Condensed ring compound and application thereof

Abstract

The invention relates to the technical field of display, in particular to a fused ring compound and application thereof. The fused ring compound provided by the invention has a structure as shown in a formula (1), a specific mother nucleus structure is formed through phenanthroline combination, and a specific substituent group is limited, so that the obtained fused ring compound can be used for an n-type charge generation layer, an electron transport layer or a hole blocking layer and can be better matched with other functional materials of an organic electroluminescent device; therefore, the organic electroluminescent device of the organic compound has lower driving voltage, higher luminous efficiency and longer service life.

Description

Technical Field

[0001] This invention relates to the field of display technology, and more specifically to a fused ring compound and its applications. Background Technology

[0002] Organic light-emitting materials can be broadly categorized by function into light-emitting materials, hole-injection materials, hole-transport materials, electron-transport materials, and electron-injection materials. Organic light-emitting diodes (OLEDs) are devices that emit light through current-driven illumination, offering advantages such as thinness, flexibility, high contrast, and wide color gamut. Due to their high current efficiency and long lifetime, stacked OLEDs have gradually become a research focus. These mainly consist of a first light-emitting layer, a second light-emitting layer, and a charge generation layer (CGL) positioned between the first and second light-emitting layers to ensure efficient charge distribution across the light-emitting layers while improving the current efficiency of each layer. However, most existing stacked materials suffer from poor matching of the charge generation layer, resulting in high driving voltage, low luminous efficiency, and short lifetime in OLEDs containing these materials, severely limiting their applications.

[0003] Therefore, there is an urgent need in related technologies for charge-generating materials that can have a higher degree of compatibility with existing multilayer materials. Summary of the Invention

[0004] The purpose of this invention is to overcome the lack of charge-generating materials in related technologies that can have a higher degree of matching with existing multilayer materials, resulting in organic electroluminescent devices containing such organic electroluminescent materials having high driving voltage, low luminous efficiency, and short lifespan, and thus to provide a fused ring compound and its applications.

[0005] In this invention, Indicates a connection key.

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

[0007] This invention provides a fused-ring compound having the structure shown in formula (1):

[0008]

[0009] In the formula,

[0010] L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C1-C60 heteroarylene;

[0011] Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C1-C60 heteroaryl groups;

[0012] a and b are each independently selected from integers from 1 to 7;

[0013] The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C6-C60 aryl, and substituted C1-C60 heteroarylene are selected from one or more of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C1-C60 heteroarylene.

[0014] single bond

[0015] In this application, the term "single bond" refers to the connection between two adjacent groups.

[0016] Substituents

[0017] 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.

[0018] Replaced or not replaced

[0019] 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 substituent Rc mentioned above can be, for example, one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamine, and C3-C60 heteroarylamine. 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 two adjacent substituents Rc exist on a functional group, the adjacent substituents Rc can exist independently or fuse with the functional group to which they are attached to form a ring.

[0020] halogen

[0021] In this application, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

[0022] alkyl

[0023] 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.

[0024] cycloalkyl

[0025] In this application, the term "cycloalkyl" refers to a cyclic alkyl group consisting of at least 3 atoms, and more specifically, to a monocyclic or polycyclic hydrocarbon derived from a main chain of 3 to 60 carbon atoms, preferably 3 to 40 carbon atoms, and even more preferably 3 to 20 carbon atoms. Of course, the cycloalkyl group includes, but is not limited to, cyclopropyl, cyclobutyl, adamantyl, etc.

[0026] Heterocyclic alkyl

[0027] In this application, the term "heterocyclic alkyl" includes one or more of O, S, Se, N, and Si as heteroatoms, and is a monocyclic or polycyclic ring having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and even more preferably 1 to 20 carbon atoms. Here, the polycyclic refers to a group in which a heterocyclic alkyl group is directly attached to or fused with another cyclic group. Here, the other cyclic group can also be a heterocyclic alkyl group, but it can also be another type of cyclic group, such as cycloalkyl, aryl, heteroaryl, 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 "heteroaryl" and "hybridoaryl" 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, pyrroloyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetraazolyl, furazolidyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophene, isobenzofuranyl, dibenzofuranyl, dibenzothiophene, benzimidazolyl, and benzyl. Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxalinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzo[m]dioxacyclopentenyl, dihydroacridyl, and their derivatives; heteroaryl groups include, but are not limited to, furanyl, phenylthio, and pyrroleyl. Imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl Azolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, ininazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazinyl, phenanthridyl, phenanthridyl, benzo[m]dioxacyclopentenyl, 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] C1-C60, C3-C60, C6-C60

[0033] In this application, "C1-C60, C3-C60, C6-C60" defines the range of carbon atoms, indicating that the number of carbon atoms is any integer within the defined range. For example, C6-C60 aryl means that the number of carbon atoms in 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, 60.

[0034] Preferably, the fused-ring compound has the following structure:

[0035]

[0036]

[0037] Preferred, L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C50 arylene, or substituted or unsubstituted C6-C50 heteroarylene;

[0038] Wherein, the substituents in the substituted C6-C50 arylene or the substituted C6-C50 heteroarylene are selected from one or more of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C50 alkyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0039] Preferred, L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C25 arylene, or substituted or unsubstituted C6-C25 heteroarylene.

[0040] Wherein, the substituents in the substituted C6-C25 arylene or the substituted C6-C25 heteroarylene are selected from one or more of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C25 alkyl, C3-C25 cycloalkyl, C1-C25 heterocycloalkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0041] Preferred, L 1 L 2and L 3 Each group is independently selected from a single bond or a group consisting of the following groups:

[0042]

[0043]

[0044] It is understood that in this invention, -* indicates a connection position.

[0045] Preferred, Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C50 aryl groups and substituted or unsubstituted C1-C50 heteroaryl groups;

[0046] The substituents in the substituted C6-C50 aryl and substituted C1-C50 heteroaryl are selected from one or more of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C50 alkyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C6-C50 aryl, and C1-C50 heteroaryl.

[0047] Preferred, Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C25 aryl groups and substituted or unsubstituted C1-C25 heteroaryl groups;

[0048] The substituents in the substituted C6-C25 aryl and substituted C1-C25 heteroaryl are selected from one or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C25 alkyl, C3-C25 cycloalkyl, C1-C25 heterocycloalkyl, C6-C25 aryl, and C1-C25 heteroaryl.

[0049] Preferred, Ar 1 Ar 2 and Ar 3 Each is independently selected from the group consisting of the following groups:

[0050]

[0051]

[0052]

[0053] Preferably, a and b are each independently selected from integers 1-6. Preferably, a and b are each independently selected from integers 1-5. Preferably, a and b are each independently selected from integers 1-4. Preferably, a and b are each independently selected from integers 1-3. Preferably, a and b are each independently selected from integers 1 or 2. Preferably, a and b are 1.

[0054] Preferably, the fused-ring compound has the following structure:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] The present invention also provides a method for synthesizing the compound shown in formula (1), and the specific synthetic route is shown below.

[0064] Among them, when Ar 2 and Ar 3 Same, L 1 and L 2 At the same time, its synthetic route is shown in reaction formula 1:

[0065]

[0066] When Ar 2 and Ar 3 Different or L 1 and L 2 At the same time, its synthetic route is shown in reaction formula 2:

[0067]

[0068] The present invention also provides an n-type charge generation layer, wherein the n-type charge generation layer comprises one or a combination of at least two of the above-mentioned fused ring compounds.

[0069] The present invention also provides an electron transport layer comprising one or a combination of at least two of the above-mentioned fused ring compounds.

[0070] The present invention also provides a hole-blocking layer, wherein the hole-blocking layer comprises one or a combination of at least two of the above-mentioned fused ring compounds.

[0071] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a cathode, an anode, and an organic layer located between the cathode and the anode, the organic layer comprising one or a combination of at least two of the above-mentioned fused ring compounds.

[0072] Preferably, the organic layer includes the above-described n-type charge generation layer and / or the above-described electron transport layer and / or the above-described hole blocking layer.

[0073] Preferably, the organic layer comprises one or more of a hole injection layer, a first organic light-emitting layer, a second organic light-emitting layer, and an electron injection layer;

[0074] Wherein, when the organic electroluminescent device includes an n-type charge generation layer, the n-type charge generation layer is located between the first organic light-emitting layer and the second organic light-emitting layer.

[0075] Preferably, the organic electroluminescent device may include an anode, a hole injection layer, a first hole transport layer, a first electron blocking layer, a first organic light-emitting layer, a first hole blocking layer, a first electron transport layer, an n-type charge generation layer, a p-type charge generation layer, a second hole transport layer, a second electron blocking layer, a second organic light-emitting layer, a second hole blocking layer, a second electron transport layer, an electron injection layer, and a cathode, all stacked together.

[0076] Preferably, the anode comprises an anode material, preferably a material with a large work function that facilitates 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.

[0077] More preferably, the anode is selected as indium tin oxide (ITO).

[0078] Preferably, the hole injection layer is used to enhance the ability to inject holes into the first 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:

[0079]

[0080]

[0081] Optionally, the first hole transport layer may include one or more hole transport materials. The first hole transport layer is a layer that receives holes from the first hole injection layer and transports the holes to the light-emitting layer. The hole transport layer material 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. The material of the first hole transport layer may, for example, be selected from the following compounds or any combination thereof:

[0082]

[0083]

[0084] More preferably, the first hole transport layer may be composed of HT-1.

[0085] Preferably, the material of the first electron blocking layer is selected from conventional materials used in the art. An electron blocking layer is a layer disposed between the light-emitting auxiliary layer and the light-emitting layer to prevent electrons injected from the cathode from transferring to the light-emitting auxiliary layer and recombinating in the light-emitting layer; it can also be called an electron blocking layer or an electron suppression layer. The electron blocking layer is preferably a material with a lower electron affinity than the electron transport layer. This application does not impose any special limitations in this regard.

[0086] More preferably, the first electron blocking layer may be composed of mCP.

[0087]

[0088] Preferably, the first organic light-emitting layer may include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, with a blue light-emitting layer being the most preferred. This application does not impose any special limitations on the blue light-emitting layer; conventional blue light-emitting layer materials in the art can be used. For example, the host material for blue light emission can be an anthracene derivative, and the guest material can be a boron nitride (BN) resonant fluorescent material.

[0089] More preferably, the first organic light-emitting layer is composed of the following materials:

[0090]

[0091] Preferably, the material of the first hole blocking layer is selected from conventional materials in the art. The hole blocking layer is a layer disposed between the electron transport layer and the light-emitting layer to prevent holes injected by the anode from being transferred to the electron transport layer and recombination in the light-emitting layer; it can also be referred to as a hole suppression layer or a hole blocking layer. The hole blocking layer is preferably made of a material with high ionization energy. This application does not impose any special limitations in this regard.

[0092] More preferably, the material of the first hole-blocking layer shown is selected from BCP.

[0093]

[0094] Preferably, the first electron transport layer can be a single-layer structure or a multi-layer structure, and it can include one or more electron transport materials. The first electron transport layer can be selected from, but is not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives or other electron transport materials. This application does not impose any special restrictions on this.

[0095] More preferably, the first electron transport layer is composed of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and lithium octahydroxyquinoline (LiQ).

[0096]

[0097] Preferably, the n-type charge generation layer may be composed of one or more of the compounds shown in formula (1) and the compounds shown in C-1-C-135.

[0098] Preferably, the p-type charge generation layer is not subject to any special restrictions and can be set in a conventional manner in the art and matched with the above-mentioned n-type charge generation layer.

[0099] More preferably, the p-type charge generation layer may be composed of HAT-CN and TCTA, and the ratio of them is not specially set in this application.

[0100] Preferably, the second hole transport layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first hole transport layer.

[0101] Preferably, the second electron blocking layer is not subject to any special restrictions and can be set in a conventional manner in the art, such as referring to the setting of the first electron blocking layer.

[0102] Preferably, the second organic light-emitting layer may include a blue light-emitting layer, a red light-emitting layer, or a green light-emitting layer, with a blue light-emitting layer being the most preferred. This application does not impose any special limitations on the blue light-emitting layer; conventional blue light-emitting layer materials in the art can be used, for example, it can be configured similarly to the first organic light-emitting layer.

[0103] Preferably, the second hole blocking layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first hole blocking layer.

[0104] Preferably, the second electron transport layer is not subject to any special restrictions and can adopt conventional settings in the field, such as referring to the settings of the first electron transport layer.

[0105] Preferably, the electron injection layer is used to enhance the ability to inject electrons into the second electron transport layer. The electron injection layer may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic materials.

[0106] More preferably, the electron-injected layer may include ytterbium (Yb).

[0107] Preferably, the cathode may comprise a cathode material that has a small work function and 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.

[0108] More preferably, the cathode may include a metal electrode containing magnesium and silver as the cathode, and the ratio of these components is not specifically set in this application.

[0109] It should be noted that the above-mentioned organic electroluminescent devices are fabricated using conventional methods in the art, such as depositing layers on a substrate.

[0110] The present invention also provides an organic electroluminescent product, which includes the above-described organic electroluminescent device.

[0111] The present invention also provides an electronic device comprising the above-described fused ring compound.

[0112] Preferably, the electronic devices include perovskite photovoltaic devices, perovskite light-emitting devices, display devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic field quenching devices, luminescent electrochemical cells, and organic laser diodes.

[0113] The above can be combined freely.

[0114] The beneficial effects of this invention are:

[0115] The present invention provides a fused ring compound having the structure shown in formula (1), which forms a specific core structure by combining o-phenanthroline and defines its specific substituents, so that the obtained fused ring compound can be better matched with other functional materials of organic electroluminescent devices for use in n-type charge generation layers, electron transport layers or hole blocking layers, so that the organic electroluminescent device of organic compound has a lower driving voltage, higher luminous efficiency and longer lifetime. Attached Figure Description

[0116] 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.

[0117] Figure 1 This is a structural diagram of the stacked organic electroluminescent device in the device embodiment of the present invention;

[0118] 1-Anode, 2-Hole injection layer, 3-First hole transport layer, 4-First electron blocking layer, 5-First organic light-emitting layer, 6-First hole blocking layer, 7-First electron transport layer, 8-n-type charge generation layer, 9-p-type charge generation layer, 10-Second hole transport layer, 11-Second electron blocking layer, 12-Second organic light-emitting layer, 13-Second hole blocking layer, 14-Second electron transport layer, 15-Electron injection layer, 16-Cathode. Detailed Implementation

[0119] 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, falls within the protection scope of the present invention.

[0120] 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.

[0121] Synthesis of intermediate CA-9:

[0122]

[0123] Synthesis of intermediate CA-9: In a 500 mL three-necked flask under nitrogen protection, starting materials CA-9-a (15.00 g, 60.22 mmol), CA-9-b (10.46 g, 66.24 mmol), dioxane:water = 4:1 (160:40 mL), tetra(triphenylphosphine)palladium (348 mg, 0.30 mmol), and potassium carbonate (20.78 g, 0.15 mol) were added. The reaction was carried out overnight at 70 °C. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate to remove the organic solvent. The crude product was purified by chromatography (n-hexane / dichloromethane, 3 / 1) to give intermediate 1-c-9 (yield 56.3%).

[0124] The intermediates shown in Table 1 were prepared using the same method as intermediate CA-9, with the difference being the replacement of the corresponding raw materials. Their elemental analysis is shown in Table 3.

[0125] Table 1 Synthesis of intermediate CA-n

[0126]

[0127]

[0128] Synthesis of intermediate CA-48:

[0129]

[0130] (1) The intermediate CA-9 was obtained by the synthesis method of intermediate CA-9.

[0131] (2) Synthesis of intermediate CA-48: In a 500 mL three-necked flask under nitrogen protection, intermediate CA-9 (11.00 g, 33.67 mmol), starting material CA-49-c (5.79 g, 37.03 mmol), dioxane:water = 4:1 (100:25 mL), tetra(triphenylphosphine)palladium (168 mg, 0.17 mmol), and potassium carbonate (11.62 g, 0.08 mol) were added. The reaction was carried out overnight at 90 °C. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate to remove the organic solvent. The crude product was purified by chromatography (n-hexane / dichloromethane, 3 / 1) to obtain intermediate CA-9 (yield 78.1%).

[0132] The intermediates shown in Table 2 were synthesized using the method of intermediate CA-48, and their elemental analysis is shown in Table 3.

[0133] Table 2 Synthesis of intermediate CA-n

[0134]

[0135]

[0136] Table 3 Elemental analysis of intermediate CA-n

[0137]

[0138]

[0139]

[0140] Synthesis Example 1

[0141] This embodiment provides a method for synthesizing compound C-1, and the synthetic route is shown in the following reaction formula:

[0142]

[0143] Synthesis of C-1: In a 500 mL three-necked flask under nitrogen protection, compound CA-1 (10.00 g, 29.83 mmol), compound CB-1 (2.65 g, 13.56 mmol), 120 mL toluene, tris(dibenzylacetone)palladium (62 mg, 0.068 mmol), sodium tert-butoxide (3.26 g, 33.93 mmol), and 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene) (79 mg, 0.14 mmol) were added. The reaction was carried out overnight at 100 °C. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate to remove the organic solvent. The crude product was recrystallized from o-dichlorobenzene to give C-1 (yield 61.8%).

[0144] Elemental analysis: C 48 H 29 N7, theoretical values: C, 81.92; H, 4.15; N, 13.93; measured values: C, 81.93; H, 4.16; N, 13.90;

[0145] HRMS(ESI)m / z(M+): Theoretical value: 703.25, measured value: 704.16.

[0146] Synthesis Example 2

[0147] Compound C-3 was prepared using the same synthetic method as in Example 1, except that CB-3 was used instead of CB-1. The synthetic route is shown below:

[0148]

[0149] Compound C-3 was obtained in 62.1% yield. Elemental analysis: C 48 H 29 N5S. Theoretical values: C, 81.45; H, 4.13; N, 9.89; S, 4.53; Measured values: C, 81.46; H, 4.14; N, 9.86; S, 4.54

[0150] HRMS(ESI)m / z[M+H]+: Theoretical value: 707.21; Measured value: 708.25.

[0151] Synthesis Example 3

[0152] This embodiment provides a method for synthesizing compound C-9, and the synthetic route is shown in the following reaction formula:

[0153]

[0154] Synthesis of C-9: In a 250 mL three-necked flask under nitrogen protection, compound CB-9 (1.55 g, 16.69 mmol), compound CA-9 (12.00 g, 36.73 mmol), 100 mL toluene, tris(dibenzylacetone)palladium (76 mg, 0.083 mmol), sodium tert-butoxide (4.01 g, 41.73 mmol), and 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene) (97 mg, 0.17 mmol) were added. The reaction was carried out overnight at 100 °C. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate to remove the organic solvent. The crude product was recrystallized from o-dichlorobenzene to give C-9 (yield 56.3%).

[0155] Elemental analysis: C 42 H 23 F4N5. Theoretical values: C, 74.88; H, 3.44; F, 11.28; N, 10.40; Measured values: C, 74.89; H, 3.45; F, 11.29; N, 10.37.

[0156] HRMS(ESI)m / z[M+H]+: Theoretical value: 673.19; Measured value: 674.16.

[0157] Synthesis Example 4

[0158] Compound C-17 was prepared using the same synthetic method as in Example 3, except that CA-17 was used instead of CA-9. The synthetic route is shown below:

[0159]

[0160] Compound C-17 was obtained in 58.1% yield. Elemental analysis: C 64 H 43 N5O2. Theoretical values: C, 84.10; H, 4.74; N, 7.66; O, 3.50; Measured values: C, 84.12; H, 4.73; N, 7.65.

[0161] HRMS(ESI)m / z[M+H]+: Theoretical value: 913.34; Measured value: 914.12.

[0162] Synthesis Example 5

[0163] Compound C-20 was prepared using the same synthetic method as in Example 3, except that CA-20 was used instead of CA-9. The synthetic route is shown below:

[0164]

[0165] Compound C-20 was obtained in 58.5% yield. Elemental analysis: C60 H 37 N7. Theoretical values: C, 84.19; H, 4.36; N, 11.45; Measured values: C, 84.19; H, 4.38; N, 11.42.

[0166] HRMS(ESI)m / z[M+H]+: Theoretical value: 855.31; Measured value: 856.12.

[0167] Synthesis Example 6

[0168] Compound C-30 was prepared using the same synthetic method as in Example 3, except that CA-30 was used instead of CA-9 and CB-30 was used instead of CB-9. The synthetic route is shown below:

[0169]

[0170] Compound C-30 was obtained in 58.2% yield. Elemental analysis: C 40 H 23 F2N7. Theoretical values: C, 75.11; H, 3.62; F, 5.94; N, 15.33; Measured values: C, 75.13; H, 3.64; F, 5.93; N, 15.30.

[0171] HRMS(ESI)m / z[M+H]+: Theoretical value: 639.20; Measured value: 640.34.

[0172] Synthesis Example 7

[0173] Compound C-45 was prepared using the same synthetic method as in Example 3, except that CA-45 was used instead of CA-9 and CB-30 was used instead of CB-9. The synthetic route is shown below:

[0174]

[0175] Compound C-45 was obtained in 56.1% yield. Elemental analysis: C 54 H 37 N7O2. Theoretical values: C, 79.49; H, 4.57; N, 12.02; O, 3.92; Measured values: C, 79.51; H, 4.56; N, 12.01;

[0176] HRMS(ESI)m / z[M+H]+: Theoretical value: 815.30; Measured value: 816.21.

[0177] Synthesis Example 8

[0178] Compound C-48 was prepared using the same synthetic method as in Example 3, except that CA-48 was used instead of CA-9 and CB-30 was used instead of CB-9. The synthetic route is shown below:

[0179]

[0180] Compound C-48 was obtained in 58.2% yield. Elemental analysis: C 52 H 29 F4N7. Theoretical values: C, 75.45; H, 3.53; F, 9.18; N, 11.84; Measured values: C, 75.47; H, 3.52; F, 9.19; N, 11.82.

[0181] HRMS(ESI)m / z[M+H]+: Theoretical value: 827.24; Measured value: 828.33.

[0182] Synthesis Example 9

[0183] Compound C-57 was prepared using the same synthetic method as in Example 3, except that CA-57 was used instead of CA-9 and CB-30 was used instead of CB-9. The synthetic route is shown below:

[0184]

[0185] Compound C-57 was obtained in 62.7% yield. Elemental analysis: C 60 H 37 N7. Theoretical values: C, 84.19; H, 4.36; N, 11.45; Measured values: C, 84.21; H, 4.37; N, 11.42;

[0186] HRMS(ESI)m / z[M+H]+: Theoretical value: 855.31; Measured value: 856.25.

[0187] Synthesis Example 10

[0188] Compound C-64 was prepared using the same synthetic method as in Synthetic Example 3, except that CA-20 was used instead of CA-9 and CB-30 was used instead of CB-9. The synthetic route is shown below:

[0189]

[0190] Compound C-64 was obtained in 61.5% yield. Elemental analysis: C 58 H 35 N9. Theoretical values: C, 81.20; H, 4.11; N, 14.69; Measured values: C, 81.23; H, 4.13; N, 14.73;

[0191] HRMS(ESI)m / z[M+H]+: Theoretical value: 857.30; Measured value: 858.46.

[0192] Synthesis Example 11

[0193] Compound C-90 was prepared using the same synthetic method as in Synthetic Example 1, except that CB-3 was used instead of CB-1. The synthetic route is shown below:

[0194]

[0195] Compound C-90 was obtained in 59.3% yield. Elemental analysis: C 46 H 29 N5. Theoretical values: C, 84.77; H, 4.48; N, 10.75; Measured values: C, 84.79; H, 4.49; N, 10.72;

[0196] HRMS(ESI)m / z[M+H]+: Theoretical value: 651.24; Measured value: 652.13.

[0197] Synthesis Example 12

[0198] Compound C-96 was prepared using the same synthetic method as in Example 3, except that CA-45 was used instead of CA-9 and CB-3 was used instead of CB-9. The synthetic route is shown below:

[0199]

[0200] Compound C-96 was obtained in 62.8% yield. Elemental analysis: C 60 H 41 N5O2. Theoretical values: C, 83.41; H, 4.78; N, 8.11; O, 3.70; Measured values: C, 83.42; H, 4.79; N, 8.09.

[0201] HRMS(ESI)m / z[M+H]+: Theoretical value: 863.33; Measured value: 864.15.

[0202] Synthesis Example 13

[0203] Compound C-100 was prepared using the same synthetic method as in Synthetic Example 3, except that CA-20 was used instead of CA-9 and CB-3 was used instead of CB-9. The synthetic route is shown below:

[0204]

[0205] Compound C-100 was obtained in 63.1% yield. Elemental analysis: C 64 H39 N7. Theoretical values: C, 84.84; H, 4.34; N, 10.82; Measured values: C, 84.85; H, 4.35; N, 10.80;

[0206] HRMS(ESI)m / z[M+H]+: Theoretical value: 905.33; Measured value: 906.14.

[0207] Synthesis Example 14

[0208] Compound C-101 was prepared using the same synthetic method as in Example 1, except that CA-101 was used instead of CA-9 and CB-3 was used instead of CB-9. The synthetic route is shown below:

[0209]

[0210] Compound C-101 was obtained in 61.9% yield. Elemental analysis: C 58 H 35 F2N5. Theoretical values: C, 82.94; H, 4.20; F, 4.52; N, 8.34; Measured values: C, 82.96; H, 4.21; F, 4.51; N, 8.32.

[0211] HRMS(ESI)m / z[M+H]+: Theoretical value: 839.29; Measured value: 840.22.

[0212] Synthesis Example 15

[0213] Compound C-102 was prepared using the same synthetic method as in Synthetic Example 1, except that CB-102 was used instead of CB-1. The synthetic route is shown below:

[0214]

[0215] Compound C-102 was obtained in 64.6% yield. Elemental analysis: C 48 H 31 N5. Theoretical values: C, 85.06; H, 4.61; N, 10.33; Measured values: C, 85.08; H, 4.64; N, 10.28;

[0216] HRMS(ESI)m / z[M+H]+: Theoretical value: 677.26; Measured value: 678.22.

[0217] Synthesis Example 16

[0218] Compound C-107 was prepared using the same synthetic method as in Example 3, except that CA-107 was used instead of CA-9 and CB-3 was used instead of CB-9. The synthetic route is shown below:

[0219]

[0220] Compound C-107 was obtained in 63.4% yield. Elemental analysis: C 60 H 41 N5O2. Theoretical values: C, 83.41; H, 4.78; N, 8.11; O, 3.70; Measured values: C, 83.42; H, 4.80; N, 8.08;

[0221] HRMS(ESI)m / z[M+H]+: Theoretical value: 863.33; Measured value: 864.13.

[0222] Synthesis Example 17

[0223] Compound C-116 was prepared using the same synthetic method as in Synthetic Example 1, except that CA-116 was used instead of CA-1 and CB-102 was used instead of CB-1. The synthetic route is shown below:

[0224]

[0225] Compound C-116 was obtained in 65.1% yield. Elemental analysis: C 46 H 29 N7. Theoretical values: C, 81.28; H, 4.30; N, 14.42; Measured values: C, 81.30; H, 4.29; N, 14.41;

[0226] HRMS(ESI)m / z[M+H]+: Theoretical value: 679.25; Measured value: 680.01.

[0227] Synthesis Example 18

[0228] Compound C-126 was prepared using the same synthetic method as in Synthetic Example 1, except that CA-126 was used instead of CA-1 and CB-9 was used instead of CB-1. The synthetic route is shown below:

[0229]

[0230] Compound C-126 was obtained in 63.2% yield. Elemental analysis: C 58 H 43 N5O4. Theoretical values: C, 79.71; H, 4.96; N, 8.01; O, 7.32; Measured values: C, 79.73; H, 4.95; N, 8.00;

[0231] HRMS(ESI)m / z[M+H]+: Theoretical value: 873.33; Measured value: 874.21.

[0232] Synthesis Example 19

[0233] Compound C-160 was prepared using the same synthetic method as in Synthetic Example 1, except that CA-160 was used instead of CA-1 and CB-9 was used instead of CB-1. The synthetic route is shown below:

[0234]

[0235] Compound C-160 was obtained in 61.8% yield. Elemental analysis: C 62 H 39 N5. Theoretical values: C, 87.20; H, 4.60; N, 8.20; Measured values: C, 87.22; H, 4.59; N, 8.19;

[0236] HRMS(ESI)m / z[M+H]+: Theoretical value: 853.32; Measured value: 854.01.

[0237] Synthesis Example 20

[0238] Compound C-179 was prepared using the same synthetic method as in Synthetic Example 1, except that CB-179 was used instead of CB-1. The synthetic route is shown below:

[0239]

[0240] Compound C-179 was obtained in 62.3% yield. Elemental analysis: C 54 H 33 N5O. Theoretical values: C, 84.46; H, 4.33; N, 9.12; O, 2.08; Measured values: C, 84.48; H, 4.32; N, 9.11;

[0241] HRMS(ESI)m / z[M+H]+: Theoretical value: 767.27; Measured value: 768.15.

[0242] Device Examples

[0243] The materials used to fabricate the following device embodiments or device comparative examples are shown in Table 4 below:

[0244] Table 4

[0245]

[0246] Device Example 1

[0247] This embodiment provides an organic electroluminescent device, such as... Figure 1As shown, it includes, in sequence, an anode 1, a hole injection layer 2, a first hole transport layer 3, a first electron blocking layer 4, a first organic light-emitting layer 5, a first hole blocking layer 6, a first electron transport layer 7, an n-type charge generation layer 8, a p-type charge generation layer 9, a second hole transport layer 10, a second electron blocking layer 11, a second organic light-emitting layer 12, a second hole blocking layer 13, a second electron transport layer 14, an electron injection layer 15, and a cathode 16. Its device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), first hole transport layer (HTL-1), first electron blocking layer (EBL-1), first organic light-emitting layer (EML-1), first hole blocking layer (HBL-1), first electron transport layer (ETL-1), n-type charge generation layer (CGL-n), p-type charge generation layer (CGL-p), second hole transport layer (HTL-2), second electron blocking layer (EBL-2), second organic light-emitting layer (EML-2), second hole blocking layer (HBL-2), second electron transport layer (ETL-2), electron injection layer (EIL), and cathode.

[0248] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0249] 1) Substrate cleaning:

[0250] 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.

[0251] 2) Preparation of organic layer:

[0252] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, in sequence, deposited on the ITO anode film the following layers: hole injection layer (HIL) / first hole transport layer (HTL-1) / first electron blocking layer (EBL-1) / first organic light-emitting layer (EML-1) / first hole blocking layer (HBL-1) / first electron transport layer (ETL-1) / n-type charge generation layer (CGL-n) / p-type charge generation layer (CGL-p) / second hole transport layer (HTL-2) / second electron blocking layer (EBL-2) / second organic light-emitting layer (EML-2) / second hole blocking layer (HBL-2) / second electron transport layer (ETL-2) / electron injection layer (EIL) / cathode (Mg:Ag mass ratio is 1:9).

[0253] in:

[0254] The anode is indium tin oxide (ITO, 10 nm thick);

[0255] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HATCN to TCTA is 3:97.

[0256] The material of the first hole transport layer (HTL-1) is TCTA (20nm thick);

[0257] The material of the first electron blocking layer (EBL-1) is mCP (5nm thick);

[0258] The first organic light-emitting layer (EML-1) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0259] The material of the first hole blocking layer (HBL-1) is BCP (5nm thick);

[0260] The first electron transport layer (ETL-1) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm);

[0261] The material of the n-type charge generation layer (CGL-n) is composed of compound C-1 and Yb from synthesis example 1, and its specific ratio and thickness are shown in Table 5.

[0262] The p-type charge generation layer (CGL-p) is made of HAT-CN and TCTA in a mass ratio of 8:2 (thickness 10nm);

[0263] The material of the second hole transport layer (HTL-2) is TCTA (20nm thick);

[0264] The material of the second electron blocking layer (EBL-2) is mCP (5nm thick);

[0265] The second organic light-emitting layer (EML-2) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0266] The material of the second hole blocking layer (HBL-2) is BCP (5nm thick);

[0267] The second electron transport layer (ETL-2) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm);

[0268] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0269] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0270] Device Example 2

[0271] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-3 in Synthesis Example 2.

[0272] Device Example 3

[0273] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-9 in Synthesis Example 3.

[0274] Device Example 4

[0275] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-17 in Synthesis Example 4.

[0276] Device Example 5

[0277] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-20 in Synthesis Example 5.

[0278] Device Example 6

[0279] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-30 in Synthesis Example 6.

[0280] Device Example 7

[0281] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-45 in Synthesis Example 7.

[0282] Device Example 8

[0283] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-48 in Synthesis Example 8.

[0284] Device Example 9

[0285] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-57 in Synthesis Example 9.

[0286] Device Example 10

[0287] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-64 in Synthesis Example 10.

[0288] Device Example 11

[0289] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-90 in Synthesis Example 11.

[0290] Device Example 12

[0291] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-96 in Synthesis Example 12.

[0292] Device Example 13

[0293] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-100 in Synthesis Example 13.

[0294] Device Example 14

[0295] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-101 in Synthesis Example 14.

[0296] Device Example 15

[0297] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-102 in Synthesis Example 15.

[0298] Device Example 16

[0299] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-107 in Synthesis Example 16.

[0300] Device Example 23

[0301] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-116 in Synthesis Example 17.

[0302] Device Example 24

[0303] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-126 in Synthesis Example 18.

[0304] Device Example 25

[0305] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-160 in Synthesis Example 19.

[0306] Device Example 26

[0307] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound C-179 in Synthesis Example 20.

[0308] Device Example 17

[0309] This embodiment provides an organic electroluminescent device, comprising, in sequence, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. The device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), emissive layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), and cathode.

[0310] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0311] 1) Substrate cleaning:

[0312] 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.

[0313] 2) Preparation of organic layer:

[0314] 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-1) / electron blocking layer (EBL-1) / light emitting layer (EML-1) / hole blocking layer (HBL-1) / electron transport layer (ETL-1) / electron injection layer (EIL) / cathode are sequentially deposited on the ITO anode film.

[0315] in:

[0316] The anode is indium tin oxide (ITO, 10 nm thick);

[0317] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HATCN to TCTA is 3:97.

[0318] The hole transport layer (HTL) is made of TCTA (20 nm thick);

[0319] The electron blocking layer (EBL) is made of mCP (5 nm thick);

[0320] The materials of the light-emitting layer (EML) are D and E, with a mass ratio of 95:5 (thickness 20nm);

[0321] The hole blocking layer (HBL) is made of compound C-1 (5 nm thick) from synthesis example 1;

[0322] The electron transport layer (ETL) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm);

[0323] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0324] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0325] Device Example 18

[0326] Similar to Device Example 17, the difference is that compound C-1 in the hole blocking layer of Device Example 17 is replaced with compound C-3 in Synthesis Example 2.

[0327] Device Example 19

[0328] Similar to Device Example 17, the difference is that compound C-1 in the hole blocking layer of Device Example 17 is replaced with compound C-9 in Synthesis Example 3.

[0329] Device Example 20

[0330] This embodiment provides an organic electroluminescent device, comprising, in sequence, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. The device structure is as follows: anode (indium tin oxide (ITO)), hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), emissive layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), and cathode.

[0331] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0332] 1) Substrate cleaning:

[0333] 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.

[0334] 2) Preparation of organic layer:

[0335] 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-1) / electron blocking layer (EBL-1) / light emitting layer (EML-1) / hole blocking layer (HBL-1) / electron transport layer (ETL-1) / electron injection layer (EIL) / cathode are sequentially deposited on the ITO anode film.

[0336] in:

[0337] The anode is indium tin oxide (ITO, 10 nm thick);

[0338] The hole injection layer (HIL) is made of HAT-CN:TCTA (10 nm thick); the mass ratio of HAT-CN to TCTA is 3:97.

[0339] The hole transport layer (HTL) is made of TCTA (20 nm thick);

[0340] The electron blocking layer (EBL) is made of mCP (5 nm thick);

[0341] The materials of the light-emitting layer (EML) are D and E, with a mass ratio of 95:5 (thickness 20nm);

[0342] The hole blocking layer (HBL) is made of BCP (5nm thick);

[0343] The electron transport layer (ETL) is made of C-1 and LiQ in synthesis example 1, with a mass ratio of 9:1 (thickness 25 nm);

[0344] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0345] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0346] Device Example 21

[0347] Similar to Device Example 20, the difference is that compound C-1 in the electron transport layer of Device Example 20 is replaced with compound C-3 in Synthesis Example 2.

[0348] Device Example 22

[0349] Similar to Device Example 20, the difference is that compound C-1 in the electron transport layer of Device Example 20 is replaced with compound C-9 in Synthesis Example 3.

[0350] Device Comparison Example 1

[0351] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with the compound REF-1 shown below.

[0352]

[0353] Device Comparison Example 2

[0354] Similar to Device Example 1, the difference is that the compound C-1 in the n-type charge layer of Device Example 1 is replaced with compound REF-2 as shown below.

[0355]

[0356] Device Comparison Example 3

[0357] Similar to Device Example 17, the difference is that the compound C-1 in the hole blocking layer of Device Example 17 is replaced with compound BCP.

[0358] Device Comparison Example 4

[0359] Similar to Device Example 20, the difference is that compound C-1 in the electron transport layer of Device Example 20 is replaced with compound TPBI.

[0360] Table 5. Composition and thickness of n-type charge generation layer

[0361]

[0362]

[0363] Device Test Examples

[0364] The organic electroluminescent devices obtained in Device Examples 1-26 and Device Comparative Examples 1-4 in the device examples were tested.

[0365] 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;

[0366] Test conditions: current density of 10 mA / cm2, room temperature.

[0367] Lifetime test: Record the time (in hours) when the device brightness drops to 95% of its original brightness.

[0368] Among them, the lifetime T95, current efficiency, and drive voltage of device embodiments 1-16 and device embodiments 23-26 relative to device comparison example 1 are set to 100. The performance test results of the other devices are shown in Table 6.

[0369] The lifetime T95, current efficiency, and drive voltage of devices in Examples 16-19 are set to 100 compared to Comparative Example 3. The performance test results of the other devices are shown in Table 7.

[0370] The lifetime T95, current efficiency, and drive voltage of devices in Examples 19-21 are set to 100 compared to Comparative Example 4. The performance test results of the other devices are shown in Table 8.

[0371] Table 6. Device performance parameters for Device Examples 1-16 and Device Comparative Examples 1 and 2

[0372]

[0373]

[0374] Table 7. Device performance parameters for Device Examples 17-19 and Device Comparative Example 3.

[0375] Example Drive voltage (V) Current efficiency Relative lifespan T95 Device Example 17 8.23 105.97 110.78 Device Example 18 8.27 104.34 108.67 Device Example 19 8.31 104.12 106.34 Device Comparison Example 3 8.96 100 100

[0376] Table 8. Device performance parameters for Device Examples 20-22 and Device Comparative Example 4

[0377] Example Drive voltage (V) Current efficiency (cd / A) Relative lifespan T95(h) Device Example 20 8.30 106.24 112.34 Device Example 21 8.29 104.89 111.23 Device Example 22 8.32 104.13 110.12 Device Comparison Example 4 8.34 100 100

[0378] As shown in Table 6, under the same current density, compared with the CGL layer in Comparative Example 1 and Comparative Example 2 of the prior art, the organic electroluminescent device improved in this application has a longer lifetime, a lower driving voltage, and good current efficiency.

[0379] The aromatic amine structure in this application is defined with two substituted phenanthroline structures, which can reduce the cost of molecular synthesis. At the same time, the lone pair electrons on the amine combined with the phenanthroline structure can suppress ion migration in optoelectronic devices, thereby improving device stability and lifespan.

[0380] 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. A fused-ring compound, characterized in that, It has the structure shown in equation (1): In the formula, L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C60 arylene, or substituted or unsubstituted C1-C60 heteroarylene; Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C1-C60 heteroaryl groups; a and b are each independently selected from integers from 1 to 7; The substituents of the substituted C6-C60 arylene, substituted C1-C60 heteroarylene, substituted C6-C60 aryl, and substituted C1-C60 heteroarylene are selected from one or more of deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, and C1-C60 heteroarylene.

2. The fused-ring compound according to claim 1, characterized in that, The fused-ring compound has the following structure:

3. The fused-ring compound according to claim 1 or 2, characterized in that, L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C50 arylene, or substituted or unsubstituted C6-C50 heteroarylene; Wherein, the substituents in the substituted C6-C50 arylene and the substituted C6-C50 heteroarylene are selected from one or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C50 alkyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C6-C50 aryl, and C1-C50 heteroaryl; Preferred, L 1 L 2 and L 3 Each is independently selected from single-bonded, substituted or unsubstituted C6-C25 arylene, or substituted or unsubstituted C6-C25 heteroarylene; Wherein, the substituents in the substituted C6-C25 arylene or the substituted C6-C25 heteroarylene are selected from one or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C25 alkyl, C3-C25 cycloalkyl, C1-C25 heterocycloalkyl, C6-C25 aryl, and C1-C25 heteroaryl; Preferably, L 1 L 2 and L 3 The same or different, and each independently selected from the group consisting of single bonds or the following groups:

4. The fused-ring compound according to any one of claims 1-3, characterized in that, Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C50 aryl groups and substituted or unsubstituted C1-C50 heteroaryl groups; The substituents in the substituted C6-C50 aryl and substituted C1-C50 heteroaryl are selected from one or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C50 alkyl, C3-C50 cycloalkyl, C1-C50 heterocycloalkyl, C6-C50 aryl, and C1-C50 heteroaryl. Preferred, Ar 1 Ar 2 and Ar 3 Each is independently selected from substituted or unsubstituted C6-C25 aryl groups and substituted or unsubstituted C1-C25 heteroaryl groups; The substituents in the substituted C6-C25 aryl and substituted C1-C25 heteroaryl are selected from one or more of the following: deuterium, cyano, halogen, halide, amino, acyl, carboxyl, silyl, trifluoromethyl, methylthio, methoxy, C1-C25 alkyl, C3-C25 cycloalkyl, C1-C25 heterocycloalkyl, C6-C25 aryl, and C1-C25 heteroaryl. Preferred, Ar 1 Ar 2 and Ar 3 Each is independently selected from the group consisting of the following groups:

5. The fused-ring compound according to any one of claims 1-4, characterized in that, a and b are each independently selected from integers from 1 to 6; preferably, a and b are each independently selected from integers from 1 to 5. Preferably, a and b are each independently selected from integers from 1 to 3; Preferably, a and b are both 1.

6. The fused-ring compound according to any one of claims 1-5, characterized in that, The compound has the following structure:

7. An n-type charge generation layer, characterized in that, The material of the n-type charge generation layer includes any one or a combination of at least two of the fused ring compounds as described in any one of claims 1-6.

8. An electron transport layer, characterized in that, The material of the electron transport layer includes any one or a combination of at least two of the fused ring compounds as described in any one of claims 1-6.

9. A hole-blocking layer, characterized in that, The material of the hole-blocking layer includes any one or a combination of at least two of the fused ring compounds as described in any one of claims 1-6.

10. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode, and an organic layer located between the cathode and the anode, wherein the organic layer includes any one or a combination of at least two of the fused-ring compounds according to any one of claims 1-6; Preferably, the organic layer includes the n-type charge generation layer as described in claim 7 and / or the electron transport layer as described in claim 8 and / or the hole blocking layer as described in claim 9.

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