Compound, intermediate and organic electroluminescent device

Abstract

The invention provides a compound, an intermediate and an organic electroluminescent device. The compound has a structure as shown in a formula I; the intermediates are used for preparing the compounds. The structure of the compound is designed, so that the compound is suitable for being used as a main body material of a light-emitting layer of the organic light-emitting device, and the organic light-emitting device has relatively 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 compound, an intermediate and an organic electroluminescent device. Background Art

[0002] Compared with other flat panel displays (for example, liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), etc.), organic electroluminescent devices (OLEDs) have a simpler structure, various processing advantages, higher brightness, excellent viewing angle characteristics, faster response speeds, and lower driving voltages. Therefore, they are also fully developed to be used as light sources for flat panel displays (for example, wall-mounted TVs, etc.), or as backlight units for displays, illuminators, billboards, etc.

[0003] The structure of an organic electroluminescent device specifically includes an anode, a cathode, and an organic layer therebetween. In order to improve the efficiency and stability of an organic electroluminescent element, the organic material layer includes multiple layers with different materials. 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, life span, etc. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a compound, an intermediate and an organic electroluminescent device. In the present invention, the structure of the compound is designed to make it suitable as a main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a higher current efficiency and a 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 compound having a structure shown in the following formula I:

[0007]

[0008] Wherein, Y represents C or Si, and X represents O or S;

[0009] m and n are each independently selected from 0 or 1;

[0010] The m is 0, and Ar1 is selected from any one of C6-C40 aryl, C6-C30 heteroaryl, or C1-C12 alkyl; or, the m is 1, and Ar1 is selected from any one of C6-C40 arylene, C6-C30 heteroarylene, or C1-C12 alkylene;

[0011] R1 and R2 are each independently selected from any one of C6-C40 aryl, C6-C30 heteroaryl, and C1-C12 alkyl, and R1 and R2 can be connected to form a ring through a single bond;

[0012] Dashed lines indicate single bonds or their absence;

[0013] The hydrogen atoms in the compound of formula I may each independently be substituted by at least one of a deuterium atom (D), -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0014] In the present invention, the structure of the compound is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0015] It should be noted that, in the present invention, "D" represents a deuterium atom, and the same applies hereinafter.

[0016] In the present invention, C6 to C40 may be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0017] C6~C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0018] C1~C12 can be C1, C2, C4, C6, C8, C10 or C12, etc.

[0019] C6~C20 can be C6, C8, C10, C12, C16 or C20, etc.

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

[0021] As a preferred technical solution of the present invention, the C6-C40 aromatic group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrene, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthofluorenyl.

[0022] Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthylene, pyrenyl, perylene, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenyl, benzoindenyl, dibenzoindenyl, naphthylene or benzonaphthylene.

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

[0024] Preferably, the C6-C30 heteroarylene group is selected from any one of a carbazolylene group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolylene group.

[0025] As a preferred technical solution of the present invention, preferably, the C1-C12 alkyl group is selected from any one of a methyl group, an ethyl group, a propyl group, a butyl group or a cyclohexyl group.

[0026] Preferably, the C1-C12 alkylene group is selected from any one of ethylene, propylene, butylene or cyclohexylene.

[0027] As a preferred technical solution of the present invention, Ar1 is selected from any one of phenyl, naphthyl, biphenyl, 9,9-dimethylfluorenyl, terphenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, phenylene, biphenylene, naphthyl, 9,9-dimethylfluorenyl, terphenylene, carbazolyl, dibenzofuranyl, and dibenzothiophenylene.

[0028] Preferably, R1 and R2 are each independently selected from any one of methyl, ethyl, butyl, phenyl, carbazolyl, biphenyl, fluorenyl, naphthyl or carbazolyl.

[0029] As a preferred technical solution of the present invention, the C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene, and fluoranthene.

[0030] As a preferred technical solution of the present invention, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy or butoxy.

[0031] As a preferred technical solution of the present invention, the hydrogen atoms in the compound represented by formula I can be independently replaced by at least one of a deuterium atom, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or butoxy.

[0032] As a preferred technical solution of the present invention, the compound includes any one of the following substituted or unsubstituted compounds:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] The substitution means that the hydrogen atoms in the above compounds can each independently be replaced by a deuterium atom;

[0044] Preferably, the compound further comprises Replace with Compounds and the above compounds Replace with Compounds and the above compounds Replace with Compounds of

[0045] Here, Y represents Si or C.

[0046] Preferably, the compound is selected from any one of the following compounds:

[0047] It should be noted that the present invention has no special restrictions on the preparation method of the above-mentioned compound, which exemplarily includes but is not limited to:

[0048] ① When n=1, the dotted line indicates that it does not exist, the synthesis method of the compound of formula I is as follows:

[0049]

[0050] Alternatively, when n=1, the dotted line indicates the absence of n, the synthesis method of the compound of formula I is as follows:

[0051]

[0052] ② When n=1 and the dotted line represents a single bond, the synthesis method of the compound of formula I is as follows:

[0053]

[0054] Alternatively, when n=1 and the dotted line represents a single bond, the synthesis method of the compound of formula I is as follows:

[0055]

[0056] ③ When n=0, the dotted line indicates that it does not exist, the synthesis method of the compound of formula I is as follows:

[0057]

[0058] ④ When n=0 and the dotted line represents a single bond, the synthesis method of the compound of formula I is as follows:

[0059]

[0060] Wherein, X1 and X2 each independently represent any one of F, Cl, Br or I; Ar1, R1, R2, X, Y, and m have the same protection scope as above.

[0061] Furthermore, in the above synthesis method, when the reactivity of X1 and X2 is different, those skilled in the art can appropriately select the types of X1 and X2 according to common knowledge to achieve the purpose of synthesis.

[0062] The present invention also provides intermediates represented by M1-M6.

[0063] In a second aspect, the present invention provides an intermediate, wherein the intermediate comprises compound M1 to compound M6:

[0064]

[0065] Wherein, X1 and X2 each independently represent any one of F, Cl, Br or I;

[0066] Ar1, R1, R2, X, Y, m have the same protection scope as above;

[0067] The intermediate is used to prepare the compound as described in the first aspect.

[0068] Preferably, the intermediate includes the following compounds:

[0069]

[0070] It should be noted that the present invention does not impose any special restrictions on the preparation method of the intermediate, and the intermediate can be prepared according to the preparation method provided in the embodiment of the present invention.

[0071] In a third aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0072] The material of the organic thin film layer includes the compound as described in the first aspect.

[0073] 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.

[0074] Preferably, the light-emitting layer is a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer includes the compound as described in the first aspect.

[0075] As a preferred technical solution of the present invention, the organic electroluminescent device is a blue light organic electroluminescent device.

[0076] The luminescent layer in the present invention includes a luminescent layer main material and a doping material, wherein the doping material is also called a dye or a phosphorescent luminescent material. The luminescent layer main material can be a single compound or a mixture of two or more compounds.

[0077] 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 blue phosphorescent light-emitting layer, and a yellow phosphorescent light-emitting layer.

[0078] The volume percentage of the main material in the phosphorescent layer is 60% to 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99.9%, etc.), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0079] In the present invention, the doping material of the light-emitting layer may be a phosphorescent material, which is also called a triplet light-emitting material, and refers to the light emitted from a triplet excited state. The specific selection of the phosphorescent material in the present invention is not particularly limited, and the doping materials of the light-emitting layer commonly used in the art are applicable, including but not limited to: a compound having a structure shown in Formula PD:

[0080]

[0081] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0082] Y1-Y4 are each independently selected from carbon or nitrogen;

[0083] 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;

[0084] Cy1 and Cy2 are each independently selected from phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothienyl, benzimidazolyl, benzoxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazine, dibenzofuranyl, dibenzothienyl, N-heterocarbazolyl, N-heterodibenzofuranyl, wherein Cy1 and Cy2 may be optionally linked to each other via a single bond or an organic linking group;

[0085] 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;

[0086] R 91 and R 92each independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphoric acid, phosphate, -SF5, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C6 C2-C60 (for example, C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) C2-C10 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) heterocycloalkyl, substituted or unsubstituted C6-C60 (for example, C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryl, substituted or unsubstituted C6-C60 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) For example, it can be any one of C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryloxy, substituted or unsubstituted C6-C60 (for example, it can be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) arylthio, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

[0087] a1 and a2 are each independently an integer selected from 1-5, for example, 1, 2, 3, 4 or 5;

[0088] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0089] a is selected from 1, 2 or 3;

[0090] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0091] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] 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.

[0099] The hole injection layer material includes a P-type dopant. The P-type dopant refers to a dopant that coexists with the hole injection layer material in the OLED device and can oxidize the hole injection layer material, thereby acting as an electron acceptor and promoting the movement of holes in the hole injection layer to the anode. In the present invention, the difference between the absolute value of the LUMO of the P-type dopant and the absolute value of the HOMO of the hole layer material is greater than -0.2V, preferably greater than -0.1eV, more preferably greater than 0eV, more preferably greater than 0.1eV, and more preferably greater than 0.2eV.

[0100] The P-type dopant is present in the hole injection layer in a volume percentage of 1% to 10% (e.g., 1%, 2%, 4%, 6%, 8% or 10%). In the present invention, there is no particular limitation on the type of the P-type dopant, and illustratively, the compounds D-1 to D-13 disclosed in CN113728453A or the compounds HI-1 to HI-9 described below can be selected:

[0101]

[0102]

[0103] 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:

[0104]

[0105] Among them, L 41 is selected from a single bond, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, or a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0106] Ar 41 ,Ar42 Each is independently selected from C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, C6-C20 (for example, C6, C8, C10, C12, C16 or C20, etc.) heteroaryl;

[0107] X is selected from CR 41 R 42 or NR 43 , where R 41 , R 42 , R 43 Each independently selected from substituted or unsubstituted phenyl (the substituted substituent is selected from C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy, dibenzofuranyl), naphthyl, triphenylene, fluoranthene, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted dibenzofuranyl (the substituted substituent is phenyl), substituted or unsubstituted dibenzothienyl (the substituted substituent is phenyl), dibenzofuran-substituted thienyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, any one of R 41 , R 42 They can be linked to form rings via single bonds.

[0108] The compound of formula HT-GH4 is selected from any one of the following compounds:

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer and the electron blocking layer) also includes a compound having a structure shown in the following formula IA or a compound having a structure shown in the following formula IB:

[0115]

[0116] Wherein, L is selected from any one of C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) arylene, dibenzofuranyl or dibenzothiophenyl;

[0117] 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;

[0118] Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene;

[0119] Ar1 and Ar2 are each independently selected from any one of a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl group, a dibenzofuranyl group or a dibenzothiophenyl group;

[0120] 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.

[0121] 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, etc.) alkyl group, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl group, a dibenzofuranyl group, or a dibenzothiophenyl group;

[0122] H in the compound of formula IB and the compound of formula IA can each independently be replaced by at least one of -F, -CN, -D (deuterium atom), C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0123] Preferably, Ar is a fluoranthenyl group, and m+n>1.

[0124] Preferably, H in the compound of formula IB and the compound of formula IA can be replaced by at least one of -F, -CN, -D, C1-C3 alkyl (for example, methyl, ethyl or propyl), C1-C3 alkoxy (for example, methoxy, ethoxy or propoxy), phenyl, biphenyl, triphenylene, and fluoranthene.

[0125] Preferably, L, Ar1, Ar2 are each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrene, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

[0126] Preferably, the compound of formula IB is selected from the following structures:

[0127]

[0128] Wherein, L is phenylene;

[0129] Ar1, Ar2, and m have the same protection scope as described above.

[0130] Preferably, the compound of formula IB is selected from any one of the following compounds 1-112:

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] In the OLED device provided by the present invention, the hole layer material may include conventional hole materials in the art in addition to the compound described in formula HT-GH4, the compound of formula IB, and the compound of formula IA, without special restrictions. Exemplary includes but is not limited to: triarylamine compounds or carbazole compounds. Triarylamine compounds or carbazole compounds containing more than 3 N atoms are preferred, because the HOMO of triarylamine compounds or carbazole compounds containing more than 3 N atoms is higher (smaller absolute value), and is more suitable for use as hole injection layer materials. Triarylamine compounds or carbazole compounds containing 2 or 1 N atoms can be used as hole transport layer materials. Some compounds or carbazole compounds containing 1 N atom, if they have a higher LUMO, can also be used as electron blocking layer materials.

[0137] The triarylamine compound or the carbazole compound is used as the hole layer material, and the hole layer material includes the following structure:

[0138]

[0139] Among them, Ar 601 ~Ar 609Each 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, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted naphthobenzofuranyl, a substituted or unsubstituted naphthobenzothiophenyl, a substituted or unsubstituted dinaphthofuranyl, a substituted or unsubstituted dinaphthothiophenyl;

[0140] 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;

[0141] 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.

[0142] The hole blocking layer (HBL) can confine holes and / or excitons within the EL to improve the current efficiency and lifetime of the device. Compared with the EL material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or higher triplet energy.

[0143] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped, and doping may be used to enhance conductivity. In the present invention, there is no particular restriction on the ETL material, and any metal complex or organic compound may be used as long as it can transport electrons. The general electron transport layer material contains the following structural fragments: at least one of a pyridine structure, a pyrimidine structure, a triazine structure, a benzimidazole structure, a benzoxazole structure, a benzothiazole structure, an N-naphthalene structure, an N-coffee structure, an N-carbazole structure, an N-dibenzofuran structure, and an N-dibenzothiophene structure.

[0144] In the present invention, there is no special restriction on the electron transport layer material, which exemplarily includes but is not limited to:

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] In the present invention, the material of the cathode is a metal with a low work function (e.g., alkaline earth metal, alkali metal, main group metal or lanthanide element (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (alloy composed of alkali metal or alkaline earth metal and silver, such as an alloy composed of magnesium and silver) or a multilayer structure. If the cathode material is a multilayer structure, in addition to the metals mentioned above, other metals with relatively high work functions, such as Ag or Al, can also be used. In this case, a combination of the metals is usually used, such as Ca / Ag, Mg / Ag or Ba / Ag.

[0154] It is also possible to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor to form a multilayer structure; the material with a high dielectric constant can also be called an electron injection material, and fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ) can be selected.

[0155] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the third aspect.

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

[0157] In the present invention, the structure of the compound is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer service life. DETAILED DESCRIPTION

[0158] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0159] Preparation Example 1 Synthesis of Intermediate P1-1

[0160] This preparation example provides an intermediate P1-1 and a synthesis method thereof, the synthesis method is as follows:

[0161]

[0162] Under nitrogen protection, 100 mL of toluene, 60 mL of ethanol and 20 mL of water were added to a 500 mL three-necked flask in sequence, and then 0.01 mol of triphenylsilylphenylboric acid, 0.01 mol of 3,6-dibromo-9-phenylcarbazole, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to reflux for reaction for 6 hours, the temperature was lowered to room temperature, water was added to separate, the organic layer was washed with water, dried with magnesium sulfate, the desiccant was removed, and the mixture was concentrated to dryness. Silica gel column chromatography was performed for separation, and petroleum ether:ethyl acetate = 10:0.2 (volume ratio) was used as the eluent to obtain 4.8 g of intermediate P1-1.

[0163] The intermediate P1-1 obtained was subjected to mass spectrometry detection, and the two peaks with the largest mass-to-charge ratio (m / z) were measured to be 657.13 and 655.13.

[0164] Preparation Example 2-6

[0165] Preparation Examples 2-6 provide the following intermediates and their synthesis methods, respectively. The synthesis method refers to the synthesis method in Preparation Example 1, reacting with the corresponding boronic acid compounds and the corresponding bromides, and performing mass spectrometry detection on the obtained compounds, respectively. The mass-to-charge ratio (m / z) of the boronic acid compounds and bromides, the prepared intermediates and their mass spectral data are shown in Table 1 below.

[0166] Table 1

[0167]

[0168]

[0169] Preparation Example 7 Synthesis of Intermediate A1-1

[0170] This preparation example provides an intermediate A1-1 and a synthesis method thereof, the synthesis method is as follows:

[0171]

[0172] Under nitrogen atmosphere, add 0.01 mol of 3,6-dibromo-9-phenylcarbazole and 300 mL of tetrahydrofuran to a 500 mL three-necked flask, then cool to -78 °C, slowly add a hexane solution containing 0.01 mol of butyl lithium, then keep the temperature at -78 °C to -60 °C for 30 min, and add 0.012 mol of 0.0001 mol Pd(dba)2, 0.0001 mol anhydrous nickel chloride, slowly heat to room temperature for 2 hours, then heat to reflux for 2 hours, cool, add water and toluene for separation, wash the organic layer with water until neutral, dry with anhydrous magnesium sulfate, filter out the desiccant, concentrate to dryness, separate by silica gel column chromatography, elute with petroleum ether: ethyl acetate = 20:1 (volume ratio), and obtain 3.8 g of intermediate A1-1.

[0173] The intermediate A1-1 obtained was subjected to mass spectrometry detection, and the two peaks with the largest mass-to-charge ratio (m / z) were measured to be 579.08 and 577.09.

[0174] Preparation Example 8 Synthesis of Intermediate B1-1

[0175] This preparation example provides an intermediate B1-1 and a synthesis method thereof, and the synthesis method is as follows:

[0176]

[0177] Referring to the synthesis method of intermediate A1-1, the only difference is that By replacing the substance with an equal amount of triphenylchlorosilane, intermediate B1-1 was obtained.

[0178] The obtained intermediate B1-1 was subjected to mass spectrometry detection, and the two peaks with the largest m / z were: 581.10 and 579.10.

[0179] Synthesis Example 1 Synthesis of Compound P1

[0180] This synthesis example provides compound P1 and its synthesis method, and the synthesis method is as follows:

[0181]

[0182] Under nitrogen protection, 100 mL of toluene, 60 mL of ethanol and 20 mL of water were added to a 500 mL three-necked flask in sequence, and then 0.01 mol of intermediate P1-1, 0.01 mol of intermediate P1-2, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to reflux for reaction for 6 hours, the temperature was lowered to room temperature, water was added to separate, the organic layer was washed with water, dried with magnesium sulfate, the desiccant was removed, and the mixture was concentrated to dryness. The mixture was separated by silica gel column chromatography and eluted with petroleum ether:ethyl acetate = 10:0.2 (volume ratio) to obtain 6.6 g of compound P1.

[0183] The obtained compound P1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 801.29.

[0184] Synthesis Example 2-11

[0185] Synthesis Examples 2-11 respectively provide a compound and a synthesis method thereof. The synthesis method refers to the synthesis method in Synthesis Example 1, reacts with the corresponding boronic acid compound and the corresponding bromide, and performs mass spectrometry detection on the obtained compounds. The mass-to-charge ratio (m / z) of the boronic acid compound and the bromide, the prepared compound and its mass spectrum data are shown in Table 2 below.

[0186] Table 2

[0187]

[0188]

[0189]

[0190] Other compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0191] The specific structures of some compounds used in the following application examples and comparative application examples are as follows:

[0192]

[0193]

[0194] Application Example 1

[0195] This application example provides a blue light organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer, and the structure of the blue light organic electroluminescent device is:

[0196] ITO / HT-1: HI-2 [5%] (80nm) / HT-1 (30nm) / electron blocking layer (20nm) / host material: PBD-1 [5%] (35nm) / ETL-1 (25nm) / LiF (0.5nm) / Al (150nm).

[0197] The preparation method of the blue light organic electroluminescent device is as follows:

[0198] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa was vacuum evaporated onto the cleaned ITO substrate in sequence to prepare an OLED device.

[0199] Among them, PBD-1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the main material to the dye PBD-1 is 95:5; HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole material HT-1 and the P-type dopant HI-2 is 95:5. HT-1 is a hole transport material; HT-1:HI-2[5%] is used as a hole injection layer, and the electron blocking layer is EB-2.

[0200] The main material of the light-emitting layer of the blue light organic electroluminescent device provided in this application example is compound P1.

[0201] Application Example 2-25

[0202] Application Examples 2-25 respectively provide a blue light organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced with other compounds (see Table 3 for details), and the electron blocking layer material is replaced as needed. The specific selection is shown in Table 3 below. The other preparation steps and conditions are the same as those of Application Example 1.

[0203] Comparative Application Example 1-2

[0204] Comparative Application Examples 1-2 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced by other compounds (see Table 3 for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0205] Performance Testing

[0206] The OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang was used to test the brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent devices provided above. Among them, 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 2The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, where the current efficiency and LT95 are relative values. The specific test results are shown in Table 3:

[0207] Table 3

[0208]

[0209]

[0210] It can be seen from the above content that the structure of the compound is designed in the present invention to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0211] From the comparison of the above-mentioned Application Examples 1, 4, 22, 23, 24 and 25, it can be seen that the performance of the organic electroluminescent device can be further improved when the compound of a specific structural formula is used as the main material of the light-emitting layer and the compound conforming to the structure shown in Formula IA or the structure shown in Formula IB (Compound EB-2 and Compound EB-3) is used as the electron blocking layer material.

[0212] Furthermore, by comparing Application Examples 1 and 4 with Application Examples 22 and 23 respectively, the present invention can further improve the current efficiency and life of the organic electroluminescent device when using a compound of a specific structural formula as the main material of the light-emitting layer and compound EB-3 as the electron blocking layer material.

[0213] In summary, the present invention designs the structure of the compound to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0214] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound, characterized in that The compound has the structure shown in the following formula I: Wherein, Y represents C or Si, and X represents O or S; m and n are each independently selected from 0 or 1; The m is 0, and Ar1 is selected from any one of C6-C40 aryl, C6-C30 heteroaryl, or C1-C12 alkyl; or, the m is 1, and Ar1 is selected from any one of C6-C40 arylene, C6-C30 heteroarylene, or C1-C12 alkylene; R1 and R2 are each independently selected from any one of C6-C40 aryl, C6-C30 heteroaryl, and C1-C12 alkyl, and R1 and R2 can be connected to form a ring through a single bond; Dashed lines indicate single bonds or their absence; The hydrogen atoms in the compound of formula I may each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

2. The compound according to claim 1, characterized in that The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthfluoroenyl; Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthylene, pyrenyl, perylene, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenyl, benzoindenyl, dibenzoindenyl, naphthylene or benzonaphthylene.

3. The compound according to claim 1 or 2, characterized in that The C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, dinaphthothiophenyl or carbazolyl; Preferably, the C6-C30 heteroarylene group is selected from any one of carbazolylene, dibenzofuranyl, dibenzothiophenylene, naphthobenzofuranylene, naphthobenzothiophenylene, dinaphthofuranylene, dinaphthothiophenylene or carbazolylene; Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl or cyclohexyl; Preferably, the C1-C12 alkylene group is selected from any one of ethylene, propylene, butylene or cyclohexylene.

4. The compound according to any one of claims 1 to 3, characterized in that Ar1 is selected from any one of phenyl, naphthyl, biphenyl, 9,9-dimethylfluorenyl, terphenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, phenylene, biphenylene, naphthyl, 9,9-dimethylfluorenyl, terphenylene, carbazolyl, dibenzofuranyl, and dibenzothiophenylene; Preferably, R1 and R2 are each independently selected from any one of methyl, ethyl, butyl, phenyl, carbazolyl, biphenyl, fluorenyl, naphthyl or carbazolyl.

5. The compound according to any one of claims 1 to 4, characterized in that The C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene, and fluoranthenyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy or butoxy.

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

7. The compound according to any one of claims 1 to 4, characterized in that The compound includes 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 deuterium atoms; Preferably, the compound further comprises Replace with Compounds and the above compounds Replace with Compounds and the above compounds Replace with Compounds of Wherein, Y represents Si or C; Preferably, the compound is selected from any one of the following compounds:

8. An intermediate, characterized in that The intermediates include compounds M1 to M6: Wherein, X1 and X2 each independently represent any one of F, Cl, Br or I; Ar1, R1, R2, X, Y, and m have the same protection scope as claim 1; The intermediate is used to prepare the compound according to any one of claims 1 to 7; Preferably, the intermediate includes the following compounds:

9. 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 material of the organic thin film layer comprises the compound according to any one of claims 1 to 7; Preferably, the organic thin film layer comprises a light-emitting layer, and the main material of the light-emitting layer comprises the compound according to any one of claims 1 to 7; Preferably, the light-emitting layer is a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer includes the compound according to any one of claims 1 to 7; Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic thin film layer includes an electron blocking layer, and the material of the electron blocking layer includes a compound having a structure shown in the following formula IA or a compound having a structure shown in the following formula IB: Wherein, L is selected from any one of C6-C40 arylene, dibenzofuranyl or dibenzothiophenyl; m is selected from an integer between 0 and 4, and n is selected from 0 or 1; Ar is selected from any one of triphenylene, fluoranthenylene, dibenzofuranylene or dibenzothiophenylene; Ar1 and Ar2 are each independently selected from any one of a C6-C40 aryl group, a dibenzofuranyl group or a dibenzothiophenyl group; 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; R, R1, and R2 are each independently selected from any one of a C1-C20 alkyl group, a C6-C40 aryl group, a dibenzofuranyl group, or a dibenzothiophenyl group; The hydrogen atoms in the compounds of formula IA and formula IB can each independently be replaced by at least one of -F, -CN, -D, C1-C6 alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrene, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

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