Condensed ring compound and application thereof

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to a fused ring compound and application thereof. The condensed ring compound provided by the invention is based on the structure shown in the formula, N atoms on three heteroaromatic rings in the structure can form multi-coordination with metal atoms, the structure is stable, good thermal / electric stability is achieved, the condensed ring compound is applied to the organic light-emitting device, the organic light-emitting device is not prone to degradation or deterioration in the working process, and the service life of the organic light-emitting device is prolonged. Therefore, the efficiency, the stability and the service life of the organic light-emitting device can be improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescence, and particularly relates to a fused ring compound and application thereof. BACKGROUND

[0002] Organic light-emitting materials can be roughly divided into light-emitting materials, hole-injection materials, hole-transport materials, electron-transport materials, electron-injection materials, etc. according to functions. An organic light-emitting diode (OLED) is a device driven by electric current to achieve light-emitting purposes, which has the advantages of lightness, flexibility, high contrast, wide color gamut, etc. Due to high current efficiency and long service life, a stacked OLED has gradually become a research direction, which mainly includes a first light-emitting stack, a second light-emitting stack, and a charge generation layer (CGL) disposed between the first light-emitting stack and the second light-emitting stack to ensure that the charges are effectively distributed to the light-emitting stacks and improve the current efficiency in each light-emitting layer. However, in the use process of the OLED, especially in the long-term operation process, the material of the charge generation layer has poor thermal / electrical stability, which leads to the reduction of the performance and service life of the OLED. SUMMARY

[0003] The present application aims to overcome the problem that the material of the charge generation layer in the existing organic electroluminescent device has poor thermal / electrical stability, which leads to the reduction of the performance and service life of the organic electroluminescent device, and further provides a fused ring compound and application thereof.

[0004] In the definition of the substituent terms of the present application:

[0005] As used in the present application, the term "halogen" can include fluorine, chlorine, bromine or iodine.

[0006] As used in the present application, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0007] As used in the present application, the term "C3-C30 cycloalkyl" refers to a monocyclic or polycyclic hydrocarbon derived from 1 to 30 ring backbone carbon atoms, which can include cyclopropyl, cyclobutyl, adamantyl, etc.

[0008] In the present application, aryl, arylene includes monocyclic, polycyclic or fused ring aryl, the rings between which can be interrupted by short non-aromatic units, and can contain a spiro structure, aryl includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, etc., arylene includes but is not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, etc.

[0009] In the present application, heteroaryl, heteroarylene includes monocyclic, polycyclic or fused ring heteroaryl, the rings between which can be interrupted by short non-aromatic units, the heteroatom includes nitrogen, oxygen, sulfur. Heteroaryl includes but is not limited to furanyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoaxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof, etc.; heteroarylene includes but is not limited to furanylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridylene, pyrazinylyene, pyrimidinylyene, pyridazinylyene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenylene, benzimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoaxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylyene, dihydroacridinylene, and derivatives thereof, etc.

[0010] As used in the present application, the term "substituted" means that a hydrogen atom in an organic compound is substituted by another substituent. The position is not limited to a specific position, as long as the hydrogen at that position can be substituted by a substituent. When two or more substituents appear, the two or more substituents can be the same or different.

[0011] As used in the present application, unless otherwise specified, a hydrogen atom includes protium, deuterium and tritium.

[0012] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms thereof can be any integer within the defined range, for example, C6-C30 aryl, which represents the number of carbon atoms of the aryl group, can be any integer within the range of 6 to 60, for example, 6, 8, 10, 13, 15, 17, 20, 22, 25, or 30, etc.

[0013] In the present invention, represents a bond.

[0014] The scheme employed in the present invention is as follows:

[0015] The present invention provides a fused ring compound having the structure shown in the following formula I:

[0016]

[0017] wherein Ar is selected from hydrogen, deuterium, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0018] L is selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;

[0019] the substituents in the substituted C6-C60 aryl, substituted C3-C60 heteroaryl, substituted C6-C30 arylene, and substituted C3-C30 heteroarylene are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, non-fused C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino;

[0020] when Ar is selected from hydrogen, deuterium, cyano, L is a spirofluorene group or an anthracene group.

[0021] Preferably, in formula I, Ar is selected from substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C3-C20 heteroaryl;

[0022] wherein the substituents in the substituted C6-C25 aryl and substituted C3-C20 heteroaryl are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino;

[0023] Preferably, in Formula I, Ar is selected from substituted or unsubstituted group B, and group B is selected from the following groups: phenyl, biphenyl, triphenyl, naphthyl, binatyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, phenanthryl, phenylphenanthryl, anthracene, indole, tetraphenyl, perylene, trefyl, fused tetraphenyl, fluoranyl or spirodifluorenyl, furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, Tetraazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiopheneyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisooxazolyl, benzooxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazolyl, phenoxazinyl, phenthiazolyl, phenanthidyl, dipyridyl, tripyridyl, phenyl tripyridyl, diazafluorenyl or phenanthrolinel;

[0024] Wherein, the substituent of the substituted group B is selected from halogen, cyano, C1-C4 alkyl, and C6-C12 aryl;

[0025] Preferably, L is selected from substituted or unsubstituted C6-C15 arylene or substituted or unsubstituted C3-C15 heteroarylene;

[0026] The substituents in the substituted C6-C15 arylene and the substituted C3-C15 heteroarylene are each independently selected from 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.

[0027] Preferably, L is selected from substituted or unsubstituted group D, and group D is selected from: phenylene, naphthylene, anthraceneylene, fluoreneylene, pyridylene, quinolineylene;

[0028] The substituent of the substituted group D is selected from 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.

[0029] Preferably, Formula I is selected from the structure shown below:

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] The present invention provides an n-type charge generation layer, wherein the n-type charge generation layer includes any one or a combination of at least two of the fused ring compounds described above.

[0040] Preferably, the n-type charge generation layer further includes a metallic material;

[0041] Preferably, the metallic material includes at least one of alkali metals, alkaline earth metals, and transition metals;

[0042] Preferably, the metallic material includes at least one of lithium, ytterbium, and silver.

[0043] The present invention provides an electron transport layer comprising any one or a combination of at least two of the fused ring compounds described above.

[0044] This invention provides 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 described above;

[0045] Preferably, the organic layer includes the n-type charge generation layer or the electron transport layer described above.

[0046] Preferably, the organic layer further comprises one or more of a hole injection layer, a first light-emitting stack, a second light-emitting stack, and an electron injection layer;

[0047] Wherein, when the organic light-emitting device includes an n-type charge generation layer, the n-type charge generation layer is located between the first light-emitting stack and the second light-emitting stack.

[0048] The present invention provides an organic electroluminescent product, wherein the organic electroluminescent product includes the organic electroluminescent device described above.

[0049] The present invention also provides an electronic device comprising the fused ring compound described above.

[0050] 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.

[0051] Optionally, electronic devices may also include electronic display devices.

[0052] In this invention, the fused-ring compound represented by Formula I can be prepared by the Suzuki reaction, specifically including the following steps: subjecting a haloaromatic hydrocarbon / haloheteroaromatic hydrocarbon to a boronic acid ester-substituted aromatic hydrocarbon / boronic acid ester-substituted heteroaromatic hydrocarbon by a Suzuki reaction to connect the aryl group in the haloaromatic hydrocarbon / heteroaromatic group in the haloaromatic hydrocarbon to the aryl group in the boronic acid ester-substituted aromatic hydrocarbon / heteroaromatic hydrocarbon, thereby introducing substituted or unsubstituted aryl / heteroaromatic groups to prepare the fused-ring compound represented by Formula I.

[0053] Specifically, the fused-ring compound of the present invention can be synthesized from starting material a and starting material b via the following synthetic route:

[0054]

[0055] The beneficial effects of this invention are:

[0056] The fused ring compound provided by this invention is based on the structure of Formula I. The N atoms on the three aromatic heterocycles in its structure can form multiple coordinations with metal atoms, resulting in a stable structure and good thermal / electrical stability. When applied to organic electroluminescent devices, the organic electroluminescent devices are less prone to degradation or deterioration during operation, exhibiting strong thermal / electrical stability, thereby improving the efficiency, stability, and lifespan of organic electroluminescent devices. Attached Figure Description

[0057] 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.

[0058] Figure 1 This is a structural diagram of the stacked organic electroluminescent device in the device embodiment of the present invention;

[0059] 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

[0060] 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.

[0061] 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.

[0062] For example, organic electroluminescent materials can be hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials (containing host materials and dopant materials), electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc.

[0063] Synthesis of intermediate 1-C-1:

[0064]

[0065] The specific synthetic steps of intermediate 1-C-1 are as follows: In a 2-liter three-necked flask, under nitrogen protection, starter a (7.37 g, 0.054 mol), starter b (18.00 g, 0.05 mol), dioxane:water = 4:1 (360:90 mL), tetra(triphenylphosphine)palladium (1.23 g, 1.07 mmol), and potassium carbonate (18.40 g, 0.13 mol) were added. The reaction was carried out overnight at 60 °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 (dichloromethane / tetrahydrofuran, 7 / 1) to give 1-C-1 (13.2 g, yield 64.2%).

[0066] Example 1

[0067] This embodiment provides a fused-ring compound C-3. The synthesis of fused-ring compound C-3 specifically includes the following steps:

[0068]

[0069] In a 250 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (4.00 g, 0.01 mol), starting material C1 (4.33 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (38 mg, 0.52 mmol), and potassium carbonate (3.58 g, 0.03 mol) were added. The reaction was carried out overnight at 95 °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 (dichloromethane / tetrahydrofuran, 5 / 1) to give C-3 (4.31 g, 74.3% yield). Elemental analysis: C 41 H 25 N3. Theoretical values: C, 87.99; H, 4.50; N, 7.51; Measured values: C, 87.95; H, 4.51; N, 7.54. HRMS(ESI) m / z(M+): Theoretical value: 559.6720, Measured value: 559.4143.

[0070] Example 2

[0071] This embodiment provides a fused cyclic compound C-6, the synthesis of which specifically includes the following steps:

[0072]

[0073] In a 250 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (4.00 g, 0.01 mol), starting material C2 (4.93 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (38 mg, 0.52 mmol), and potassium carbonate (3.58 g, 0.03 mol) were added. The reaction was carried out overnight at 95 °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 (dichloromethane / tetrahydrofuran, 5 / 1), and recrystallized from toluene to give C-6 (3.57 g, 56.4% yield). Elemental analysis: C 45 H 29 N3. Theoretical values: C, 88.35; H, 4.78; N, 6.87; Measured values: C, 88.31; H, 4.79; N, 6.90. HRMS(ESI) m / z(M+): Theoretical value: 611.7480, Measured value: 611.4217.

[0074] Example 3

[0075] This embodiment provides fused cyclic compound C-8, and the synthesis of fused cyclic compound C-8 specifically includes the following steps:

[0076]

[0077] In a 250 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (4.00 g, 0.01 mol), starting material C3 (4.81 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), tetra(triphenylphosphine)palladium (598 mg, 0.52 mmol), and potassium carbonate (3.60 g, 0.03 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 over anhydrous magnesium sulfate to remove the organic solvent. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1), and recrystallized from toluene to give C-8 (5.11 g, 79.4% yield). Elemental analysis: C 46 H 27 N3. Theoretical values: C, 88.86; H, 4.38; N, 6.76; Measured values: C, 88.81; H, 4.39; N, 6.80. HRMS(ESI) m / z(M+): Theoretical value: 621.7430, Measured value: 621.7211.

[0078] Example 4

[0079] This embodiment provides a fused-ring compound C-12. The synthesis of fused-ring compound C-12 specifically includes the following steps:

[0080]

[0081] In a 250 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (4.00 g, 0.01 mol), starting material C4 (4.81 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), tetra(triphenylphosphine)palladium (598 mg, 0.52 mmol), and potassium carbonate (3.60 g, 0.03 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 over anhydrous magnesium sulfate to remove the organic solvent. The crude product was purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1), and recrystallized from toluene to give C-12 (5.61 g, 87.1% yield). Elemental analysis: C 46 H 27 N3. Theoretical values: C, 88.86; H, 4.38; N, 6.76; Measured values: C, 88.81; H, 4.41; N, 6.78. HRMS(ESI) m / z(M+): Theoretical value: 621.7430, Measured value: 621.7812.

[0082] Examples 5-14

[0083] The preparation of Examples 5-14 is similar to that of the above examples. Specifically, the raw material c used in Examples 4-16 and the products obtained are shown in the table below:

[0084]

[0085]

[0086]

[0087] Example 15

[0088] This embodiment provides a fused-ring compound C-13. The synthesis of fused-ring compound C-13 specifically includes the following steps:

[0089]

[0090] Synthesis of intermediate 1-C-2: In a 1-liter three-necked flask under nitrogen protection, 3,5-dibromopyridine (25.00 g, 0.11 mol), (3,5-diphenylbenzene)boronic acid (26.04 g, 0.10 mol), dioxane:water = 4:1 (300:75 mL), tetra(triphenylphosphine)palladium (3.66 g, 3.17 mmol), and potassium carbonate (36.46 g, 0.26 mol) 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 purified by chromatography (petroleum ether / dichloromethane, 2 / 1) to give 1-C-2 (22.30 g, yield 54.7%).

[0091]

[0092] Synthesis of intermediate 2-C-2: In a 1-L three-necked flask under nitrogen protection, intermediate 1-C-2 (22.00 g, 0.06 mol), pinacol diborate (17.35 g, 0.07 mol), dioxane (300 mL), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (833 mg, 1.14 mmol), and potassium acetate (13.97 g, 0.14 mol) were added. The reaction was carried out overnight at 100 °C. After the reaction was completed, the solution was evaporated to dryness and dissolved in toluene and passed through a fast column to remove the organic solvent, yielding 2-C-2 (21.88 g, yield 88.7%).

[0093]

[0094] Synthesis of C-13: In a 250 mL three-necked flask under nitrogen protection, intermediates 1-C-1 (4.00 g, 0.01 mol), 2-C-2 (4.93 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (38 mg, 0.52 mmol), and potassium carbonate (3.58 g, 0.03 mol) were added. The reaction was carried out overnight at 95 °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 (dichloromethane / tetrahydrofuran, 5 / 1), and recrystallized from toluene to give C-13 (4.11 g, 64.9% yield). Elemental analysis: C 44 H 28 N4. Theoretical values: C, 86.25; H, 4.61; N, 9.14; Measured values: C, 86.29; H, 4.62; N, 9.09. HRMS(ESI) m / z(M+): Theoretical value: 612.7360, Measured value: 612.1232.

[0095] Example 16

[0096] This embodiment provides a fused-ring compound C-16. The synthesis of fused-ring compound C-16 specifically includes the following steps:

[0097]

[0098] Synthesis of intermediate 1-C-3: In a 500 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (6.00 g, 0.02 mol), 1,3-phenyldiboronic acid (6.44 g, 0.04 mol), dioxane:water = 4:1 (100:25 mL), tetra(triphenylphosphine)palladium (180 mg, 0.16 mmol), and potassium carbonate (5.37 g, 0.37 mol) 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 purified by chromatography (dichloromethane / tetrahydrofuran, 3 / 1) to give 1-C-3 (4.52 g, yield 68.1%).

[0099]

[0100] Synthesis of C-16: In a 250 mL three-necked flask under nitrogen protection, intermediate 1-C-3 (4.50 g, 0.01 mol), 2-bromo-9-phenyl-1,10-phenanthroline (3.88 g, 0.01 mol), dioxane:water = 4:1 (80:20 mL), tetra(triphenylphosphine)palladium (365 mg, 0.32 mmol), and potassium carbonate (3.64 g, 0.03 mol) were added. The reaction was carried out overnight at 95 °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 (dichloromethane / tetrahydrofuran, 7 / 1) and recrystallized from toluene to give C-16 (4.57 g, 68.0% yield). Elemental analysis: C 45 H 27 N5. Theoretical values: C, 84.75; H, 4.27; N, 10.98; Measured values: C, 84.78; H, 4.26; N, 10.96. HRMS(ESI) m / z(M+): Theoretical value: 637.7460, Measured value: 637.1436.

[0101] Example 17

[0102] This embodiment provides a fused-ring compound C-17. The synthesis of fused-ring compound C-17 specifically includes the following steps:

[0103]

[0104] In a 500 mL three-necked flask under nitrogen protection, intermediate 1-C-1 (7.69 g, 0.02 mol), 1,3-phenylenediboric acid (1.50 g, 0.01 mol), dioxane:water = 4:1 (100:25 mL), tetra(triphenylphosphine)palladium (523 mg, 0.45 mmol), and potassium carbonate (3.13 g, 0.02 mol) 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 purified by chromatography (dichloromethane / tetrahydrofuran, 5 / 1) to give C-17 (4.18 g, 67.1% yield). Elemental analysis: C 48 H 28 N6. Theoretical values: C, 83.70; H, 4.10; N, 12.20; Measured values: C, 83.68; H, 4.11; N, 12.21. HRMS(ESI) m / z(M+): Theoretical value: 688.7940, Measured value: 688.5124.

[0105] Compound testing examples:

[0106] 1. Determining the thermal decomposition temperature of compounds

[0107] Determination of thermal decomposition temperature of compounds: The thermal decomposition temperature (Td) of the fused ring compounds in Examples 1-17 of this invention was tested using a thermogravimetric analyzer (TATGA55, USA). The test range was from room temperature to 800°C, with a heating rate of 10°C / min. Under a nitrogen atmosphere, the temperature at which the weight loss was 5% was defined as the decomposition temperature. The test results are shown in Table 1.

[0108] Table 1 Thermal decomposition temperatures of compounds

[0109]

[0110]

[0111] 2. Energy level testing

[0112] HOMO level measurement conditions: The HOMO level of the compound was measured by reflected electron spectroscopy (Model IPS-4, Nanjing SunnyTech Ltd.) under a nitrogen atmosphere, with a measurement range of 4V-7.3V. The LUMO level of the material molecule was calculated using the material's band gap and HOMO. Wherein, the band gap E... g Calculate using the following formula, E g =1240 / E onset E onset The wavelength corresponding to the absorption boundary.

[0113] Triple-state energy level testing conditions: The compound to be tested was prepared into a solution using toluene as a solvent (concentration 2*10). - 5 The above solution (mol / L) was tested at -78°C using a fluorescence spectrophotometer (Hitachi F-4600). E T1 (eV) represents the triplet energy level of the compound, which is calculated using the following formula, E T1 =1240 / shortest absorption wavelength. The test results are shown in Table 2.

[0114] Table 2 Energy level test results of fused ring compounds

[0115]

[0116]

[0117] Device Examples

[0118] This embodiment provides a stacked organic light-emitting device (OLED), which includes two light-emitting stacks, namely a first light-emitting stack and a second light-emitting stack. The first light-emitting stack includes a first hole transport layer, a first electron blocking layer, a first organic light-emitting layer, a first hole blocking layer, and a first electron transport layer. The second light-emitting stack includes a second hole transport layer, a second electron blocking layer, a second organic light-emitting layer, a second hole blocking layer, and a second electron transport layer. The stack also includes a hole injection layer HIL, an electron injection layer EIL, an n-type charge generation layer CGL-n, and a p-type charge generation layer CGL-p.

[0119] The thickness of each of the above layers can be the conventional thickness of such layers in the art; the material of each of the above layers can be the conventional material of such layers in the art.

[0120] The charge generation layer includes a p-type charge generation layer (CGL-p) and an n-type charge generation layer (CGL-n). The n-type charge generation layer includes the fused ring compound having the structure shown in Formula 1. Furthermore, the n-type charge generation layer also includes a metal, and the fused ring compound interacts with the metal to form n-type doping, exhibiting good thermal / electrical stability and facilitating electron transport.

[0121] In one specific embodiment, the metal in the n-type charge generation layer includes at least one of alkali metals, alkaline earth metals, and transition metals. In a more specific embodiment, the metal in the n-type charge generation layer may include a low work function metal, such as lithium or ytterbium, or a non-low work function metal, such as silver.

[0122] In some preferred embodiments, the metal in the n-type charge generation layer includes at least one of lithium (Li), ytterbium (Yb), and silver (Ag), which is more conducive to coordination with the fused ring compound shown in Formula 1 and improves the electron transport and other properties of the n-type charge generation layer.

[0123] In some specific embodiments, the mass percentage (doping concentration) of the metal in the n-type charge generation layer is 0.25% to 5%.

[0124] In one specific embodiment, the above-mentioned organic electroluminescent device is a stacked OLED, which includes an anode, a cathode, and at least two light-emitting stacks disposed between the anode and the cathode, and a charge generation layer is disposed between two adjacent light-emitting stacks.

[0125] In one embodiment, the anode material can be any combination of oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO); the cathode material can be any combination of metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag).

[0126] In one embodiment, the hole injection layer comprises 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN) and 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA); the hole transport layer comprises TCTA; the electron blocking layer comprises m-CP; and the p-type charge generation layer comprises HAT-CN and TCTA.

[0127] In one embodiment, the organic light-emitting layer includes a blue light-emitting layer comprising a host material and a guest material. The host material includes anthracene derivatives, such as compound D, and the guest material includes boron nitrogen (BN) resonant fluorescent materials, such as compound E.

[0128]

[0129] In one embodiment, the electron injection layer comprises Yb, the electron transport layer comprises 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and lithium octahydroxyquinoline (LiQ), and the hole blocking layer comprises 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthrene (BCP).

[0130] In one embodiment, the stacked OLED can be fabricated using methods conventional in the art, such as sequentially depositing layers on a substrate.

[0131] This invention also provides a display device including the aforementioned organic electroluminescent device. Specifically, the display device can be an OLED display or other display device, as well as any product or component with display function, such as a television, digital camera, mobile phone, or tablet computer, that includes the aforementioned display device. The advantages of this display device over the prior art are the same as those of the aforementioned organic electroluminescent device, and will not be repeated here.

[0132] Specifically, this embodiment provides a stacked 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.

[0133] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0134] 1) Substrate cleaning:

[0135] 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.

[0136] 2) Preparation of organic layer:

[0137] 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).

[0138] The materials required to fabricate the device are as follows:

[0139]

[0140] in:

[0141] The anode is indium tin oxide (ITO, 10 nm thick);

[0142] The hole injection layer (HIL) is made of HAT-CN:TCTA (10nm thick);

[0143] The material of the first hole transport layer (HTL-1) is TCTA (20nm thick);

[0144] The material of the first electron blocking layer (EBL-1) is mCP (5nm thick);

[0145] The first organic light-emitting layer (EML-1) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0146] The material of the first hole blocking layer (HBL-1) is BCP (5nm thick);

[0147] The first electron transport layer (ETL-1) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm);

[0148] The n-type charge generation layer (CGL-n) is shown in Table 3;

[0149] The p-type charge generation layer (CGL-p) is made of HAT-CN and TCTA in a mass ratio of 8:2 (thickness 10nm);

[0150] The material of the second hole transport layer (HTL-2) is TCTA (20nm thick);

[0151] The material of the second electron blocking layer (EBL-2) is mCP (5nm thick);

[0152] The second organic light-emitting layer (EML-2) is made of D and E in a mass ratio of 95:5 (thickness 20nm);

[0153] The material of the second hole blocking layer (HBL-2) is BCP (5nm thick);

[0154] The second electron transport layer (ETL-2) is made of TPBI and LiQ in a mass ratio of 9:1 (thickness 25nm);

[0155] The electron injection layer (EIL) is made of Yb (1 nm thick);

[0156] The cathode is made of Mg and Ag in a mass ratio of 1:9 (thickness 11 nm).

[0157] Table 3 shows some of the layers of organic electroluminescent devices, their materials, and thicknesses.

[0158] Table 3

[0159]

[0160]

[0161] Device Test Examples

[0162] The organic electroluminescent devices obtained in Device Examples 1-9 and Device Comparative Example 1 in the device examples were tested.

[0163] 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;

[0164] Test conditions: Current density 10 mA / cm² 2 , room temperature.

[0165] Lifetime test: The time (in hours) when the device brightness drops to 95% of its original brightness was recorded. The device performance test results are shown in Table 4:

[0166] Table 4

[0167]

[0168]

[0169] It can be seen that, under the same current density, compared with Comparative Example 1, the OLEDs of Examples 1-9 have a longer lifetime, a lower driving voltage, and good current efficiency. This indicates that, when applied to CGL-n, they exhibit better thermal / electrical stability and are less prone to degradation or deterioration during device operation, thereby improving the efficiency, stability, and lifetime performance of the OLED.

[0170] 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 by, having the structure of Formula I: wherein Ar is selected from hydrogen, deuterium, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; L is selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; each of the substituents in the substituted C6-C60 aryl, substituted C3-C60 heteroaryl, substituted C6-C30 arylene, substituted C3-C30 heteroarylene is independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, non-fused C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino; when Ar is selected from hydrogen, deuterium, cyano, L is a spirofluorene or anthracene group.

2. The fused ring compound according to claim 1, characterized by In Formula I, Ar is selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C20 heteroaryl; wherein each of the substituents in the substituted C6-C25 aryl, substituted C3-C20 heteroaryl is independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino; Preferably, in Formula I, Ar is selected from substituted or unsubstituted group B, group B is selected from phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthryl, indenyl, naphthacenyl, perylenyl, chrysenyl, tetracenyl, fluoranthenyl, spirobifluorenyl, furanyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoaxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, bipyridyl, terpyridyl, phenylterpyridyl, diazafuorenyl, or phenophenanthrolinyl; wherein the substituents of the substituted group B are selected from halogen, cyano, C1-C4 alkyl, C6-C12 aryl; Preferably, L is selected from substituted or unsubstituted C6-C15 arylene, substituted or unsubstituted C3-C15 heteroarylene; wherein the substituents in the substituted C6-C15 arylene, substituted C3-C15 heteroarylene are each independently selected from one or a combination of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamine, C3-C60 heteroarylamine; Preferably, L is selected from substituted or unsubstituted group D, group D is selected from phenylene, naphthylene, anthrylene, fluorenylene, pyridylene, quinolylene; wherein the substituents in the substituted group D are selected from one or a combination of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamine, C3-C60 heteroarylamine.

3. The fused ring compound according to claim 1 or 2, characterized by Formula I is selected from the following structures:

4. An n-type charge generation layer, characterized by, The n-type charge generation layer material comprises any one or a combination of at least two of the fused ring compounds of any one of claims 1-3.

5. The n-type charge generation layer according to claim 4, characterized in that, The n-type charge generation layer further comprises a metal material; Preferably, the metal material comprises at least one of alkali metal, alkaline earth metal, transition metal. Preferably, the metal material comprises at least one of lithium, ytterbium, silver.

6. An electron transport layer, characterized in that, The electron transport layer material comprises any one or a combination of at least two of the fused ring compounds of any one of claims 1-3.

7. An organic electroluminescent device, characterized by comprising The organic electroluminescent device comprises a cathode, an anode, and an organic layer between the cathode and the anode, the organic layer comprising any one or a combination of at least two of the fused ring compounds of any one of claims 1-3; Preferably, the organic layer comprises the n-type charge generation layer of claim 4 and / or the electron transport layer of claim 5.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic layer comprises one or more of a hole injection layer, a first light-emitting stack, a second light-emitting stack, an electron injection layer. When the organic light-emitting device comprises an n-type charge generation layer, the n-type charge generation layer is between the first light-emitting stack and the second light-emitting stack.

9. An organic electroluminescent product, characterized by comprising the compound according to claim 1. The organic electroluminescent product comprises the organic electroluminescent device of claim 7 or 8.

10. An electronic device, characterized by The electronic device comprises the fused ring compound of any one of claims 1-3.

11. Electronic device according to claim 10, characterized in that The electronic device comprises 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 quenching devices, light-emitting electrochemical cells, and organic laser diodes.

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