A triazine compound containing a quinoline group and an organic electroluminescent device
By designing triazine compounds containing quinoline groups as electron transport layer materials, the problem of material loss during the manufacturing process of organic electroluminescent devices was solved, improving the driving voltage, current efficiency, and lifetime of the devices, and enhancing the overall performance of the devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUYANG SINEVA MATERIAL TECHNOLOGY CO LTD
- Filing Date
- 2026-02-14
- Publication Date
- 2026-06-02
AI Technical Summary
Existing organic electroluminescent devices suffer from material loss during manufacturing, resulting in low production efficiency. Furthermore, existing materials cannot effectively improve the driving voltage, current efficiency, and lifespan of the devices in solution processing.
By using triazine compounds containing quinoline groups as electron transport layer materials and designing their structures, organic electroluminescent devices were prepared that exhibited low driving voltage, high current efficiency, and long lifetime.
This achieves low driving voltage, high current efficiency, and long lifespan for organic electroluminescent devices, improving the overall performance of the devices.
Smart Images
Figure SMS_8 
Figure SMS_11 
Figure SMS_13
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a triazine compound containing a quinoline group and an organic electroluminescent device. Background Technology
[0002] Organic light emission (OLED) generally refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) typically have a structure comprising a positive electrode, a negative electrode, and an organic material layer in between. In many cases, the organic material layer has a multilayer structure composed of different materials to improve the efficiency and stability of the OLED. For example, the organic material layer can be composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer. In such an OLED structure, if a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic material layer, and electrons are injected from the negative electrode into the organic material layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons return to the ground state. Such OLEDs are known to possess characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, and high contrast. Organic electroluminescent elements are self-luminescent elements that utilize the recombination energy of holes injected from the anode and electrons injected from the cathode to cause fluorescent materials to emit light by applying an electric field. It has the following structure: an anode, a cathode, and an organic material layer between them. To improve the efficiency and stability of organic electroluminescent devices, the organic material layer typically comprises multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer, an electron transport layer (ETL), and an electron injection layer (EIL). In this type of organic light-emitting device, when a voltage is applied between the anode and cathode, holes from the anode and electrons from the cathode are injected into the organic material layer, and the resulting excitons generate light with a specific wavelength when they migrate to the ground state.
[0003] Deposition methods are commonly used to manufacture organic light-emitting devices (OLEDs) in related fields. However, deposition methods for manufacturing OLEDs often suffer from material loss. To address this issue, solution-based methods have been developed to improve production efficiency by reducing material loss, and materials that can be used during solution-based methods have also been developed.
[0004] To fully exhibit the superior characteristics of the aforementioned organic light-emitting devices, it is necessary to use stable and effective materials to support the organic material layers in the devices, such as hole injection materials, hole transport materials, light-emitting materials, electron blocking materials, electron transport materials, and electron injection materials. Therefore, it is always necessary to develop new organic electroluminescent materials. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a triazine compound containing a quinoline group and an organic electroluminescent device. The present invention designs the structure of a triazine compound containing a quinoline group to obtain a high-performance triazine compound. Using this triazine compound containing a quinoline group as an electron transport layer material, the resulting organic electroluminescent device exhibits low driving voltage, high current efficiency, and long lifetime.
[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a triazine compound containing a quinoline group, said triazine compound having the structure shown in Formula I: ; Wherein, L1, L2, and Ar each independently represent any one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C3-C30 cycloalkylene. R1 represents substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkoxy. Any of the following, with dashed lines representing connection points; R2 represents a hydrogen atom, a substituted or unsubstituted C1-C30 straight-chain or branched alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C1-C30 alkoxy group. Any of the following, with dashed lines representing connection points; R a R b R c Each independently represents any one of the following: substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, or substituted or unsubstituted C6-C30 aryl, and R a R b R c At least one of the following represents any one of substituted or unsubstituted C1-C30 straight-chain or branched alkyl groups, or substituted or unsubstituted C3-C30 cycloalkyl groups; L1, L2, R1, R2, R a R b R c The substituents mentioned in Ar represent any one of cyano, halogen atom, C1-C10 straight-chain or branched alkyl, and C1-C10 alkoxy. n is 0 or 1; Each hydrogen atom in the compound of formula I may be independently replaced by a deuterium atom.
[0007] In the present invention, through the design of the structure of the triazine compound containing a quinoline group, a triazine compound containing a quinoline group with excellent properties is obtained. Using this triazine compound containing a quinoline group as an electron transport layer material, an organic electroluminescent device prepared has a lower driving voltage, a higher current efficiency and a longer lifespan.
[0008] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or multiple substituents. When there are multiple (at least two) substituents, they may be the same or different substituents; when the same expression is involved hereinafter, it has the same meaning, and the selection range of substituents is as shown above and will not be elaborated one by one.
[0009] In the present invention, for the description of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.
[0010] In the present invention, unless otherwise specified, the heteroatoms of the heteroaryl group are selected from atoms or atomic groups of N, O, S, P, B, Si or Se, preferably N, O, S.
[0011] In the present invention, the expression of a ring structure with a "-" or "------" drawn across it indicates that the connection site is at any position on the ring structure where a bond can be formed.
[0012] In the present invention, the expression Ca-Cb represents that the group has a carbon atom number of a-b. Unless otherwise specified, generally speaking, this carbon atom number does not include the carbon atom number of the substituent.
[0013] In the present invention, "independently of each other" means that when its subject has multiple ones, they may be the same or different from each other.
[0014] In this invention, the C1-C30 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C24, C26, or C28, preferably C1-C20 straight-chain or branched alkyl groups, and more preferably C1-C10 straight-chain or branched alkyl groups; exemplary, including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl, or n-decyl, etc.
[0015] Specific examples of the C1-C30 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C24, C26, or C28, etc.) alkoxy groups can be exemplified by the monovalent groups obtained by connecting the above-mentioned straight-chain or branched alkyl groups with O.
[0016] In this invention, the C3-C30 cycloalkyl groups can all be cycloalkyl groups of C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C24, C26, or C28, etc.; exemplary examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Specific examples of the C3-C30 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C24, C26, or C28, etc.) cycloalkylene groups can be exemplified by removing one hydrogen atom from the aforementioned cycloalkyl groups to obtain a divalent group.
[0017] In this invention, the C6-C30 aryl groups can all be aryl groups of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc., preferably C6-C20 aryl groups, including monocyclic aryl groups or fused-ring aryl groups. The monocyclic aryl group refers to a group containing at least one phenyl group. When it contains at least two phenyl groups, the phenyl groups are linked by single bonds. Examples include, but are not limited to, phenyl, biphenyl, and terphenyl groups. The fused-ring aryl group refers to a group containing at least two aromatic rings, where the aromatic rings share two adjacent carbon atoms that are fused together. Examples include, but are not limited to, naphthyl, naphthylphenyl, phenylnaphthyl, anthraceneyl, phenanthryl, indene, fluorenyl and its derivatives (9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirodifluorenyl, benzo[a]fluorenyl, etc.), fluoranyl, triphenylene, pyrene, peryl, phenanthryl or tetraphenyl, etc. The groups listed above include all possible linkage methods.
[0018] In this invention, the C3-C30 heteroaryl groups can be heteroaryl groups of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, including monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thiophene, pyrrole, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazoleyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), and the two share two adjacent atoms fused together in a group. Examples include, but are not limited to: benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazoleyl and its derivatives (N-phenylcarbazoleyl, N-naphthylcarbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, indolocarbazoleyl, azacarbazoleyl, etc.), acridineyl, phenazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, pyridinylpyrimidinyl, pyridopyrazinyl, etc.; the aforementioned groups include all possible linkages.
[0019] Specific examples of the C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) arylene groups can be exemplified by removing one hydrogen atom from the aforementioned aryl examples to obtain a divalent group; specific examples of the C3-C30 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) heteroarylene groups can be exemplified by removing one hydrogen atom from the aforementioned heteroarylene examples to obtain a divalent group.
[0020] In this invention, the halogen includes fluorine, chlorine, bromine, or iodine; the same descriptions used below have the same meaning.
[0021] In this invention, "halogenated" means that at least one H in the group is replaced by a halogen (fluorine, chlorine, bromine or iodine).
[0022] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.
[0023] Preferably, L1 represents any one of the following: single bond, phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, and cyclohexylene.
[0024] Preferably, L1 represents a single bond.
[0025] Preferably, R2 represents any one of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, phenyl, naphthyl, biphenyl, and 9,9-dimethylfluorenyl.
[0026] Preferably, R2 represents a hydrogen atom.
[0027] Preferably, the triazine compound containing a quinoline group has the structure shown in Formula II: ; L2, R1, Ar and n have the same definitions as above.
[0028] Preferably, L2 represents any one of mono- or meta-phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, or cyclohexylene.
[0029] Preferably, L2 represents any one of phenylene, biphenylene, or naphthylene.
[0030] Preferably, Ar represents any one of phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, or cyclohexylene.
[0031] Preferably, Ar represents any one of phenylene, naphthylene, or biphenylene.
[0032] Preferably, the triazine compound containing a quinoline group has any one of the structures shown in Formula II-1, Formula II-2, or Formula II-3: ; R1 and n have the same definitions as above.
[0033] Preferably, the triazine compound containing a quinoline group has any one of the structures shown in Formula II-1A, Formula II-1B, Formula II-1C, Formula II-1D, Formula II-2A, Formula II-2B, Formula II-2C, Formula II-2D, Formula II-3A, or Formula II-3B: ; R1 and n have the same definitions as above.
[0034] R1 represents any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, phenyl, naphthyl, biphenyl, or 9,9-dimethylfluorenyl.
[0035] Preferably, R1 represents any one of phenyl, naphthyl, or biphenyl.
[0036] Preferably, the triazine compound containing a quinoline group includes the following compounds: .
[0037] Preferably, the triazine compound containing a quinoline group includes compounds 1-6: .
[0038] It should be noted that the present invention lists some specific structural forms of the triazine compounds containing quinoline groups, but the triazine compounds containing quinoline groups described in the present invention are not limited to the listed chemical structures. Any structure based on the structure shown in Formula I, where L1, L2, R1, and R2 satisfy the above-mentioned limiting conditions should be included.
[0039] It should also be noted that the present invention does not impose any special restrictions on the specific synthetic methods of the above-mentioned triazine compounds containing quinoline groups, and commonly used synthetic methods in the art are applicable.
[0040] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising a triazine compound containing a quinoline group as described in the first aspect.
[0041] Preferably, the organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer includes triazine compounds containing quinoline groups as described in the first aspect.
[0042] Preferably, the organic layer includes an electron transport layer, the material of which includes a triazine compound containing a quinoline group as described in the first aspect.
[0043] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.
[0044] Compared with the prior art, the present invention has the following beneficial effects: This invention designs the structure of triazine compounds containing quinoline groups, resulting in triazine compounds with excellent luminescent properties. Using these triazine compounds as electron transport layer materials, organic electroluminescent devices are fabricated with low driving voltage, high current efficiency, and long lifetime. Detailed Implementation
[0045] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.
[0046] It should be noted that in the following examples, "10 V / W" means that when the amount of reactant is 1 g, the amount of solvent is 10 mL. Similarly, "5 V / W" means that when the amount of reactant is 1 g, the amount of solvent is 5 mL. For details, please refer to the specific descriptions in the following examples.
[0047] Example 1 This embodiment provides compound 1 and its synthesis method, which is as follows: (1) Dissolve raw material 1-A (1.0 mmol) and raw material 1-B (1.5 mmol) in toluene (10 V / W) solution, then purge with nitrogen three times. Under nitrogen protection, add potassium acetate (3.0 mmol) and bis(triphenylphosphine)dichloropalladium (Pd(PPh3)2Cl2, 0.01 mmol), stir until homogeneous, heat to 115 °C, and reflux for 6 h. After the reaction is complete, cool the filtrate to room temperature, wash three times with water, retain the organic phase, and then extract the aqueous phase with ethyl acetate. After combining the organic phases, dry with anhydrous magnesium sulfate and remove the solvent using a rotary evaporator to obtain intermediate 1-1 (yield 94.7%). The mass spectrometry data of intermediate 1-1 were tested, and its mass-to-charge ratio (m / z) was measured to be 331.17.
[0048] (2) Under nitrogen protection, intermediate 1-1 (1.0 mmol) and starting material 1-C (0.95 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). Then, nitrogen was purged three times. Under nitrogen protection, potassium carbonate (2.0 mmol) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol) were added, stirred evenly, heated to 90 °C, and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly, and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then, the aqueous phase was extracted with ethyl acetate. After combining the organic phases, the mixture was dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain intermediate 1-2 (yield 81.8%). The mass spectrometry data of intermediates 1-2 were tested, and their mass-to-charge ratio (m / z) was measured to be 470.13.
[0049] (3) Intermediate 1-2 (1.0 mmol) and raw material 1-D (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W), and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos, 0.04 eq) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 minutes. h; After the reaction was completed, the temperature was lowered slightly, and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tris(dibenzylacetone)palladium. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to give compound 1 (yield: 71.4%). The mass spectrometry data of compound 1 were tested, and its mass-to-charge ratio (m / z) was measured to be 662.25.
[0050] In step (1) of this embodiment, toluene (10 V / W) means that when the amount of raw material 1-A is 1 g, the amount of toluene is 10 mL; in steps (2) and (3), toluene (10 V / W), ethanol (5 V / W) and water (5 V / W) mean that when the amount of raw material 1-A is 1 g in step (1), the amount of toluene is 10 mL, the amount of ethanol is 5 mL and the amount of water is 5 mL.
[0051] Example 2 This embodiment provides compound 2 and its synthesis method, which is as follows: (1) Intermediate 1-1 was synthesized according to the synthesis method provided in Example 1; (2) Under nitrogen protection, intermediate 1-1 (1.0 mmol) and starting material 2-A (0.95 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). Then, nitrogen was purged three times. Under nitrogen protection, potassium carbonate (2.0 mmol) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol) were added, stirred evenly, heated to 90 °C, and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly, and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then, the aqueous phase was extracted with ethyl acetate. After combining the organic phases, the mixture was dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain intermediate 2-1 (yield 79.5%). The mass spectrometry data of intermediate 2-1 were tested, and its mass-to-charge ratio (m / z) was measured to be 546.16.
[0052] (3) Intermediate 2-1 (1.0 mmol) and starting material 1-D (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.04 mmol) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tris(dibenzylacetone)dipalladium. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain compound 2 (yield 68.2%). The mass spectrometry data of compound 2 were tested, and its mass-to-charge ratio (m / z) was measured to be 764.29.
[0053] In steps (2) and (3) of this embodiment, toluene (10 V / W), ethanol (5 V / W) and water (5 V / W) refer to the following amounts in sequence: when the amount of raw material 1-A used in the synthesis of intermediate 1-1 in step (1) is 1 g, the amount of toluene is 10 mL, the amount of ethanol is 5 mL and the amount of water is 5 mL.
[0054] Example 3 This embodiment provides compound 3 and its synthesis method, which is as follows: (1) Intermediate 1-1 was synthesized according to the synthesis method provided in Example 1; (2) Under nitrogen protection, intermediate 1-1 (1.0 mmol) and starting material 3-A (0.95 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). Then, nitrogen was purged three times. Under nitrogen protection, potassium carbonate (2.0 eq) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol) were added, stirred evenly, heated to 90 °C, and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly, and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then, the aqueous phase was extracted with ethyl acetate. After combining the organic phases, the mixture was dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain intermediate 3-1 (yield 85.5%). The mass spectrometry data of intermediate 3-1 were tested, and its mass-to-charge ratio (m / z) was measured to be 520.15.
[0055] (3) Intermediate 3-1 (1.0 mmol) and starting material 1-D (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.04 mmol) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth. The potassium carbonate and tris(dibenzylacetone)dipalladium were cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain compound 3 (yield 68.2%). The mass spectrometry data of compound 3 were tested, and its mass-to-charge ratio (m / z) was measured to be 712.26.
[0056] In steps (2) and (3) of this embodiment, toluene (10 V / W), ethanol (5 V / W) and water (5 V / W) refer to the following amounts in sequence: when the amount of raw material 1-A used in the synthesis of intermediate 1-1 in step (1) is 1 g, the amount of toluene is 10 mL, the amount of ethanol is 5 mL and the amount of water is 5 mL.
[0057] Example 4 This embodiment provides compound 4 and its synthesis method, which is as follows: (1) Dissolve raw material 4-A (1.0 mmol) and raw material 4-B (1.1 mmol) in a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W), then purge with nitrogen three times. Under nitrogen protection, add potassium carbonate (2.0 mmol) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol), stir until homogeneous, heat to 90 °C, and reflux for 12 h. After the reaction is complete, lower the temperature slightly, filter with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium, cool the filtrate to room temperature, wash with water three times, retain the organic phase, and then extract the aqueous phase with ethyl acetate. After combining the organic phases, dry with anhydrous magnesium sulfate and remove the solvent using a rotary evaporator to obtain intermediate 4-1 (yield 73.5%). The mass spectrometry data of intermediate 4-1 were tested, and its mass-to-charge ratio (m / z) was measured to be 264.05.
[0058] (2) Under nitrogen protection, intermediate 4-1 (1.0 mmol) and starting material 1-B (1.5 mmol) were dissolved in toluene (10 V / W) solution, followed by nitrogen purging three times. Under nitrogen protection, potassium acetate (3.0 mmol) and bis(triphenylphosphine)dichloropalladium (Pd(PPh3)2Cl2, 0.01 mmol) were added, stirred until homogeneous, heated to 115 °C, and refluxed for 6 h. After the reaction was completed, the filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. After combining the organic phases, the mixture was dried with anhydrous magnesium sulfate, and the toluene solvent was removed using a rotary evaporator to obtain intermediate 4-2 (yield 92.8%). The mass spectrometry data of intermediate 4-2 were tested, and its mass-to-charge ratio (m / z) was measured to be 356.17.
[0059] (3) Intermediate 4-2 (1.0 mmol) and starting material 4-C (0.95 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol) were added. The mixture was stirred until homogeneous and heated to 90 °C. The mixture was then refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain intermediate 4-3 (yield 93.6%). The mass spectrometry data of intermediate 4-3 were tested, and its mass-to-charge ratio (m / z) was measured to be 495.13.
[0060] (4) Intermediate 4-3 (1.0 mmol) and starting material 4-D (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.04 mmol) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth. The potassium carbonate and tris(dibenzylacetone)dipalladium were removed. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain compound 4 (yield 56.9%). The mass spectrometry data of compound 4 were tested, and its mass-to-charge ratio (m / z) was measured to be 687.24.
[0061] In steps (1), (3), and (4) of this embodiment, toluene (10 V / W), ethanol (5 V / W), and water (5 V / W) refer to the following respectively: when the amount of raw material 4-A in step (1) is 1 g, the amount of toluene is 10 mL, the amount of ethanol is 5 mL, and the amount of water is 5 mL; in step (2), toluene (10 V / W) refers to the following: when the amount of raw material 4-A in step (1) is 1 g, the amount of toluene is 10 mL.
[0062] Example 5 This embodiment provides compound 5 and its synthesis method, which is as follows: (1) Intermediate 1-1 was synthesized according to the synthesis method provided in Example 1; (2) Under nitrogen protection, intermediate 1-1 (1.0 mmol) and starting material 5-A (0.95 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). Then, nitrogen was purged three times. Under nitrogen protection, potassium carbonate (2.0 mmol) and tetrakis(triphenylphosphine)palladium (Pd(pph3)4, 0.02 mmol) were added, stirred until homogeneous, heated to 90 °C, and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly, and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tetrakis(triphenylphosphine)palladium. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. After combining the organic phases, the mixture was dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain intermediate 5-1 (yield 84.7%). The mass spectrometry data of intermediate 5-1 were tested, and its mass-to-charge ratio (m / z) was measured to be 520.15.
[0063] (3) Intermediate 5-1 (1.0 mmol) and starting material 1-D (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbenzylphosphine (0.04 mmol) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tris(dibenzylacetone)dipalladium. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain intermediate 5-2 (yield 68.2%). The mass spectrometry data of intermediate 5-2 were tested, and its mass-to-charge ratio (m / z) was measured to be 712.26.
[0064] (4) Under nitrogen protection, intermediate 5-2 (1.0 mmol) was added to a deuterated benzene (15 V / W) solution, followed by nitrogen purging three times. Trifluoromethanesulfonic acid (TfOH) (1.0 mmol) was slowly added dropwise under nitrogen protection, stirred until homogeneous, heated to 80 °C, and refluxed for 6 h. After the reaction was completed, the temperature was lowered to room temperature, and sodium bicarbonate aqueous solution (NaHCO3) was added to neutralize it. The deuterated benzene was distilled off under reduced pressure, filtered directly, washed three times with water, and dried with anhydrous magnesium sulfate. After filtration, compound 5 was obtained (yield 88.2%). The mass spectrometry data of compound 5 were tested, and its mass-to-charge ratio (m / z) was measured to be 744.26.
[0065] In steps (2) and (3) of this embodiment, toluene (10 V / W), ethanol (5 V / W) and water (5 V / W) refer to the following respectively: when the amount of raw material 1-A used in the synthesis of intermediate 1-1 in step (1) is 1 g, the amount of toluene is 10 mL, the amount of ethanol is 5 mL and the amount of water is 5 mL; in step (4), deuterium benzene (15 V / W) refers to the following: when the amount of raw material 1-A used in the synthesis of intermediate 1-1 in step (1) is 1 g, the amount of deuterium benzene is 15 mL.
[0066] Example 6 This embodiment provides compound 6 and its synthesis method, which is as follows: (1) Intermediate 1-1 was synthesized according to the synthesis method provided in Example 1; (2) Intermediates 1-2 were synthesized according to the synthesis method provided in Example 1; (3) Intermediate 1-2 (1.0 mmol) and starting material 6-A (1.1 mmol) were added to a mixed solution of toluene (10 V / W), ethanol (5 V / W) and water (5 V / W). The mixture was then purged with nitrogen three times. Under nitrogen protection, potassium carbonate (2.0 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.02 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.04 mmol) were added and stirred until homogeneous. The mixture was heated to 90 °C and refluxed for 12 h. After the reaction was completed, the temperature was lowered slightly and the mixture was filtered with diatomaceous earth to remove potassium carbonate and tris(dibenzylacetone)dipalladium. The filtrate was cooled to room temperature and washed three times with water. The organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain compound 6 (yield 73.8%). The mass spectrometry data of compound 6 were tested, and its mass-to-charge ratio (m / z) was measured to be 738.28.
[0067] In step (3) of this embodiment, toluene (10 V / W), ethanol (5 V / W) and water (5 V / W) refer to the following amounts in sequence: when the amount of raw material 1-A used in the synthesis of intermediate 1-1 in step (1) is 1 g, the amount of toluene is 10 mL, the amount of ethanol is 5 mL and the amount of water is 5 mL.
[0068] For other compounds whose specific synthesis methods are not listed, they can be synthesized by referring to the above examples and combining them with common knowledge in the field.
[0069] The specific structures of some of the materials used in the following device embodiments and device comparison examples are as follows: .
[0070] Application Example 1 This application example provides an organic electroluminescent device and its fabrication method. The organic electroluminescent device has the following structure: ITO / NPB (40nm) / EM1 (30nm) / electron transport material (30nm) / LiF (0.5nm) / Al (150nm).
[0071] The fabrication method of the above-mentioned organic electroluminescent device includes the following steps: A glass substrate coated with an ITO transparent conductive layer (as the anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixture of acetone and ethanol, and then baked in a clean environment until completely dehydrated. It was then cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam to improve surface properties and enhance its bonding ability with the hole injection layer. The glass substrate was then placed in a vacuum chamber and evacuated to a vacuum level of 1 × 10⁻⁶.-5 ~9×10 -3 Pa, NPB was vacuum-deposited on the anode as a hole transport layer at a deposition rate of 0.1 nm / s and a film thickness of 40 nm. EM1 was vacuum-deposited on top of the hole transport layer as the organic light-emitting layer of the device at a deposition rate of 0.1 nm / s and a film thickness of 30 nm. Compound 1 was vacuum-deposited on top of the organic light-emitting layer as the electron transport layer of the organic electroluminescent device; the deposition rate was 0.1 nm / s and the deposition film thickness was 30 nm. Organic electroluminescent devices were fabricated by vacuum evaporation of 0.5 nm LiF and 150 nm Al on the electron transport layer as the electron injection layer and cathode, respectively.
[0072] Application Examples 2-6 Application Examples 2-6 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the electron transport material is different (see Table 1 below), while other conditions are the same as in Application Example 1.
[0073] Comparative Application Examples 1-4 Comparative Application Examples 1-4 each provide an organic electroluminescent device, differing from Application Example 1 only in the electron transport material (see Table 1 below), while other conditions are the same as in Application Example 1.
[0074] Performance testing The driving voltage, current efficiency, and lifetime (LT90) of the OLED devices provided above were tested. LT90 refers to the time required for the brightness to decrease to 90% of its original brightness while maintaining an initial brightness of 1000 nits at a constant current density. Test items included the brightness, driving voltage, and current efficiency of the organic electroluminescent device. The driving voltage, current efficiency, and LT90 data were all based on a brightness of 1000 cd / m². 2 The relative values are based on the test data of Comparative Application Example 1. All performance characterization data for other comparative application examples and application examples are relative values. The performance test results of the organic electroluminescent devices are shown in Table 1 below: Table 1 As can be seen from the above, this invention designs the structure of triazine compounds containing quinoline groups, resulting in triazine compounds with excellent luminescent properties. Using these triazine compounds containing quinoline groups as electron transport layer materials, the resulting organic electroluminescent devices exhibit low driving voltage, high current efficiency, and long lifetime.
[0075] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.
Claims
1. A triazine compound containing a quinoline group, characterized in that, The triazine compound containing the quinoline group has the structure shown in Formula I: ； Wherein, L1, L2, and Ar each independently represent any one of the following: single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C3-C30 cycloalkylene. R1 represents substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkoxy. Any of the following, with dashed lines representing connection points; R2 represents a hydrogen atom, a substituted or unsubstituted C1-C30 straight-chain or branched alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C1-C30 alkoxy group. Any of the following, with dashed lines representing connection points; R a R b R c Each independently represents any one of the following: substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, or substituted or unsubstituted C6-C30 aryl, and R a R b R c At least one of the following represents any one of substituted or unsubstituted C1-C30 straight-chain or branched alkyl groups, or substituted or unsubstituted C3-C30 cycloalkyl groups; L1, L2, Ar, R1, R2, R a R b R c The substituents mentioned herein represent any one of cyano, halogen atom, C1-C10 straight-chain or branched alkyl, and C1-C10 alkoxy; n is 0 or 1; In the compound of formula I, each hydrogen atom can be independently replaced by a deuterium atom.
2. The triazine compound containing a quinoline group according to claim 1, characterized in that, L1 represents any one of the following: single bond, phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, or cyclohexylene, preferably any one of the following: single bond, phenylene, naphthylene, or biphenylene, more preferably single bond; Preferably, R2 represents any one of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, phenyl, naphthyl, biphenyl, or 9,9-dimethylfluorenyl, and more preferably hydrogen atom.
3. The triazine compound containing a quinoline group according to claim 1 or 2, characterized in that, The triazine compound containing the quinoline group has the structure shown in Formula II: ； Wherein, L2, R1, Ar and n have the same definition as in claim 1.
4. The triazine compound containing a quinoline group according to any one of claims 1-3, characterized in that, L2 represents any one of the following: mono-, phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, and cyclohexylene, preferably any one of phenylene, biphenylene, or naphthylene; Preferably, Ar represents any one of phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirofluorene, triphenylene, dibenzofuranyl, dibenzothiophene, naphthanobenzofuranyl, naphthanobenzothiophene, carbazolyl, cyclopentylene, or cyclohexylene, and more preferably any one of phenylene, naphthylene, or biphenylene.
5. The triazine compound containing a quinoline group according to any one of claims 1-4, characterized in that, The triazine compounds containing quinoline groups have any one of the structures shown in Formula II-1, Formula II-2, or Formula II-3: ； Wherein, R1 and n have the same definitions as in claim 1; Preferably, the triazine compound containing a quinoline group has any one of the structures shown in Formula II-1A, Formula II-1B, Formula II-1C, Formula II-1D, Formula II-2A, Formula II-2B, Formula II-2C, Formula II-2D, Formula II-3A, or Formula II-3B: ； R1 and n have the same definitions as above.
6. The triazine compound containing a quinoline group according to any one of claims 1-5, characterized in that, R1 represents any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, phenyl, naphthyl, biphenyl, or 9,9-dimethylfluorenyl, preferably any one of phenyl, naphthyl, or biphenyl.
7. The triazine compound containing a quinoline group according to any one of claims 1-6, characterized in that, The triazine compounds containing quinoline groups include the following compounds: ； Preferably, the triazine compound containing a quinoline group includes compounds 1-6: 。 8. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a triazine compound containing a quinoline group as described in any one of claims 1-7.
9. The organic electroluminescent device according to claim 8, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer includes a triazine compound containing a quinoline group as described in any one of claims 1-7.
10. The organic electroluminescent device according to claim 9, characterized in that, The organic layer includes an electron transport layer, the material of which includes a triazine compound containing a quinoline group as described in any one of claims 1-7.