Carbazole compound containing heterocyclic substituent, intermediate and organic electroluminescent device

Abstract

The invention provides a carbazole compound containing a heterocyclic substituent, an intermediate and an organic electroluminescent device. The carbazole compound containing the heterocyclic substituent has a structure as shown in a formula I or a formula II. According to the invention, the structure of the carbazole compound containing the heterocyclic substituent is designed, and the carbazole compound containing the heterocyclic substituent with excellent performance is prepared, so that the carbazole compound containing the heterocyclic substituent is used as a material of a luminescent layer; and the prepared organic light-emitting device has relatively high current efficiency, relatively long service life and relatively low driving voltage.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a carbazole compound with a heterocyclic substituent, an intermediate, and an organic electroluminescent device. Background Art

[0002] Compared with other flat panel displays (such as 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 speed, and lower driving voltage. Therefore, they are also fully developed for use as light sources for flat panel displays (such as wall-mounted TVs, etc.), or as backlight units for displays, illuminators, advertising boards, etc.

[0003] The structure of an organic electroluminescent device is specifically: an anode, a cathode, and an organic layer therebetween. To improve the efficiency and stability of the organic electroluminescent element, the organic material layer includes multiple layers with different materials. To meet people's higher requirements for OLED devices, there is an urgent need in this field 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] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a carbazole compound with a heterocyclic substituent, an intermediate, and an organic electroluminescent device. By designing the structure of the carbazole compound with a heterocyclic substituent, the present invention prepares a carbazole compound with a heterocyclic substituent having excellent performance. Thus, the carbazole compound with a heterocyclic substituent is used as a material for the light-emitting layer, and the prepared organic electroluminescent device has a high current efficiency, a long lifespan, and a low driving voltage.

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

[0006] In a first aspect, the present invention provides a carbazole compound with a heterocyclic substituent, and the carbazole compound with a heterocyclic substituent has a structure shown in the following formula I or formula II:

[0007]

[0008] X is selected from O or S;

[0009] The hydrogen atoms in the compound of formula I or the compound of formula II can each independently be deuterium atoms (D), -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, triphenylsilyl ( The dashed line indicates the connection site, the same hereinafter), triphenylmethyl Substituted with at least one of C6-C20 aryl or C6-C20 heteroaryl.

[0010] Through the design of carbazole compounds with heterocyclic substituents, the present invention prepares carbazole compounds with heterocyclic substituents having excellent performance. This compound has relatively appropriate HOMO and LUMO energy levels, good film-forming properties of the molecule, and strong charge transport ability. Therefore, the carbazole compound with heterocyclic substituents as the material of the light-emitting layer is used to prepare an organic electroluminescent device with high current efficiency, long lifespan, and low driving voltage.

[0011] In the present invention, C1-C12 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, or C12.

[0012] C6-C20 can be C6, C10, C12, C15, C18, or C20, etc.

[0013] In the present invention, "D" represents a deuterium atom. If not separately indicated in the present invention, H and hydrogen therein both represent "protium", and the same applies hereinafter.

[0014] The following are the preferred technical solutions of the present invention, but do not 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.

[0015] As a preferred technical solution of the present invention, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, methylcyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl, adamantyl, bicyclo[2.2.1]heptyl, or bicyclo[2.2.2]octyl.

[0016] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy, or hexyloxy.

[0017] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, or 9,9-dimethylfluorenyl.

[0018] Preferably, the C6-C20 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, or dibenzothiophenyl.

[0019] As a preferred technical solution of the present invention, the hydrogen atoms in the compound of formula I or the compound of formula II can each independently be replaced by at least one of deuterium atom (D), -F, -CN, methoxy, ethoxy, propoxy, methyl, ethyl, propyl, tert-butyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, triphenylsilyl or triphenylmethyl. As a preferred technical solution of the present invention, the carbazole compound containing a heterocyclic substituent has a structure shown in the following formula I-1 or formula II-1:

[0020]

[0021] Wherein, X has the same definition as above;

[0022] Ar is selected from at least one of -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, triphenylsilyl, triphenylmethyl, C6-C20 aryl or C6-C20 heteroaryl;

[0023] The hydrogen atoms in the compound of formula I-1 or the compound of formula II-1 can each independently be replaced by at least one of deuterium atom (D), -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, triphenylsilyl, triphenylmethyl, C6-C20 aryl or C6-C20 heteroaryl.

[0024] Preferably, Ar is selected from at least one of -F, -CN, methoxy, ethoxy, propoxy, methyl, ethyl, propyl, tert-butyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, triphenylsilyl or triphenylmethyl;

[0025] As a preferred technical solution of the present invention, the carbazole compound containing a heterocyclic substituent is selected from any one of the following substituted or unsubstituted compounds:

[0026]

[0027]

[0028]

[0029] The substitution means that the hydrogen atoms in the carbazole compound containing a heterocyclic substituent can each independently be replaced by deuterium atoms.

[0030] Preferably, the carbazole compound containing a heterocyclic substituent is selected from any one of the following compounds:

[0031]

[0032]

[0033] It should be noted that in the present invention, there are no special restrictions on the preparation method of carbazole compounds containing heterocyclic substituents, and the commonly used preparation methods in the art are applicable.

[0034] In a second aspect, the present invention provides an intermediate, and the intermediate includes the following compounds:

[0035]

[0036] wherein X and Ar have the same definitions as above;

[0037] X 2 is selected from any one of -F, -Cl, -Br, and -I;

[0038] The hydrogen atoms in the compound of formula MA can each independently be replaced by deuterium atoms (D);

[0039] The intermediate is used for preparing the carbazole compounds containing heterocyclic substituents as described in the first aspect.

[0040] Preferably, the intermediate includes the following compounds:

[0041]

[0042] It should be noted that in the present invention, there are no special restrictions on the preparation method of the above intermediate compounds, and the commonly used preparation methods in the art are applicable.

[0043] The synthesis method of the intermediate MA of the present invention is illustrated as including the following steps:

[0044]

[0045] wherein X and Ar have the same definitions as above;

[0046] wherein X 1 and X 2 are each independently selected from any one of -F, -Cl, -Br, and -I; and those skilled in the art can select the types of X 1 and X 2 according to the common general knowledge in the art. For example, X 1 is selected as -I, and X 2 is selected from any one of -F, -Cl, and -Br; X 1 is selected as -Br, and X 2 is selected as -F or -Cl; X 1 is selected as Cl, and X 2 is selected as F.

[0047] It should be noted that the hydrogen atoms in the starting material compounds for preparing the intermediates and the finally obtained intermediate products can each independently be replaced by deuterium atoms (D).

[0048] In a third aspect, the present invention provides an organic electroluminescent device, which includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;

[0049] The material of the organic thin film layer includes a carbazole compound with a heterocyclic substituent as described in the first aspect.

[0050] Preferably, the organic thin film layer includes a light-emitting layer, and the host material of the light-emitting layer includes a carbazole compound with a heterocyclic substituent as described in the first aspect.

[0051] Preferably, the light-emitting layer is a phosphorescent light-emitting layer.

[0052] As a preferred technical solution of the present invention, the organic electroluminescent device is a blue organic electroluminescent device.

[0053] In the present invention, the light-emitting layer includes a light-emitting layer host material and a doping material, where the doping material is also called a dye or a phosphorescent light-emitting material. The light-emitting layer host material can be a single compound or a mixture formed by two or more compounds.

[0054] 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.

[0055] The volume percentage content of the host material in the phosphorescent light-emitting layer is 60% - 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99.9%, etc.), preferably 70% - 99.5%, and further preferably 85% - 95%.

[0056] In the present invention, the doping material of the light-emitting layer can be a phosphorescent light-emitting material. The phosphorescent light-emitting material, also known as a triplet light-emitting material, refers to the light emitted by a substance from a triplet excited state. In the present invention, the specific selection of the phosphorescent material is not particularly limited, and the commonly used doping materials for the light-emitting layer in the art are applicable. Exemplarily, it includes but is not limited to: a compound having a structure shown by formula PD:

[0057]

[0058] Among them, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0059] Y 1 -Y4 Each independently selected from carbon or nitrogen;

[0060] Y 1 and Y 2 may be connected by a single bond or a double bond, and Y 3 and Y 4 may be connected by a single bond or a double bond;

[0061] Cy 1 and Cy 2 Each independently selected from phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, benzoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothienyl, benzimidazolyazolyl, benzazolyl, triazolyl, tetrazolyl, dioxazolyl, triazinyl, dibenzofuranyl, dibenzothienyl, N-heterocarbazolyl, N-heterodibenzofuranyl, and any one of them, wherein Cy 1 and Cy 2 may optionally be connected to each other via a single bond or an organic linking group;

[0062] Between any two ligands of M, between two or more ligands, they can be connected by a single bond, a double bond, or can be bridged by O, S, or can be connected by any chemical group or chemical structure to form a chemical principle-compliant structural form;

[0063] R 91 and R 92 Each independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazino, hydrazono, carboxylic acid group, carboxylate group, sulfonic acid group, sulfonate group, phosphoric acid group, phosphate group, -SF 5, any one of substituted or unsubstituted C1-C60 (such as C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C60 (such as C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkenyl, substituted or unsubstituted C2-C60 (such as C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (such as C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkoxy, substituted or unsubstituted C2-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9 or C10) heterocycloalkyl, substituted or unsubstituted C6-C60 (such as C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) aryl, substituted or unsubstituted C6-C60 (such as C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) aryloxy, substituted or unsubstituted C6-C60 (such as C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60, etc.) arylthio, substituted or unsubstituted monovalent non-aromatic fused polycyclic group, substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

[0064] a 1 and a 2 each independently is an integer selected from 1-5, such as 1, 2, 3, 4 or 5;

[0065] b is selected from integers from 0-4, such as 0, 1, 2, 3 or 4;

[0066] a is selected from 1, 2 or 3;

[0067] L 1 is a monovalent organic ligand, divalent organic ligand or trivalent organic ligand.

[0068] Preferably, the PD compound of the formula is any one of the following compounds:

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] 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.

[0075] The material of the hole injection layer includes a P-type dopant. The P-type dopant refers to a substance that coexists with the material of the hole injection layer in the OLED device and can oxidize the material of the hole injection layer, thereby acting as an electron acceptor and promoting the movement of holes in the hole injection layer towards 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 -0.2 V, preferably greater than -0.1 eV, more preferably greater than 0 eV, still more preferably greater than 0.1 eV, and even more preferably greater than 0.2 eV.

[0076] The P-type dopant exists in the hole injection layer in a volume ratio of 1% to 10% by volume (for example, it can be 1%, 2%, 4%, 6%, 8%, or 10%, etc.). In the present invention, no special limitation is imposed on the type of the P-type dopant. Exemplarily, the compounds shown as D-1 to D-13 disclosed in CN113728453A or the compounds shown as HI-1 to HI-9 described below can be selected:

[0077]

[0078] In the present invention, the hole layer material (including the hole injection layer, the hole transport layer, and the electron blocking layer) has the structure shown by the following formula HT-GH4:

[0079]

[0080] Among them, L 41 is selected from a single bond, an aryl group of C6-C40 (for example, it can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.), and a heteroaryl group of C6-C20 (for example, it can be C6, C8, C10, C12, C16, or C20, etc.);

[0081] Ar 41 and Ar 42 each independently is selected from an aryl group of C6-C40 (for example, it can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) and a heteroaryl group of C6-C20 (for example, it can be C6, C8, C10, C12, C16, or C20, etc.);

[0082] X is selected from CR 41 R 42 or NR 43 , wherein R 41 、R 42 、R 43 are each independently selected from substituted or unsubstituted phenyl (the substituents of the substituted phenyl are selected from C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkyl, C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkoxy, dibenzofuranyl), naphthyl, triphenylene, fluoranthenyl, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted dibenzofuranyl (the substituents of the substituted dibenzofuranyl are phenyl), substituted or unsubstituted dibenzothiophenyl (the substituents of the substituted dibenzothiophenyl are phenyl), dibenzofuran-substituted thiophenyl, any one of C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkyl, and R 41 、R 42 can be connected into a ring through a single bond.

[0083] 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 the structure shown in Formula IA or a compound having the structure shown in Formula IB:

[0084]

[0085] wherein, L is selected from any one of C6-C40 (such as C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) arylene, di(dibenzofuranyl) or di(dibenzothiophenyl);

[0086] m is an integer between 0 and 4 (such as 0, 1, 2, 3 or 4), and n is selected from 0 or 1;

[0087] Ar is selected from any one of triphenylene, fluoranthene, dibenzofuranyl or dibenzothiophenyl;

[0088] Ar 1 and Ar 2 are each independently selected from any one of C6-C40 (such as C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, dibenzofuranyl or dibenzothiophenyl;

[0089] Ar 1 and between Ar 2 and Ar, between Ar 1 、Ar 2independently of each other can be connected or bridged by a single bond, O, S, CR 1 R 2 , NR connection or bridging.

[0090] R, R 1 、R 2 each independently selected from C1-C20 (such as C1, C2, C4, C6, C8, C10, C12, C14, C16, C18 or C20, etc.) alkyl, C6-C40 (such as C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, dibenzofuranyl or dibenzothiophenyl;

[0091] The hydrogen atoms 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, spirofluorene, indenofluorene or hydrogenated benzoanthracenyl.

[0092] Preferably, the Ar is subfluoranthenyl and m + n > 1.

[0093] Preferably, the 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 (such as methyl, ethyl or propyl), C1-C3 alkoxy (such as methoxy, ethoxy or propoxy), phenyl, biphenyl, triphenylene, fluoranthenyl.

[0094] Preferably, the L, Ar 1 、Ar 2 each independently selected from at least one of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorene, indenofluorene or hydrogenated benzoanthracenyl.

[0095] Preferably, the compound of formula IB is selected from any one of the following compounds:

[0096]

[0097]

[0098] In the OLED device provided by the present invention, in addition to the compounds represented by formula HT-GH4, formula IB compounds, and formula IA compounds, the hole layer material may simultaneously include conventional hole materials in the art, without particular limitation. Exemplarily, it includes but is not limited to: triarylamine compounds or carbazole compounds. Preferably, triarylamine compounds or carbazole compounds containing more than 3 N atoms are used because the HOMO of triarylamine compounds or carbazole compounds containing more than 3 N atoms is relatively high (smaller absolute value), and they are more suitable 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 containing 1 N atom or carbazole compounds, if they have a relatively high LUMO, can also be used as electron blocking layer materials.

[0099] As the hole layer material, the triarylamine compound or carbazole compound has the following structure:

[0100]

[0101] Wherein, Ar 601 ~Ar 609 Each independently selected from substituted or unsubstituted C6-C40 (such as C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted naphthobenzofuranyl groups, substituted or unsubstituted naphthobenzothiophenyl groups, substituted or unsubstituted dinaphthofuranyl groups, substituted or unsubstituted dinaphthothiophenyl groups;

[0102] And Ar 601 ~Ar 609 Among them, Ar 601 ~Ar 609 Adjacent or connected to the same N atom can be connected by a single bond or bridged by O, S, CR 701 R 702 、NR 703 ;

[0103] R 701 、R 702 、R 703 Are selected from C6-C40 (such as C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aromatic groups, C6-C20 (such as C6, C8, C10, C12, C16 or C20, etc.) heteroaromatic groups, C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkyl groups, and R 701 、R702 It can be connected by a single key.

[0104] The hole blocking layer (HBL) can confine holes and / or excitons within the light-emitting layer to improve the current efficiency and lifetime of the device. Compared with the light-emitting layer material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or a higher triplet energy.

[0105] The electron transport layer (ETL) can include materials capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or doped, and doping can be used to enhance conductivity. In the present invention, there is no special limitation on the ETL material, and any metal complex or organic compound can 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, naphthyridine structure, phenanthridine structure, carbazole structure, dibenzofuran structure, dibenzothiophene structure.

[0106] In the present invention, there is no special limitation on the electron transport layer material, and exemplary ones include but are not limited to:

[0107]

[0108]

[0109]

[0110]

[0111] In the present invention, the material of the cathode is a metal with a low work function (such as alkaline earth metals, alkali metals, main group metals or lanthanide elements (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (an alloy composed of an 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 a relatively high work function, 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.

[0112] It is also possible to select a thin intermediate layer introducing 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, as well as corresponding oxides or carbonates (such as LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs2 CO 3 etc.) or lithium quinolate (LiQ).

[0113] Compared with the prior art, the present invention has the following beneficial effects:

[0114] By designing the structure of the carbazole compounds with heterocyclic substituents, the present invention prepares carbazole compounds with heterocyclic substituents having excellent properties. Thus, the organic electroluminescent device prepared by using the carbazole compounds with heterocyclic substituents as the material of the light-emitting layer has a high current efficiency, a long lifespan and a low driving voltage. Detailed implementation manners

[0115] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0116] Preparation Example 1 Synthesis of Intermediate P6-1

[0117] This preparation example provides intermediate P6-1 and its synthesis method. The synthesis method is as follows:

[0118]

[0119] Under the protection of nitrogen, 2.9 g of intermediate 2-iodo-dibenzofuran, 2.6 g of 3-bromo-6-methylcarbazole, 2.5 g of anhydrous potassium carbonate, 60 mL of o-dichlorobenzene, 3 mL of DMF, 0.1 g of cuprous oxide and 0.2 g of o-phenanthroline were added to a three-necked flask. First, the reaction was carried out at 80 °C for 4 hours, then the temperature was raised to 120 °C and the reaction was carried out for 8 hours. After cooling, the insoluble substances were filtered off, washed with water, separated by liquid separation, the organic layer was washed with water until neutral, dried over anhydrous magnesium sulfate, the desiccant was filtered off, and then concentrated to dryness. Crystallization with ethanol was carried out to obtain intermediate P6-1 (2.1 g).

[0120] The obtained intermediate P6-1 was subjected to mass spectrometry detection, and the m / z was 425.04.

[0121] Preparation Example 2 Synthesis of Intermediate P7-1

[0122] This preparation example provides intermediate P7-1 and its synthesis method. The synthesis method is as follows:

[0123]

[0124] Referring to the synthesis of intermediate P6-1, intermediate P7-1 was prepared.

[0125] The obtained intermediate P7-1 was subjected to mass spectrometry detection, and the m / z was 487.06.

[0126] Synthesis of Intermediate P8-1 in Preparation Example 3

[0127] This preparation example provides intermediate P8-1 and its synthesis method, and the synthesis method is as follows:

[0128]

[0129] Referring to the synthesis of intermediate P6-1, intermediate P8-1 was prepared.

[0130] The obtained intermediate P8-1 was subjected to mass spectrometry detection, and the m / z was 576.08.

[0131] Synthesis of Intermediate P9-1 in Preparation Example 4

[0132] This preparation example provides intermediate P9-1 and its synthesis method, and the synthesis method is as follows:

[0133]

[0134] Referring to the synthesis of intermediate P6-1, intermediate P9-1 was prepared.

[0135] The obtained intermediate P9-1 was subjected to mass spectrometry detection, and the m / z was 669.11.

[0136] Among them, the synthesis of P9-0 is as follows:

[0137]

[0138] To a three-necked flask, 4.2 g of intermediate P9-M and 50 mL of DMF were added, and 1.9 g of NBS (N-bromosuccinimide) was added in portions at 25-30 °C. After the addition, the mixture was reacted at 25-30 °C for 6 hours, poured into water, and the obtained solid was filtered, washed with water, dried, and crystallized with a mixed solvent of ethanol and toluene to obtain intermediate P9-0 (3.7 g).

[0139] The obtained intermediate P9-0 was subjected to mass spectrometry detection, and the m / z was 503.07.

[0140] Synthesis of Intermediate P10-1 in Preparation Example 5

[0141] This preparation example provides intermediate P10-1 and its synthesis method, and the synthesis method is as follows:

[0142]

[0143] Referring to the synthesis of intermediate P6-1, intermediate P10-1 was prepared.

[0144] The obtained intermediate P10-1 was subjected to mass spectrometry detection, and the m / z was 487.06.

[0145] Synthesis Example 1 Synthesis of Compound P1

[0146] This synthesis example provides compound P1 and its synthesis method, the synthesis method is as follows:

[0147]

[0148] Under nitrogen atmosphere, dry toluene (90 mL), intermediate P1-1 (4.1 g), intermediate P1-2 (3.2 g), Pd (dba) were added to a three-necked flask. 2 (bis(dibenzylideneacetonepalladium, 0.1 g), 10% by mass of tri-tert-butylphosphine toluene solution 0.8 g (the mass of tri-tert-butylphosphine is 0.08 g) and sodium tert-butoxide (1.2 g), heated to reflux temperature, reacted for 8 hours, cooled to room temperature, separated by adding water, and then the organic layer was washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, and eluted with petroleum ether: dichloromethane = 10: 1 (volume ratio) to obtain compound P1 (5.1 g).

[0149] The mass spectrometry detection of compound P1 was performed: the mass-to-charge ratio (m / z) was measured to be 650.24.

[0150] Synthesis Example 2-13

[0151] Synthesis Examples 2-13 provide a compound and a synthesis method thereof, respectively. The synthesis method of the corresponding compound refers to the preparation method of compound P1, and the corresponding bromide and amine compounds (as shown in Table 1 below) are used to prepare the corresponding compound, and the mass spectrum of the prepared compound is measured to record m / z. See Table 1 below for details:

[0152] Table 1

[0153]

[0154]

[0155]

[0156]

[0157] The specific structures of some compounds used in the following application examples and comparative application examples are as follows:

[0158]

[0159]

[0160] Application Example 1

[0161] This application example provides a blue organic electroluminescent device, using the compound P1 provided by the present invention as the host material of the light-emitting layer. The structure of the blue organic electroluminescent device is as follows:

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

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

[0164] Place the materials in a vacuum chamber, evacuate to 1×10 -5 ~1×10 -6 Pa, and sequentially vacuum deposit the above materials onto the cleaned ITO substrate to prepare the OLED device.

[0165] Among them, PBD-1 [5%] refers to the doping ratio of the dye, that is, the volume ratio of the host 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 transport material HT-1 and the P-type dopant HI-2 is 95:5, and HT-1 is a hole transport material; HT-1: HI-2 [5%] is used as the hole injection layer material, and EB-1 is an electron blocking layer material.

[0166] Application Example 2-13

[0167] Application Example 2-13 respectively provides a blue organic electroluminescent device. The difference from Application Example 1 is only that the host material compound P1 of the light-emitting layer is replaced with other compounds (see Table 2 below), and other preparation steps and conditions are the same as those in Application Example 1.

[0168] Comparative Application Example 1-2

[0169] Comparative Application Example 1-2 respectively provides a blue organic electroluminescent device. The difference from Application Example 1 is only that the host material compound P1 of the light-emitting layer is replaced with other compounds (see Table 2 below), and other preparation steps and conditions are the same as those in Application Example 1.

[0170] Performance Test

[0171] Test the brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent devices provided above. Among them, the current efficiency is the corresponding value when the brightness is 1000 cd / m 2 , and LT95 refers to maintaining the initial current density of the device at 10 mA / cm 2The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, where the driving voltage, current efficiency, and LT95 are relative values. The specific test results are shown in Table 2 below:

[0172] Table 2

[0173] Host material Dye <![CDATA[Luminance / (cd / m 2 )]]> Driving voltage Current efficiency LT95 Application Example 1 P1 PBD-1 1000 0.88 1.12 1.21 Application Example 2 P2 PBD-1 1000 0.89 1.47 1.32 Application Example 3 P3 PBD-1 1000 0.85 1.21 1.56 Application Example 4 P4 PBD-1 1000 0.72 1.19 1.39 Application Example 5 P5 PBD-1 1000 0.66 1.74 1.12 Application Example 6 P6 PBD-1 1000 0.92 1.89 1.18 Application Example 7 P7 PBD-1 1000 0.93 2.03 1.19 Application Example 8 P8 PBD-1 1000 0.79 2.55 1.09 Application Example 9 P9 PBD-1 1000 0.98 2.01 2.02 Application Example 10 P10 PBD-1 1000 0.98 2.56 1.28 Application Example 11 P11 PBD-1 1000 0.92 1.37 1.11 Application Example 12 P12 PBD-1 1000 0.93 1.47 1.13 Application Example 13 P13 PBD-1 1000 0.99 2.61 1.09 Comparative Application Example 1 D1 PBD-1 1000 1 1 1 Comparative Application Example 2 D2 PBD-1 1000 1.05 0.98 1.09

[0174] It can be seen from the comparison between Application Examples 1-4 and Application Examples 5-10 and Application Example 13 that using a carbazole compound with a heterocyclic substituent conforming to the structure shown in Formula I-1 or Formula II-1 as the host material of the light-emitting layer of the organic electroluminescent device results in better current efficiency of the prepared organic electroluminescent device.

[0175] It can be seen from the comparison between Application Example 1 and Application Examples 11-12 that using a carbazole compound with a heterocyclic substituent conforming to the structure shown in Formula II as the host material of the light-emitting layer of the organic electroluminescent device results in better current efficiency of the prepared organic electroluminescent device; using a carbazole compound with a heterocyclic substituent conforming to the structure shown in Formula I as the host material of the light-emitting layer of the organic electroluminescent device results in a lower driving voltage and a longer lifespan of the prepared organic electroluminescent device.

[0176] From the above content, it can be seen that in the present invention, by designing the structure of the carbazole compound with a heterocyclic substituent, it is suitable as the host material of the light-emitting layer of the organic electroluminescent device, enabling the organic electroluminescent device to have a high current efficiency, a long lifespan, and a low driving voltage.

[0177] The applicant declares that the present invention uses the above embodiments to illustrate the detailed process flow of the present invention, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A carbazole compound containing a heterocyclic substituent, characterized in that: The carbazole compound containing a heterocyclic substituent has a structure shown in the following formula I or formula II: X is selected from O or S; The hydrogen atoms in the compound of formula I or formula II may each independently be substituted by at least one of a deuterium atom, -F, -CN, a C1-C12 alkyl group, a C1-C12 alkoxy group, a triphenylsilyl group, a triphenylmethyl group, a C6-C20 aryl group or a C6-C20 heteroaryl group.

2. The carbazole compound containing a heterocyclic substituent according to claim 1, characterized in that: The C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, methylcyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl or adamantyl, bicyclo[2.2.1]heptyl or bicyclo[2.2.2]octyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy; Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl or 9,9-dimethylfluorenyl; Preferably, the C6-C20 heteroaryl group is selected from any one of a carbazolyl group, a dibenzofuranyl group or a dibenzothiophenyl group.

3. The carbazole compound containing a heterocyclic substituent according to claim 1 or 2, characterized in that: The hydrogen atoms in the compound of formula I or formula II can each independently be replaced by at least one of a deuterium atom, -F, -CN, a methoxy group, an ethoxy group, a propoxy group, a methyl group, an ethyl group, a propyl group, a tert-butyl group, a phenyl group, a biphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a triphenylsilyl group or a triphenylmethyl group.

4. The carbazole compound containing a heterocyclic substituent according to any one of claims 1 to 3, characterized in that: The carbazole compound containing a heterocyclic substituent has a structure shown in the following formula I-1 or formula II-1: Wherein, X has the same definition as in claim 1; Ar is selected from at least one of -F, -CN, C1-C12 alkyl, C1-C12 alkoxy, triphenylsilyl, triphenylmethyl, C6-C20 aryl or C6-C20 heteroaryl; The hydrogen atoms in the compound of formula I-1 or formula II-1 can each independently be substituted by at least one of a deuterium atom, -F, -CN, a C1-C12 alkyl group, a C1-C12 alkoxy group, a triphenylsilyl group, a triphenylmethyl group, a C6-C20 aryl group or a C6-C20 heteroaryl group.

5. The carbazole compound containing a heterocyclic substituent according to claim 4, characterized in that: The Ar is selected from at least one of -F, -CN, methoxy, ethoxy, propoxy, methyl, ethyl, propyl, tert-butyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, triphenylsilyl or triphenylmethyl.

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

7. An intermediate, characterized in that The intermediates include the following compounds: Wherein, X has the same definition as in claim 1; Ar has the same definition as in claim 4; X2 is selected from any one of -F, -Cl, -Br, -I; The hydrogen atoms in the compound of formula MA may each independently be replaced by a deuterium atom; The intermediate is used to prepare the carbazole compound containing a heterocyclic substituent as claimed in any one of claims 1 to 6.

8. The intermediate according to claim 7, characterized in that The intermediates include 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 carbazole compound containing heterocyclic substituents as claimed in any one of claims 1 to 6; Preferably, the organic thin film layer comprises a light-emitting layer, and a main material of the light-emitting layer comprises the carbazole compound containing a heterocyclic substituent as claimed in any one of claims 1 to 6.

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

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