1[5%] refers to the dye doping ratio, meaning the volume ratio of the host material to the dye PRD-1 is 95:5. HT-1:HI-2[5%] refers to the p-type dopant ratio, 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.

[0175] The main material of the light-emitting layer of the red organic electroluminescent device provided in this application example is compound P1.

[0176] Application Example 2-20 vs. Application Example 1-2

[0177] Application Examples 2-20 and Comparative Application Examples 1-2 respectively provide a red 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 2 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0178] Performance Testing

[0179] 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 2 below:

[0180] Table 2

[0181] Main material <![CDATA[Brightness / (cd / m 2 )]]> Voltage Current efficiency LT95 Application Example 1 P1 1000 0.73 1.01 1.53 Application Example 2 P2 1000 0.89 1.07 1.45 Application Example 3 P3 1000 0.87 1.22 1.55 Application Example 4 P4 1000 0.89 0.99 1.99 Application Example 5 P5 1000 0.72 1.31 1.24 Application Example 6 P9 1000 0.55 1.10 1.19 Application Example 7 P10 1000 0.79 1.13 1.36 Application Example 8 P11 1000 0.89 1.75 1.41 Application Example 9 P12 1000 0.72 1.67 1.21 Application Example 10 P13 1000 0.92 1.07 1.21 Application Example 11 P14 1000 0.73 1.28 1.41 Application Example 12 P15 1000 0.73 1.12 2.63 Application Example 13 P16 1000 0.88 1.14 1.39 Application Example 14 P17 1000 0.68 1.03 1.22 Application Example 15 P18 1000 0.87 1.24 1.45 Application Example 16 P19 1000 0.89 1.07 1.48 Application Example 17 P20 1000 0.84 1.14 1.28 Application Example 18 P21 1000 0.9 1.14 1.36 Application Example 19 P22 1000 0.93 1.32 1.39 Application Example 20 P23 1000 0.82 1.02 1.28 Comparative Application Example 1 D1 1000 1 1 1 Comparative Application Example 2 D2 1000 1.09 0.88 0.65

[0182] As can be seen from the above, 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.

[0183] It can be seen from Application Example 6 that if a triphenylene compound in which one of Ar1 and Ar2 is a dibenzofuran group is selected, the driving voltage of the OLED device prepared from the compound is lower.

[0184] It can be seen from Application Examples 8-9 that if a triphenylene compound in which one of Ar1 and Ar2 is a carbazole group is selected, the OLED device prepared from the compound has a higher current efficiency.

[0185] It can be seen from Application Example 12 that if a triphenylene compound is selected in which one of R1 and R2 is H and the other is phenyl, the OLED device prepared from the compound has a longer lifespan.

[0186] As can be seen from Application Examples 1-20 and Comparative Application Example 1, the present invention designs the two substituents on the triphenylene group to be located at the ortho position, and uses such compounds as the main material of the light-emitting layer of the OLED device to prepare an OLED device with lower driving voltage, higher current efficiency and longer life.

[0187] As can be seen from Application Examples 1-20 and Comparative Application Example 2, the present invention designs a triphenylene compound in which ring A and ring B are phenyl and naphthyl respectively, and uses such a compound as the main material of the light-emitting layer of the OLED device to prepare an OLED device with lower driving voltage, higher current efficiency and longer life.

[0188] Application Examples 21-23 vs. Application Example 3

[0189] Application Examples 21-23 provide a red organic electroluminescent device in comparison with Application Example 3. The only difference from Application Example 1 is that the main material of the light-emitting layer is replaced by other compounds, and the dye is replaced by PRD-2 (see Table 3 below for details). The other preparation steps and conditions are the same as those of Application Example 1.

[0190] Performance Testing

[0191] 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:

[0192] Table 3

[0193] Main material <![CDATA[Brightness / (cd / m 2 )]]> Voltage Current efficiency LT95 Application Example 21 P6 1000 0.88 1.35 1.10 Application Example 22 P7 1000 0.77 1.39 1.46 Application Example 23 P8 1000 0.76 1.57 1.21 Comparative Application Example 3 D3 1000 1 1 1

[0194] It can be seen from Application Example 21 and Comparative Application Example 3 that the present invention designs the triphenylene compounds such that one of ring A and ring B is a phenyl group and the other is a naphthyl group, and uses such compounds as the main material of the light-emitting layer of the OLED device to prepare an OLED device with lower driving voltage, higher current efficiency and longer life.

[0195] It can be seen from Application Example 22 that when Ar1 and Ar2 are both selected from biphenyl groups, and the outer benzene ring of the biphenyl group in one of them (the benzene ring not directly connected to the triazine ring) is in the meta position with the triazine ring, and the outer benzene ring of the biphenyl group in the other is in the para position with the triazine ring, the life of the OLED device can be further improved.

[0196] It can be seen from Application Example 23 that when Ar1 and Ar2 are both selected from biphenyl groups, and the outer benzene ring in the biphenyl group (the benzene ring not directly connected to the triazine ring) and the triazine ring are both in the meta position, the current efficiency of the OLED device can be further improved.

[0197] It can be seen from Application Examples 21-23 that when Ar1 and Ar2 are both selected from biphenyl groups, and the outer benzene ring and the triazine ring in the biphenyl group are both in para position, the performance of the prepared OLED device is poor.

[0198] Application Example 24, Comparative Application Examples 4-5

[0199] Application Example 24 and Comparative Application Examples 4-5 respectively provide a red organic electroluminescent device. 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 is 1:1 (see Table 4 below for details). The other preparation steps and conditions are the same as those of Application Example 1.

[0200] Performance Testing

[0201] 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:

[0202] Table 4

[0203] Main material 1 Main material 2 <![CDATA[Brightness / (cd / m 2 )]]> Current efficiency LT95 Application Example 24 P1 H-26 1000 1 1 Comparative Application Example 4 D1 H-26 1000 0.78 0.89 Comparative Application Example 5 D2 H-26 1000 0.71 0.77

[0204] From the above, it can be seen that the present invention designs the structure of triphenylene compounds to make them suitable as one of the main materials of the phosphorescent light-emitting layer of organic electroluminescent devices, so that the organic electroluminescent devices have lower driving voltage, higher current efficiency and longer life.

[0205] In summary, the present invention designs the structure of triphenylene compounds to make them suitable as the host material of the phosphorescent light-emitting layer of organic electroluminescent devices, so that the organic electroluminescent devices have lower driving voltage, higher current efficiency and longer life.

[0206] 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 one of ring A and ring B is selected from a benzene ring, and the other is selected from a naphthalene ring; Ar is selected from any one of a single bond, a C6-C40 arylene group, or a C6-C30 heteroarylene group; Ar1 and Ar2 are each independently selected from any one of H, C6-C40 aryl or C6-C30 heteroaryl; A1, A2, A3 are each independently selected from N or CR, and at least one is selected from N; R is selected from any one of H, C6-C20 aryl or C1-C12 alkyl; 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 naphthobenzofuranyl group, a naphthobenzothiophenylene group, a dinaphthofuranyl group, a dinaphthothiophenylene group or a carbazolylene group; Preferably, the C6-C40 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthrofluorenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthrofluorenyl, tetraphenylmethane or benzonaphthofluorenyl; Preferably, the C6-C30 heteroaryl group is selected from any one or a combination of at least two of carbazolyl, dibenzothiophenyl, dibenzofuranyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl; Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, fluorenyl, triphenylene or fluoranthenyl; 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 dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, or a carbazolylene group; Preferably, 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; Preferably, Ar1 and Ar2 are each independently selected from any one or a combination of at least two of H, phenyl, carbazolyl, biphenyl, 9,9-dimethylfluorenyl, naphthyl, triphenylene, fluoranthenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl or naphthobenzothiophenyl; Preferably, Ar1 and Ar2 are each independently selected from at least one of H, phenyl, carbazolyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothiophenyl, biphenyl, dibenzofuranyl, triphenylene or fluoranthenyl; preferably, one of A1, A2 and A3 is selected from N, and two are CR; Preferably, two of A1, A2, and A3 are selected from N, and one is CR; Preferably, A1, A2, and A3 are all selected from N; Preferably, R is selected from any one of H, phenyl or biphenyl; Preferably, R1, R2, and R3 are each independently selected from any one of H, phenyl, biphenyl, naphthyl, and dibenzofuranyl.

4. The triphenylene compound according to any one of claims 1 to 3, characterized in that The hydrogen atoms in the compound of formula I and the compound of formula II may each independently be substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, triphenylmethyl, triphenylsilyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy; Preferably, 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 -D, -F, -CN, phenyl, naphthyl, methyl, ethyl, tert-butylmethoxy, ethoxy, and propoxy.

5. The triphenylene compound according to any one of claims 1 to 4, characterized in that The triphenylene compound has a structure shown in Formula I.

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 above compounds can each be independently replaced by a deuterium atom.

7. An intermediate, characterized in that The intermediate includes a compound having a structure shown in the following formula M1: Ar, Ar1, Ar2, A1, A2, A3 have the same definitions as in claim 1; The hydrogen atoms in the compound of formula M may each independently be replaced by a deuterium atom; The intermediates do not include the following compounds: 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 represented by 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 represented by 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 the 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; Preferably, the organic electroluminescent device is a red organic electroluminescent device.

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