Organic electroluminescent compound and use thereof

Abstract

This invention relates to the field of display technology, specifically to an organic electroluminescent compound and its applications. An organic electroluminescent compound has the structure shown in formula (1). Based on the structure of formula (1), further limiting the types of substituents can improve the structural stability of the compound. Furthermore, the HOMO and LUMO energy levels of the organic electroluminescent compound have a high degree of matching with adjacent energy levels. The introduction of polycyclic aromatic hydrocarbons is beneficial for mobility and energy level regulation, resulting in a more balanced carrier mobility of the organic electroluminescent compound. Consequently, organic electroluminescent devices containing this organic electroluminescent compound exhibit lower driving voltage, higher luminous efficiency, and longer lifetime.

Description

Technical Field

[0001] This invention relates to the field of display technology, and more specifically to an organic electroluminescent compound and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are devices that convert electrical energy into light by applying electricity to organic light-emitting materials. They generally have a structure comprising an anode, a cathode, and an organic layer between the anode and cathode. The organic layer of an organic OLED can consist of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (containing a host material and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The materials used in the organic layer are classified according to their function as hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials. In these organic OLEDs, due to the application of voltage, holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. The recombination of holes and electrons forms high-energy excitons. With this energy, the organic light-emitting compound reaches an excited state, and light is emitted by the energy generated when the excited state of the organic light-emitting compound returns to its ground state.

[0003] The most important factor determining the luminescence efficiency of organic EL devices is the luminescent material. The luminescent material must possess high quantum efficiency and high electron and hole mobility, and the resulting luminescent material layer must be uniform and stable. Luminescent materials are classified according to the color of their emission into blue, green, and red luminescent materials, as well as yellow and orange luminescent materials. Furthermore, luminescent materials can also be classified according to their function into host materials and dopant materials.

[0004] However, existing organic electroluminescent materials have low stability and poor matching between HOMO and LUMO energy levels and adjacent energy levels, resulting in an imbalance in carrier mobility. This leads to problems such as high driving voltage, low luminous efficiency, and short lifetime in organic electroluminescent devices containing these materials, which severely limits the application of organic electroluminescent devices. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of low stability and poor matching degree between HOMO and LUMO energy levels and adjacent energy levels in existing organic electroluminescent materials, which leads to an imbalance in carrier mobility. This results in organic electroluminescent devices containing such materials having high driving voltage, low luminous efficiency, and short lifetime. The invention aims to provide an organic electroluminescent compound and its application.

[0006] The solution adopted in this invention is as follows:

[0007] This invention provides an organic electroluminescent compound having the structure shown in formula (1):

[0008]

[0009] L is selected from single-bonded, substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C5-C60 heteroarylene;

[0010] X is selected from O or S;

[0011] Ar is selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl;

[0012] R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C60 aryl groups;

[0013] n1 is an integer selected from 0 to 8;

[0014] n2 is selected from integers between 0 and 6;

[0015] n3 and n4 are integers selected from 0 to 5;

[0016] The substituents in the substituted C6-C60 arylene, substituted C5-C60 heteroarylene, substituted C6-C60 aryl, and substituted C5-C60 heteroarylene are selected from one or more of deuterium, halogen, cyano, C1-C60 alkyl, C2-C60 alkenyl, C3-C60 cycloalkyl, C3-C60 cycloalkenyl, and C6-C60 aryl.

[0017] Substituents

[0018] In this application, the term "substituent" has the common meaning known in the art, referring to a chemical moiety covalently attached to or, where appropriate, fused to a parent nucleus group.

[0019] Replaced or not replaced

[0020] In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have substituents (hereinafter, for ease of description, substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The aforementioned substituent, i.e., Rc, can be, for example, deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, or C1-C60 heteroaryl. Optionally, it can be, for example, deuterium, a halogen group, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, etc. Of course, the number of substituents Rc can be one or more. When two substituents Rc are attached to the same atom, the two substituents Rc can exist independently or be connected to each other to form a ring with the atom; when there are two adjacent substituents Rc on a functional group, the two adjacent substituents Rc can exist independently or fused with the functional group to which they are attached to form a ring.

[0021] The definition of "unsubstituted" is as follows: it refers to being replaced by hydrogen atoms, and the hydrogen atoms in this invention include protium, deuterium, and tritium.

[0022] C1-C60, C3-C60, C6-C60

[0023] In this application, C1-C60, C3-C60, and C6-C60 define the range of carbon atoms, and the number of carbon atoms is any integer within the defined range. For example, C6-C60 aryl means that the number of carbon atoms representing the aryl group can be any integer within the range of 6-60, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60.

[0024] alkyl

[0025] In this application, the term "alkyl" refers, whether as part of other terms or used alone, to a saturated hydrocarbon group, which may be straight-chain or branched. The term "C1-C60 alkyl" is derived from a monovalent substituent of a straight-chain or branched saturated hydrocarbon having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms. Examples of such substituents include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0026] alkenyl

[0027] In this application, the term "alkenyl" refers, whether as part of other terms or used alone, to a saturated hydrocarbon group, which may be straight-chain or branched and has at least one carbon-carbon double bond. The term "C2-C60 alkenyl" refers to an alkenyl group having 2 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and even more preferably 1 to 20 carbon atoms. Of course, the alkenyl group includes, but is not limited to, vinyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, etc.

[0028] Aryl, aryl

[0029] In this application, the terms "aryl" and "arylene" include monocyclic, polycyclic, or fused-ring aryl groups, wherein the rings may be interrupted by short non-aromatic units and may contain a spirostructure. Aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracene, fluorene, and spirodifluorene. Arylene groups include, but are not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthracene, fluorene, and spirodifluorene. Arylene refers to a divalent or polyvalent group formed by the further loss of one or more hydrogen atoms from an aryl group.

[0030] heteroaryl, hypoaryl

[0031] In this application, the terms "hybrid aryl" and "heteroaryl" include monocyclic, polycyclic, or fused-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, and sulfur. Heteroaryl groups include, but are not limited to, furanyl, phenylthio, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetrazolyl, furanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl, and benzyl. Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalolinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzodioxacyclopentenyl, dihydroacridyl, and their derivatives; heteroaryl groups include, but are not limited to, furanyl, phenylthioyl, and pyrroleyl. Imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furanyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl Azolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, ininazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, quinolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazinyl, phenanthridineyl, benzodioxacyclopentenyl, dihydroacridyl, and their derivatives, etc. As used herein, the term "substituted" means that a hydrogen atom in the compound is replaced by another substituent. This position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0032] halogen

[0033] In this application, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0034] hydrogen

[0035] In this application, unless otherwise stated, hydrogen atoms include protium, deuterium, and tritium.

[0036] Preferably, the organic electroluminescent compound has the structure shown in formula (2):

[0037]

[0038] Among them, R 1 R2 R 3 R 4 The definitions of L, Ar, n1, n2, n3, and n4 are as described above.

[0039] Preferably, the organic electroluminescent compound has the following structure:

[0040]

[0041]

[0042] Preferably, L is selected from single-bonded, substituted or unsubstituted C6-C50 arylene or substituted or unsubstituted C5-C50 heteroarylene.

[0043] Preferably, the substituents in the substituted C6-C50 arylene or the substituted C5-C50 heteroarylene are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl.

[0044] Preferably, L is selected from single-bonded, substituted or unsubstituted C6-C25 arylene or substituted or unsubstituted C5-C25 heteroarylene.

[0045] Preferably, the substituents in the substituted C6-C25 arylene or the substituted C5-C25 heteroarylene are selected from one or more of deuterium, halogen, cyano, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C3-C25 cycloalkenyl, and C6-C25 aryl.

[0046] Preferably, L is selected from the group consisting of single bonds or the following groups:

[0047]

[0048] Preferably, Ar is selected from substituted or unsubstituted C6-C50 aryl or substituted or unsubstituted C5-C50 heteroaryl.

[0049] Preferably, the substituents in the substituted C6-C50 aryl and substituted C5-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl.

[0050] Preferably, Ar is selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C5-C25 heteroaryl.

[0051] Preferably, the substituents in the substituted C6-C25 aryl and substituted C5-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C3-C25 cycloalkenyl, and C6-C25 aryl.

[0052] Preferably, Ar is selected from substituted or unsubstituted C6-C15 aryl or substituted or unsubstituted C5-C15 heteroaryl;

[0053] Preferably, the total substituents of the substituted C6-C15 aryl and substituted C5-C15 heteroaryl are selected from one or more of deuterium, halogen, cyano, C1-C15 alkyl, C2-C15 alkenyl, C3-C15 cycloalkyl, C3-C15 cycloalkenyl, and C6-C15 aryl.

[0054] Preferably, Ar is selected from the group consisting of:

[0055]

[0056] Preferred, R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C50 aryl groups.

[0057] Preferably, the substituents of the substituted C6-C50 aryl group are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl.

[0058] Preferred, R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C25 aryl groups.

[0059] Preferably, the substituents of the substituted C6-C25 aryl group are selected from one or more of deuterium, halogen, cyano, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C3-C25 cycloalkenyl, and C6-C25 aryl.

[0060] Preferred, R 1 R 2 R 3 R 4 The same or different, and each independently selected from the group consisting of hydrogen, deuterium, or the following groups:

[0061]

[0062] Optionally, in this invention, -* represents a connection key.

[0063] Preferably, the compound is selected from one of the following structures:

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] Optionally, D4-D28 indicates that the number of deuterium atoms replacing hydrogen atoms is 4 to 28, specifically 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28.

[0091] This invention also provides a method for synthesizing the above-mentioned organic electroluminescent compounds:

[0092]

[0093] The present invention also provides an organic electroluminescent material comprising the above-mentioned organic electroluminescent compound.

[0094] The present invention also provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0095] Preferably, the organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises the aforementioned organic electroluminescent compound or the aforementioned organic electroluminescent material.

[0096] Preferably, the organic layer can be composed of a single-layer structure or a multi-layer structure with two or more layers stacked on top of each other. For example, the organic electroluminescent device may include one or more of the following sequentially arranged elements: a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

[0097] Preferably, the light-emitting layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0098] Preferably, the organic electroluminescent device may be, for example, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode sequentially stacked on a substrate.

[0099] Preferably, the anode comprises anode materials, particularly those with a high work function that facilitate hole injection into the first hole transport layer. For example, the anode material may include: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but is not limited thereto.

[0100] Preferably, the hole injection layer is used to enhance the ability to inject holes into the hole transport layer. The hole injection layer can be selected from benzidine derivatives, starburst-like aryl amine compounds, phthalocyanine derivatives, or other materials; this application does not impose any special limitations on this. The material of the hole injection layer can, for example, be selected from the following compounds or any combination thereof:

[0101]

[0102]

[0103] Preferably, the hole transport layer may include one or more hole transport materials. The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The material of the hole transport layer may be selected from carbazole polymers, carbazole-linked triarylamine compounds, or other types of compounds. This application does not impose any special limitations on this. For example, the material of the hole transport layer may be selected from the following compounds or any combination thereof:

[0104]

[0105]

[0106] Preferably, the light-emitting layer is capable of receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them to emit light in the visible light region.

[0107] Preferably, the light-emitting layer can be composed of a single light-emitting material, or it can include a host material and a guest material. For example, the light-emitting layer includes a host material and a guest material. Holes injected into the light-emitting layer and then electrons injected into the light-emitting layer can recombine in the light-emitting layer to form excitons. The excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby causing the guest material to emit light.

[0108] Preferably, the host material of the light-emitting layer may include metal chelating compounds, bis(phenylacetyl) derivatives, aromatic amine derivatives, dibenzofuran derivatives, and other types of materials. For example, the host material may include the above-mentioned nitrogen-containing compounds or the above-mentioned organic electroluminescent materials.

[0109] Preferably, the guest material of the luminescent layer may comprise a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other types of materials, which are not limited herein. The guest material is also called a dopant or dopant, and can be classified into fluorescent dopant and phosphorescent dopant according to the type of luminescence.

[0110] Preferably, the electron transport layer can be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light-emitting layer, and suppresses hole transfer from the light-emitting layer. The electron transport material is suitably one that can effectively receive electron injection from the cathode and transfer electrons to the light-emitting layer, and has a high electron mobility. The electron transport layer may be selected from, but is not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but is not limited to these.

[0111] Preferably, the electron transport layer includes, but is not limited to, the following structures:

[0112]

[0113]

[0114] Preferably, the electron injection layer is used to enhance the ability to inject electrons into the electron transport layer 8. The electron injection layer may include fluorenone, anthraquinone dimethane, biphenylquinone, thiamethane dioxide, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenemethane, anthrone, and their derivatives; inorganic materials such as alkali metal sulfides and alkali metal halides; or may include complexes of alkali metals and organic compounds.

[0115] Preferably, the cathode is a material with a small overflow function that facilitates electron injection into the functional layers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca.

[0116] The present invention also provides an application of the organic electroluminescent device as described above in optical fiber equipment, lighting equipment, electrophotographic photosensitive equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field-effect transistors, image sensors or dye lasers.

[0117] The above can be combined freely.

[0118] The beneficial effects of this invention are:

[0119] The present invention provides an organic electroluminescent compound having the structure shown in formula (1). Based on the structure of formula (1), further limiting the types of substituents can improve the structural stability of the compound. Moreover, the HOMO and LUMO energy levels of the organic electroluminescent compound have a high degree of matching with adjacent energy levels. The introduction of polycyclic aromatic hydrocarbons is beneficial to the mobility and energy level regulation, making the carrier mobility of the organic electroluminescent compound more balanced. As a result, the organic electroluminescent device containing the organic electroluminescent compound has a lower driving voltage, higher luminous efficiency and longer lifetime. Attached Figure Description

[0120] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0121] Figure 1 This is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0122] 1 – Substrate; 2 – Anode; 3 – Hole injection layer; 4 – Hole transport layer; 5 – Light emission layer; 6 – Electron transport layer; 7 – Electron injection layer; 8 – Cathode. Detailed Implementation

[0123] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, is within the scope of protection of the present invention.

[0124] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0125] Synthesis Example 1

[0126] This synthetic example provides the synthesis of compound B-1, and the synthetic route is shown below:

[0127]

[0128] (1) Preparation of intermediate B1-1

[0129] Under nitrogen protection, in a 250 mL four-necked flask, 14.0 g (50 mmol) of compound B1-A, 12.3 g (50 mmol) of compound B1-B, 0.4 g (0.5 mmol) of Pd(dppf)Cl2.CH2Cl2, and 13.8 g (100 mmol) of potassium carbonate were dissolved in a mixture of 140 mL toluene and 30 mL of water at room temperature. The reaction was quenched by reflux and stirring at 90 °C for 2 hours. After extraction with dichloromethane, the intermediate B1-1 was obtained by column chromatography (yield 84%).

[0130] (2) Preparation of intermediate B1-2

[0131] Under nitrogen protection, 17.0 g (42 mmol) of B1-1, 21.3 g (84 mmol) of pinacol diboronate, 0.4 g (0.5 mmol) of Pd(dppf)Cl2.CH2Cl2 and 12.3 g (126 mmol) of potassium acetate were dissolved in 180 mL of dioxane in a 250 mL four-necked flask at room temperature. The reaction was quenched by stirring under reflux at 100 °C for 8 hours. After extraction with dichloromethane, the intermediate B1-2 was obtained by column chromatography (yield 90%).

[0132] (3) Preparation of compound B-1

[0133] Under nitrogen protection, 18.6 g (38 mmol) of compound B1-2, 2.6 g (38 mmol) of compound B1-C1, 0.33 g (0.4 mmol) of Pd(dppf)Cl2.CH2Cl2, and 11 g (80 mmol) of potassium carbonate were dissolved in a mixture of 140 mL toluene and 30 mL of water in a 250 mL four-necked flask at room temperature. The reaction was quenched by reflux and stirring at 90 °C for 2 hours. After extraction with dichloromethane, compound B-1 was obtained by column chromatography (yield 80%).

[0134] Elemental analysis: C 48 H 28 Theoretical values: C, 92.88; H, 4.55; O, 2.58; Measured values: C, 92.90; H, 4.53. HRMS(ESI) m / z [M+H] + Theoretical value: 620.21; Measured value: 621.14.

[0135] Synthesis Example 2

[0136] This synthetic example provides the synthesis of compound B-5, and the synthetic route is shown below:

[0137]

[0138] (1) Preparation of intermediate B1-1

[0139] Under nitrogen protection, in a 250 mL four-necked flask, 14.0 g (50 mmol) of compound B1-A, 12.3 g (50 mmol) of compound B1-B, 0.4 g (0.5 mmol) of Pd(dppf)Cl2.CH2Cl2, and 13.8 g (100 mmol) of potassium carbonate were dissolved in a mixture of 140 mL toluene and 30 mL of water at room temperature. The reaction was quenched by stirring under reflux at 90 °C for 2 hours. After extraction with dichloromethane, the intermediate compound B1-1 was obtained by column chromatography (yield 84%).

[0140] (2) Preparation of intermediate B1-2

[0141] Under nitrogen protection, 17.0 g (42 mmol) of compound B1-1, 21.3 g (84 mmol) of pinacol diboronate, 0.4 g (0.5 mmol) of Pd(dppf)Cl2.CH2Cl2 and 12.3 g (126 mmol) of potassium acetate were dissolved in 180 mL of dioxane in a 250 mL four-necked flask at room temperature. The reaction was quenched by stirring under reflux at 105 °C for 8 hours. After extraction with dichloromethane, the intermediate B1-2 was obtained by column chromatography (yield 90%).

[0142] (3) Preparation of compound B-5

[0143] Under nitrogen protection, 18.6 g (38 mmol) of compound B1-2, 4.8 g (38 mmol) of compound B5-C1, 0.33 g (0.4 mmol) of Pd(dppf)Cl2.CH2Cl2, and 11 g (80 mmol) of potassium carbonate were dissolved in a mixture of 140 mL toluene and 30 mL of water in a 250 mL four-necked flask at room temperature. The reaction was quenched by reflux and stirring at 90 °C for 2 hours. After extraction with dichloromethane, compound B-5 was obtained by column chromatography (yield 82%).

[0144] Elemental analysis: C 52 H 23 Theoretical D7O values: C, 92.14; H, 5.50; O, 2.36; Measured values: C, 92.16; H, 5.48. HRMS(ESI) m / z [M+H] + Theoretical value: 677.27; Measured value: 678.16.

[0145] Synthesis Example 3

[0146] Compound B-15 was prepared using the same synthetic method as in Example 1, except that starting material B15-A was used instead of B1-A and B15-C was used instead of B1-C. The synthetic route is shown below:

[0147]

[0148] Compound B-15 was obtained in 85% yield. Elemental analysis: C 48 H 28 Theoretical values ​​for O: C, 92.88; H, 4.55; O, 2.58; Measured values: C, 92.89; H, 4.54. HRMS(ESI) m / z [M+H] + Theoretical value: 620.21; Measured value: 621.24.

[0149] Synthesis Example 4

[0150] Compound B-18 was prepared using the same synthetic method as in Example 1, except that starting material B15-A was used instead of B1-A and B18-C was used instead of B1-C. The synthetic route is shown below:

[0151]

[0152] Compound B-18 was obtained in 84% yield. Elemental analysis: C 48 H 23 Theoretical D5O values: C, 92.13; H, 5.31; O, 2.56; Measured values: C, 92.16; H, 5.28. HRMS(ESI) m / z [M+H] + Theoretical value: 625.25; Measured value: 626.14.

[0153] Synthesis Example 5

[0154] Compound B-26 was prepared using the same synthetic method as in Example 1, except that starting material B26-A was used instead of B1-A and B26-C was used instead of B1-C. The synthetic route is shown below:

[0155]

[0156] Compound B-26 was obtained in 81% yield. Elemental analysis: C 52 H 23 Theoretical D7O values: C, 92.14; H, 5.50; O, 2.36; Measured values: C, 92.15; H, 5.49. HRMS(ESI) m / z [M+H] + Theoretical value: 677.27; Measured value: 678.25.

[0157] Synthesis Example 6

[0158] Compound B-45 was prepared using the same synthetic method as in Example 1, except that starting material B45-B was used instead of B1-B and B45-C was used instead of B1-C. The synthetic route is shown below:

[0159]

[0160] Compound B-45 was obtained in 80% yield. Elemental analysis: C 48 H 28 Theoretical values: C, 92.88; H, 4.55; O, 2.58; Measured values: C, 92.86; H, 4.57. HRMS(ESI) m / z [M+H] + Theoretical value: 620.21; Measured value: 621.17.

[0161] Synthesis Example 7

[0162] Compound B-70 was prepared using the same synthetic method as in Example 1, except that starting material B26-A was used instead of B1-A and B70-C was used instead of B1-C. The synthetic route is shown below:

[0163]

[0164] Compound B-70 was obtained in 79% yield. Elemental analysis: C 52 H 30 Theoretical values ​​for O: C, 93.11; H, 4.51; O, 2.39; Measured values: C, 93.13; H, 4.09. HRMS(ESI) m / z [M+H] + Theoretical value: 670.23; Measured value: 671.31.

[0165] Synthesis Example 8

[0166] Compound B-96 was prepared using the same synthetic method as in Example 1, except that starting material B96-A was used instead of B1-A and B18-C was used instead of B1-C. The synthetic route is shown below:

[0167]

[0168] Compound B-96 was obtained in 84% yield. Elemental analysis: C 48 H 23 Theoretical D5O values: C, 92.13; H, 5.31; O, 2.56; Measured values: C, 92.14; H, 5.30. HRMS(ESI) m / z [M+H] +Theoretical value: 625.25; Measured value: 626.17.

[0169] Synthesis Example 9

[0170] Compound B-126 was prepared using the same synthetic method as in Example 1, except that starting material B126-A was used instead of B1-A, B126-B instead of B1-B, and B18-C instead of B1-C. The synthetic route is shown below:

[0171]

[0172] Compound B-126 was obtained in 82% yield. Elemental analysis: C 48 H 23 Theoretical D5O values: C, 92.13; H, 5.31; O, 2.56; Measured values: C, 92.15; H, 5.29. HRMS(ESI) m / z [M+H] + Theoretical value: 625.25; Measured value: 626.13.

[0173] Synthesis Example 10

[0174] Compound B-158 was prepared using the same synthetic method as in Example 1, except that starting material B96-A was used instead of B1-A and B158-C was used instead of B1-C. The synthetic route is shown below:

[0175]

[0176] Compound B-158 was obtained in 81% yield. Elemental analysis: C 58 H 34 Theoretical values ​​for O: C, 93.27; H, 4.59; O, 2.14; Measured values: C, 93.29; H, 4.57. HRMS(ESI) m / z [M+H] + Theoretical value: 746.26; Measured value: 747.20.

[0177] Synthesis Example 11

[0178] Compound B-158 was prepared using the same synthetic method as in Example 1, except that starting material B126-A was used instead of B1-A, B126-B instead of B1-B, and B5-C instead of B1-C. The synthetic route is shown below:

[0179]

[0180] Compound B-158 was obtained in 81% yield. Elemental analysis: C 52 H 23Theoretical D7S values: C, 90.01; H, 5.37; S, 4.62; Measured values: C, 90.03; H, 5.38; S, 4.59. HRMS(ESI) m / z [M+H] + Theoretical value: 693.25; Measured value: 694.13.

[0181] Synthesis Example 12

[0182] Compound B-258 was prepared using the same synthetic method as in Example 1, except that starting materials B258-A, B45-B, and B70-C were used instead of B1-A, and the synthetic route is shown below:

[0183]

[0184] Compound B-258 was obtained in 80% yield. Elemental analysis: C 52 H 30 Theoretical values: C, 90.93; H, 4.40; S, 4.67; Measured values: C, 90.95; H, 4.39; S, 4.66. HRMS(ESI) m / z [M+H] + Theoretical value: 686.21; Measured value: 687.19.

[0185] Synthesis Example 13

[0186] Compound B-302 was prepared using the same synthetic method as in Example 1, except that starting material B302-A was used instead of B1-A, B302-B instead of B1-B, and B302-C instead of B1-C. The synthetic route is shown below:

[0187]

[0188] Compound B-302 was obtained in 78% yield. Elemental analysis: C 52 H7D 23 Theoretical values: C, 90.00; H, 7.69; O, 2.31; Measured values: C, 90.02; H, 7.67. HRMS(ESI) m / z [M+H] + Theoretical value: 693.37; Measured value: 694.23.

[0189] Synthesis Example 14

[0190] Compound B-336 was prepared using the same synthetic method as in Example 1, except that starting material B302-A was used instead of B1-A and B302-C was used instead of B1-C. The synthetic route is shown below:

[0191]

[0192] Compound B-336 was obtained in 77% yield. Elemental analysis: C 52 H9D 21 Theoretical values ​​for O: C, 90.26; H, 7.42; O, 2.31; Measured values: C, 90.27; H, 7.41. HRMS(ESI) m / z [M+H] + Theoretical value: 691.36; Measured value: 692.21.

[0193] Synthesis Example 15

[0194] Compound B-352 was prepared using the same synthetic method as in Example 1, except that starting material B15-A was used instead of B1-A, B352-B instead of B1-B, and B352-C instead of B1-C. The synthetic route is shown below:

[0195]

[0196] Compound B-352 was obtained in 79% yield. Elemental analysis: C 48 H 15 D 13 Theoretical values: C, 90.96; H, 6.52; O, 2.52; Measured values: C, 90.98; H, 6.50. HRMS(ESI) m / z [M+H] + Theoretical value: 633.30; Measured value: 634.12.

[0197] Synthesis Example 16

[0198] Compound B-372 was prepared using the same synthetic method as in Example 1, except that starting material B15-A was used instead of B1-A, B352-B instead of B1-B, and B336-C instead of B1-C. The synthetic route is shown below:

[0199]

[0200] Compound B-372 was obtained in 78% yield. Elemental analysis: C 52 H9D 21 Theoretical values ​​for O: C, 90.26; H, 7.42; O, 2.31; Measured values: C, 90.29; H, 7.39. HRMS(ESI) m / z [M+H] + Theoretical value: 691.36; Measured value: 692.30.

[0201] Synthesis Example 17

[0202] Compound B-442 was prepared using the same synthetic method as in Example 1, except that starting materials B442-A, B45-B, and B352-C were used instead of B1-A, and the synthetic route is shown below:

[0203]

[0204] Compound B-442 was obtained in 76% yield. Elemental analysis: C 48 H9D 19 Theoretical values ​​for O: C, 90.10; H, 7.40; O, 2.50; Measured values: C, 90.13; H, 7.17. HRMS(ESI) m / z [M+H] + Theoretical value: 639.33; Measured value: 640.11.

[0205] Device Examples

[0206] The materials used to prepare the following device embodiments or device comparative examples are shown in Table 1 below.

[0207] Table 1

[0208]

[0209]

[0210] Device Example 1

[0211] This embodiment provides an organic electroluminescent device, such as... Figure 1 As shown, the device includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8, which are sequentially stacked on a substrate 1. The device structure is: anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0212] The specific preparation process is as follows:

[0213] 1) Substrate cleaning:

[0214] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0215] 2) Preparation of organic layer:

[0216] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, hole injection layer (HIL) / hole transport layer (HTL) / light emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / thick cathode (Al) are sequentially deposited on the anode film.

[0217] in:

[0218] The hole injection layer (HIL) is made of F4-TCNQ with a thickness of 10 nm and a total evaporation rate of 0.1 nm / s.

[0219] The hole transport layer (HTL) is made of HT-1 material, has a thickness of 80 nm, and a total evaporation rate of 0.1 nm / s.

[0220] The light-emitting layer (EML) is vacuum-deposited by co-evaporation. The material of the light-emitting layer includes a host material and a dopant material, wherein the guest material is BD, and the host material is composed of B-1 and BD compound from Synthesis Example 1. The weight ratio of the host material to the dopant material is 97:3, the thickness is 35nm, and the total evaporation rate is 0.1nm / s.

[0221] The electron transport layer (ETL) is a binary mixture of ET and LiQ in a mass ratio of 1:1, with a thickness of 30 nm and a total evaporation rate of 0.1 nm / s.

[0222] The electron injection layer (EIL) is made of LiQ with a thickness of 1 nm and a total evaporation rate of 0.1 nm / s.

[0223] The cathode is made of aluminum with a thickness of 90 nm and a deposition rate of 1 nm / s.

[0224] Device Example 2

[0225] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-5 in Synthesis Example 2.

[0226] Device Example 3

[0227] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-15 in Synthesis Example 3.

[0228] Device Example 4

[0229] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-18 in Synthesis Example 4.

[0230] Device Example 5

[0231] Similar to Device Example 1, the difference is that material N-1 in Device Example 1 is replaced with N-26 in Synthesis Example 5.

[0232] Device Example 6

[0233] Similar to Device Example 1, the difference is that material N-1 in Device Example 1 is replaced with N-45 in Synthesis Example 6.

[0234] Device Example 7

[0235] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-70 in Synthesis Example 7.

[0236] Device Example 8

[0237] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-96 in Synthesis Example 8.

[0238] Device Example 9

[0239] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-126 in Synthesis Example 9.

[0240] Device Example 10

[0241] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-158 in Synthesis Example 10.

[0242] Device Example 11

[0243] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-169 in Synthesis Example 11.

[0244] Device Example 12

[0245] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-258 in Synthesis Example 12.

[0246] Device Example 13

[0247] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-302 in Synthesis Example 13.

[0248] Device Example 14

[0249] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-336 in Synthesis Example 14.

[0250] Device Example 15

[0251] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-352 in Synthesis Example 15.

[0252] Device Example 16

[0253] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-372 in Synthesis Example 16.

[0254] Device Example 17

[0255] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with B-442 in Synthesis Example 17.

[0256] Device Comparison Example 1

[0257] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with the following structure REF-1.

[0258]

[0259] Device Comparison Example 2

[0260] Similar to Device Example 1, the difference is that material B-1 in Device Example 1 is replaced with the following structure REF-2.

[0261]

[0262] Device Test Examples

[0263] The organic electroluminescent devices obtained in Device Examples 1-17 and Device Comparative Examples 1-2 in the device examples were tested.

[0264] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0265] Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 .

[0266] Lifetime test: Current density 10mA / cm 2 The time (in hours) when the device brightness drops to 95% of its original brightness is recorded. The lifetime T95 and current efficiency of Comparative Example 1 are set to 100. The lifetime T95 and current efficiency results of Device Examples 1-17 and Comparative Example 2 relative to Comparative Example 1 are shown in Table 2.

[0267] Table 2. Photoelectric property test table for Device Examples 1 to 17 and Device Comparative Examples 1-2

[0268] Serial Number Drive voltage (V) relative current efficiency Relative lifespan T95 Device Example 1 4.03 111.37 177.53 Device Example 2 3.99 115.76 197.12 Device Example 3 4.02 110.52 176.46 Device Example 4 4.04 111.47 178.61 Device Example 5 4.00 114.85 193.28 Device Example 6 4.01 110.88 176.92 Device Example 7 4.01 114.23 190.21 Device Example 8 4.02 111.76 179.59 Device Example 9 4.03 112.14 180.49 Device Example 10 4.05 110.11 175.83 Device Example 11 3.97 115.21 195.39 Device Example 12 4.01 114.65 188.49 Device Example 13 4.01 118.11 204.67 Device Example 14 3.99 117.67 202.31 Device Example 15 3.98 116.21 199.45 Device Example 16 3.97 117.34 202.56 Device Example 17 4.00 117.21 203.12 Device Comparison Example 1 4.24 100 100 Device Comparison Example 2 4.16 103.54 105.78

[0269] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An organic electroluminescent compound, characterized in that, The organic electroluminescent compound has the structure shown in formula (1): L is selected from single-bonded, substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C5-C60 heteroarylene; X is selected from O or S; Ar is selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl; R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C60 aryl groups; n1 is an integer selected from 0 to 8; n2 is selected from integers between 0 and 6; n3 and n4 are integers selected from 0 to 5; The substituents in the substituted C6-C60 arylene, substituted C5-C60 heteroarylene, substituted C6-C60 aryl, and substituted C5-C60 heteroarylene are selected from one or more of deuterium, halogen, cyano, C1-C60 alkyl, C2-C60 alkenyl, C3-C60 cycloalkyl, C3-C60 cycloalkenyl, and C6-C60 aryl.

2. The organic electroluminescent compound according to claim 1, characterized in that, The compound has the following structure:

3. The organic electroluminescent compound according to claim 1 or 2, characterized in that, L is selected from single bonds, substituted or unsubstituted C6-C50 arylene groups, or substituted or unsubstituted C5-C50 heteroarylene groups; wherein the substituents in the substituted C6-C50 arylene groups or the substituted C5-C50 heteroarylene groups are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl.

4. The organic electroluminescent compound according to any one of claims 1-3, characterized in that, L is selected from the group consisting of single bonds or the following groups:

5. The organic electroluminescent compound according to any one of claims 1-4, characterized in that, Ar is selected from substituted or unsubstituted C6-C50 aryl or substituted or unsubstituted C5-C50 heteroaryl; The substituents in the substituted C6-C50 aryl and substituted C5-C50 heteroaryl are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl. Preferably, Ar is selected from substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C5-C25 heteroaryl; The substituents in the substituted C6-C25 aryl and substituted C5-C25 heteroaryl are selected from one or more of deuterium, halogen, cyano, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C3-C25 cycloalkenyl, and C6-C25 aryl. Preferably, Ar is selected from substituted or unsubstituted C6-C15 aryl or substituted or unsubstituted C5-C15 heteroaryl; The substituted C6-C15 aryl and substituted C5-C15 heteroaryl groups are selected from one or more of deuterium, halogen, cyano, C1-C15 alkyl, C2-C15 alkenyl, C3-C15 cycloalkyl, C3-C15 cycloalkenyl, and C6-C15 aryl. Preferably, Ar is selected from the group consisting of:

6. The organic electroluminescent compound according to any one of claims 1-5, characterized in that, R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C50 aryl groups; The substituents of the substituted C6-C50 aryl group are selected from one or more of deuterium, halogen, cyano, C1-C50 alkyl, C2-C50 alkenyl, C3-C50 cycloalkyl, C3-C50 cycloalkenyl, and C6-C50 aryl. Preferred, R 1 R 2 R 3 R 4 They may be the same or different, and each is independently selected from hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C6-C25 aryl groups; The substituents of the substituted C6-C25 aryl group are selected from one or more of deuterium, halogen, cyano, C1-C25 alkyl, C2-C25 alkenyl, C3-C25 cycloalkyl, C3-C25 cycloalkenyl, and C6-C25 aryl. Preferred, R 1 R 2 R 3 R 4 The same or different, and each independently selected from the group consisting of hydrogen, deuterium, or the following groups:

7. The organic electroluminescent compound according to any one of claims 1-6, characterized in that, The organic electroluminescent compound is selected from one of the following structures:

8. An organic electroluminescent material, characterized in that, The organic electroluminescent material comprises the organic electroluminescent compound as described in any one of claims 1-7.

9. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises an organic electroluminescent compound as described in any one of claims 1-7 or an organic electroluminescent material as described in claim 8.

10. The application of an organic electroluminescent compound as described in any one of claims 1-7, or an organic electroluminescent material as described in claim 8, or an organic electroluminescent device as described in claim 9, in fiber optic devices, lighting devices, electrophotographic photosensitive devices, photoelectric converters, organic solar cells, switching element devices, organic light-emitting field-effect transistors, image sensors, or dye lasers.

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