Aza-cyclic organic compound, use thereof, and organic electroluminescent device

Abstract

This invention relates to the field of organic electroluminescent device technology, and discloses a nitrogen heterocyclic organic compound and its application, as well as an organic electroluminescent device. The compound has a structure shown in A-L-B; A is an unsubstituted group or a group substituted by at least one group in combination A, as shown in formula (I-1); the combination A contains C. 1‑20 Alkyl, C 1‑20 Alkoxy, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene. When the nitrogen heterocyclic organic compounds provided by this invention are used in organic light-emitting devices, the organic light-emitting devices containing these nitrogen heterocyclic organic compounds have the advantages of low driving voltage, high luminous efficiency, and long service life.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent device technology, specifically to a nitrogen heterocyclic organic compound and its application, and an organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a display technology with broad application prospects. OLEDs are self-emissive and do not require a backlight, giving them significant advantages in contrast and color performance. They are also thin, light, and flexible, gradually becoming one of the mainstream display technologies.

[0003] Currently, stacked organic light-emitting diodes (OLEDs) have attracted widespread attention. Their light-emitting principle is the same as that of traditional single-layer OLED devices. A single-layer OLED device is a single light-emitting unit, typically containing an emissive layer and associated electron transport and hole transport layers. When a voltage is applied across the device, electrons and holes are injected into the electrodes under the influence of an external electric field. Electrons travel from the cathode through the electron transport layer into the emissive layer, while holes travel from the anode through the hole transport layer into the emissive layer. In the emissive layer, electrons and holes meet and recombine to form excitons. When these excitons transition from the excited state back to the ground state, they emit photons, thus producing light emission. For stacked structures, multiple such light-emitting units are stacked together. Light generated by one unit can pass through the intermediate charge generation layer (CGL) to reach the next unit. Composed of multiple stacked organic light-emitting layers, various colors and spectra can be achieved through different combinations of light emission from these layers, while also offering higher luminous efficiency, color purity, brightness, and lifespan.

[0004] In multilayer devices, the main function of CGL is to generate holes and electrons under the action of an electric field, provide the required charge for the light-emitting layer, and effectively transfer the generated charge to the adjacent light-emitting layer to ensure the uniform distribution of charge in the device.

[0005] Therefore, the performance of the CGL layer has a crucial impact on the overall performance of the stacked device. Furthermore, the CGL material needs to possess excellent charge transport properties, optical transmittance, and stability to ensure efficient charge transfer and collection between the light-emitting units while minimizing energy loss.

[0006] In summary, developing high-performance CGL materials to reduce the energy level barrier between the CGL layer and the light-emitting unit, improve the energy level matching between the CGL layer and the light-emitting unit, thereby reducing the driving voltage of the device and improving the luminous efficiency and lifespan of the device, is of great significance. Summary of the Invention

[0007] The purpose of this invention is to provide a new class of nitrogen heterocyclic organic compounds so that organic light-emitting devices containing such nitrogen heterocyclic organic compounds have the advantages of high luminous efficiency and long lifespan.

[0008] To achieve the above objectives, a first aspect of the present invention provides a nitrogen heterocyclic organic compound having the structure shown in ALB;

[0009] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0010] B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-30 Aromatic groups; combination B contains C 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, triphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0011] L is composed of C, which may or may not contain type A heteroatoms. 3-30 An aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave;

[0012] The type A heteroatoms include at least one of N, O, and S;

[0013]

[0014] A second aspect of the invention provides the use of the nitrogen heterocyclic organic compounds described in the first aspect in organic electroluminescent devices and / or perovskite solar cells.

[0015] A third aspect of the present invention provides an organic electroluminescent device comprising a first electrode; a second electrode disposed opposite to the first electrode; and at least one organic material layer between the first electrode and the second electrode, wherein the organic electroluminescent device comprises at least one of the nitrogen heterocyclic organic compounds described in the first aspect of the present invention.

[0016] The solution provided by this invention has at least the following specific advantages:

[0017] 1. The compounds of the present invention have good planarity and high electron mobility, that is, they have strong electron transport capabilities. When the compounds of the present invention are applied to organic electroluminescent devices, they can improve the luminous efficiency of the devices.

[0018] 2. The compound of the present invention has a high glass transition temperature, which makes the film thermally stable and thus improves the service life of the device.

[0019] In summary, when the nitrogen heterocyclic organic compounds provided by this invention are used in organic light-emitting devices, the organic light-emitting devices containing such nitrogen heterocyclic organic compounds have the advantages of high luminous efficiency and long service life. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0022] In this invention, "aromatic compound" and "aromatic group" are interpreted broadly to refer to cyclic compounds or groups that contain at least one delocalized bond and are thus "aromatic".

[0023] "C containing or not containing type A heteroatoms" 3-30 The aromatic compound is described as having at least one of the following linkage groups formed by the departure of any two H atoms: 3-30 carbon atoms (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms). The aromatic compound may or may not contain heteroatoms. The linkage group may also be selected from C atoms containing or not containing type A heteroatoms. 3-30 Aromatic compounds can form two or more linking groups by removing any two H atoms that can leave their bonds. For example, naphthalene and benzene both remove two H atoms and bond with each other to form linking groups.

[0024] “C 1-20 "Alkyl" refers to a straight-chain or branched alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. 1-10 Alkyl" "C" 1～8 Alkyl", C 1～6 Alkyl", C 1～3Alkyl groups have similar definitions, differing only in the total number of carbon atoms.

[0025] “C 1-20 "Alkoxy" indicates "C 1-20 The alkyl group contains at least one oxygen atom inserted into its chain, including straight-chain alkoxy and branched-chain alkoxy groups, and this oxygen atom is connected to the parent nucleus. Examples include methoxy, ethoxy, and n-propoxy. "C" 1～8 Alkoxy, C 1～6 Alkoxy, C 1～3 "Alkoxy" and similar terms have similar definitions, differing only in the total number of carbon atoms.

[0026] In the structural formula of this invention, the dashed lines indicate that there are no special requirements for the connection sites, and connections can be made at any possible connection sites.

[0027] When the compounds of the present invention contain substituents, there are no particular requirements on the specific substitution position of the substituents; they can be any position that can be substituted.

[0028] As previously described, a first aspect of the present invention provides a nitrogen heterocyclic organic compound having the structure shown in ALB;

[0029] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0030] B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-30 Aromatic groups; combination B contains C 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, triphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0031] L is composed of C, which may or may not contain type A heteroatoms. 3-30 An aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave;

[0032] The type A heteroatoms include at least one of N, O, and S;

[0033]

[0034] According to a preferred embodiment, in the structure shown in ALB...

[0035] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-12 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0036] B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-24 Aromatic groups; combination B contains C 1-12 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0037] L is composed of C, which may or may not contain type A heteroatoms. 3-24 An aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave;

[0038] The type A heteroatoms include at least one of N, O, and S.

[0039] According to another preferred embodiment, in the structure shown in ALB...

[0040] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-8 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0041] B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-20 Aromatic groups; combination B contains C 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; the class A heteroatoms include at least one of N, O, and S;

[0042] L is one or two of the following linkage groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyridine, dibenzothiophene, dibenzofuran, fluorene, or carbazole.

[0043] According to a further preferred embodiment, in the structure shown in ALB, B is any one of the following: a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; a group of formula (II-2) that is unsubstituted or substituted by at least one group in combination B; and a group of formula (II-3) that is unsubstituted or substituted by at least one group in combination B; wherein combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0044]

[0045] X1, X2, and X3 are each independently N or CH;

[0046] In formula (II-3), X4 is -N(R1)-, O, S or -C(R1)(R2)-; R1 and R2 are each independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

[0047] In a preferred embodiment (hereinafter referred to as preferred specific embodiment 1), in the structure shown in ALB,

[0048] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0049] B is a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0050]

[0051] In equation (II-1), X1 and X2 are each independently N or CH;

[0052] L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine.

[0053] In the preferred embodiment 1, more preferably, X1 and X2 in formula (II-1) are both N.

[0054] In a preferred embodiment 1, more preferably, the nitrogen heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

[0055]

[0056] In a preferred embodiment (hereinafter referred to as preferred specific embodiment 2), in the structure shown in ALB,

[0057] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0058] B is a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0059]

[0060] In equation (II-1), both X1 and X2 are CH;

[0061] L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine.

[0062] In the preferred embodiment 2, more preferably, the nitrogen heterocyclic organic compound with the structure shown in ALB is selected from any one of the following;

[0063]

[0064] In a preferred embodiment (hereinafter referred to as preferred specific embodiment 3), in the structure shown in ALB,

[0065] A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0066] B is a group of formula (II-2) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0067]

[0068] In equation (II-2), X1, X2, and X3 are each independently N or CH;

[0069] L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine.

[0070] In the preferred embodiment 3, more preferably, in formula (II-2), X2 is N; one of X1 and X3 is H, and the other is CH.

[0071] In a preferred embodiment 3, the nitrogen heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

[0072]

[0073] In the preferred embodiment 3, more preferably, in formula (II-2), X1, X2 and X3 are all CH.

[0074] In a preferred embodiment 3, the nitrogen heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

[0075]

[0076] In a preferred embodiment (hereinafter referred to as preferred embodiment 4), in the structure shown in ALB, A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene;

[0077] B is a group of formula (II-3) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene;

[0078]

[0079] In formula (II-3), X4 is -N(R1)-, O, S or -C(R1)(R2)-; R1 and R2 are each independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl;

[0080] L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine.

[0081] In the preferred embodiment 4, more preferably, the nitrogen heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

[0082]

[0083]

[0084] More preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of compounds 1 to 44 and compounds 89 to 120.

[0085] This invention does not impose any particular limitation on the specific methods for preparing the aforementioned organic compounds. Those skilled in the art can obtain the aforementioned compounds of this invention by combining the specific structural formulas provided by this invention with known knowledge in the field of organic synthesis. Furthermore, several examples are exemplarily listed below to illustrate the methods for preparing the organic compounds of this invention. Those skilled in the art can also obtain specific methods for preparing all other organic compounds by changing the types of raw materials according to the methods for preparing the organic compounds described below. This invention will not further describe the preparation methods for all organic compounds in detail, and this should not be construed as a limitation of the invention.

[0086] As previously stated, a second aspect of the present invention provides the use of the nitrogen heterocyclic organic compounds described in the first aspect in organic electroluminescent devices and / or perovskite solar cells.

[0087] Preferably, the nitrogen heterocyclic organic compound is present in the electron transport layer of the organic electroluminescent device.

[0088] Preferably, the nitrogen heterocyclic organic compound is present in the charge-generating layer of the organic electroluminescent device.

[0089] As previously described, a third aspect of the present invention provides an organic electroluminescent device comprising a first electrode; a second electrode disposed opposite to the first electrode; and at least one organic material layer between the first electrode and the second electrode, wherein the organic electroluminescent device comprises at least one of the nitrogen heterocyclic organic compounds described in the first aspect of the present invention.

[0090] In a preferred embodiment, the organic material layer of the organic electroluminescent device of the present invention includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer, and an electron injection layer.

[0091] According to a particularly preferred embodiment, the organic compound is present in the electron transport layer of the organic electroluminescent device.

[0092] Particularly preferably, the organic compound serves as the electron transport material in the electron transport layer of the organic electroluminescent device.

[0093] According to another preferred embodiment, the organic electroluminescent device of the present invention contains at least two organic material layers, each organic material layer forming a light-emitting portion, and at least one charge-generating layer between the two light-emitting portions, wherein the charge-generating layer contains at least one of the organic compounds described in the first aspect of the present invention.

[0094] In a preferred embodiment, the organic electroluminescent device of the present invention comprises a first light-emitting portion, a second light-emitting portion, and a first charge-generating layer located between the first light-emitting portion and the second light-emitting portion, wherein the first charge-generating layer contains at least one of the organic compounds described in the first aspect of the present invention.

[0095] Particularly preferably, the first light-emitting part contains a hole injection layer, a first hole transport layer, a first light-emitting layer, and a first electron transport layer; and the second light-emitting part contains a second hole transport layer, a second light-emitting layer, and a second electron transport layer.

[0096] According to another particularly preferred embodiment, the organic compound of the present invention is present in the charge-generating layer of the organic electroluminescent device.

[0097] Particularly preferred is that the organic compound of the present invention is used as the charge generation layer material in the charge generation layer of the organic electroluminescent device.

[0098] Preferably, the charge-generating layer contains an n-type doped host and a p-type doped host, wherein the n-type doped host contains at least one of the nitrogen-containing heterocyclic organic compounds.

[0099] Preferably, the organic electroluminescent device is a stacked organic electroluminescent device.

[0100] More preferably, the stacked organic light-emitting device contains a CGL layer, and the CGL layer contains an n-type doped layer and a p-type doped layer. The energy level difference between the LUMO level of the n-type doped layer material and the HOMO level of the p-type doped layer material of the present invention is small, which enables the generation of charge carriers at a lower driving voltage.

[0101] Preferably, the n-type doped layer is composed of an n-type dopant and an n-type dopant, the p-type doped layer is composed of a p-type dopant and a p-type dopant, and the organic compound is an n-type dopant between the light-emitting units in the stacked organic electroluminescent device.

[0102] Preferably, the n-type doped host is selected from at least one of the nitrogen heterocyclic organic compounds described in the first aspect of the present invention.

[0103] Preferably, the n-type dopant is selected from alkali metals, alkaline earth metals, transition metals, or main group metals; more preferably, the n-type dopant is selected from one or a mixture of several of lithium, sodium, potassium, calcium, magnesium, gold, silver, ytterbium, and aluminum.

[0104] The p-type dopant described in this invention is an organic semiconductor material with strong electron-withdrawing ability.

[0105] According to another preferred embodiment, the p-type dopant is selected from at least one of HAT-CN, NPD-9, F4TCNQ, and F6TCNNQ, but is not limited thereto:

[0106]

[0107] More preferably, in the CGL layer, the weight ratio of the material of the n-type doped layer to the material of the p-type doped layer is 1:0.1-2; particularly preferably, the weight ratio of the material of the n-type doped layer to the material of the p-type doped layer is 1:0.5-1.

[0108] Preferably, the content ratio of the n-type dopant is 0.2-20 wt%, based on the total amount of the n-type doped host; particularly preferably, the content ratio of the n-type dopant is 1-10 wt%.

[0109] Preferably, the content ratio of the p-type dopant is 0.2-20 wt%, based on the total amount of the p-type doped host; particularly preferably, the content ratio of the p-type dopant is 1-10 wt%.

[0110] Preferably, the organic electroluminescent device of the present invention is coated with one or more layers by means of a sublimation method. In this case, in a vacuum sublimation system, at less than 10 -3 Pa, preferably less than 10 -6 The organic compound provided by the present invention is applied by vapor deposition at an initial pressure of Pa.

[0111] The organic electroluminescent device of the present invention is preferably coated with one or more layers by organic vapor deposition or by means of carrier gas sublimation. In this case, at 10 -6 The material is applied under pressures ranging from Pa to 100 Pa. A particular example of this method is the organic vapor deposition method, in which the compound provided by the present invention is applied directly through a nozzle to form a device structure.

[0112] The organic electroluminescent device of the present invention preferably forms one or more layers of structure by photo-induced thermal imaging or thermal transfer.

[0113] The organic electroluminescent device of the present invention preferably uses the organic compound of the present invention to form a solution, and forms one or more layers by spin coating or by any printing method, such as screen printing, flexographic printing, inkjet printing, offset printing, and more preferably inkjet printing.

[0114] The organic compounds provided by this invention can be structurally modified to allow for cross-linking under heating or ultraviolet exposure, thereby maintaining an intact layer without damage. The organic compounds of this invention can also be applied from solution and subsequently cross-linked in a polymer network or immobilized in the corresponding layers.

[0115] Preferably, the organic electroluminescent device of the present invention is manufactured by applying one or more layers from a solution and by applying one or more layers by a sublimation method.

[0116] Preferably, in preparing the organic electroluminescent device of the present invention, the organic compound of the present invention, or other compounds, are first thoroughly mixed, and then one or more layers are formed by the above-described application method. More preferably, in a vacuum sublimation system, at a temperature of less than 10... -3 Pa, preferably less than 10 -6 At an initial pressure of Pa, compounds are applied by vapor deposition to form one or more layers.

[0117] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available products. Unless otherwise specified, room temperature or ambient temperature as used below refers to 25±1℃.

[0118] This invention provides methods for preparing some of the compounds in the following specific structural formulas. The preparation methods for the remaining compounds can be carried out with reference to the methods provided below. Those skilled in the art should not understand this as a limitation of the invention.

[0119] Synthesis of intermediate A:

[0120]

[0121] Synthesis of intermediate A-1: ​​In a 500 mL three-necked flask, 1-naphthylamine (60 mmol) was dissolved in dichlorobenzene (200 mL). Hydrogen chloride was bubbled into the solution until 1-naphthylamine precipitated as hydrochloride. Triphosgene (20.2 mmol) was then added, and the mixture was rapidly heated to reflux with vigorous stirring. Heating was continued until a clear solution of isocyanate was obtained, and the solution was cooled for 10 min. Then, 4-(cyclohexyl-1-en-1-yl)morpholine (66 mmol) was rapidly added, and the mixture was heated and stirred to reflux, followed by heating for another 15 min. The solution was cooled to room temperature, and the precipitate was filtered and washed successively with water, ethanol, and dichloromethane. After drying, intermediate A-1 was obtained (yield: 55.3%).

[0122] Synthesis of intermediate A-2: In a 200 mL three-necked flask, intermediate A-1 (25 mmol) was added and dissolved in diphenyl ether (60 mL). Palladium on carbon catalyst (0.5 g) was added, and the mixture was heated to reflux for 24 h. Then, n-heptane was added for dilution and the mixture was filtered to obtain intermediate A-2 (yield: 72.5%).

[0123] Synthesis of intermediate A: In a 200 ml three-necked flask, intermediate A-2 (22 mmol) was added and dissolved in 40 ml of trichlorophosphorus oxychloride solvent. After heating for 2 h, a large amount of ice water was introduced into the mixture, and the mixture was alkalized with concentrated ammonia to pH = 8. The precipitate was filtered, washed with water, and dried to obtain intermediate A (yield: 62.7%).

[0124] Mass spectrometry: C16H9ClN2, theoretical value: 264.05, measured value: 264.09. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.50~7.61 (3H, m), 7.63~7.68 (1H, m), 7.70~7.74 (1H, m), 7.76~7.80 (1H, m), 7.92~7.96 (1H, m), 8.42~8.47 (1H, m), 8.78~8.83 (1H, m).

[0125] Synthesis of intermediate B:

[0126]

[0127] Synthesis of intermediate B-1: In a 500 mL double-necked round-bottom flask, a solution of 4-bromo-2-nitroaniline (9.2 mmol) in AcOH (25 mL) was added and heated to 80 °C. N-iodosuccinimide (18.4 mmol) was added in portions to the reaction flask, and the mixture was stirred for 2 h. The reaction mixture was poured into ice water (50 mL) to give an orange solid. The solid was filtered, washed with DCM (50 mL), and dried under vacuum. The aqueous fraction was adjusted to neutral with saturated sodium bicarbonate (50 mL) solution and then extracted with ethyl acetate (100 mL) to give intermediate B-1 (yield: 85%).

[0128] Synthesis of intermediate B-2: In a 350 mL three-necked flask under nitrogen protection, tetrakis(triphenylphosphine)palladium (0.34 mmol) and DME (50 mL) were added, followed by intermediate B-1 (1.53 mmol), 2-formylphenylboronic acid (7.37 mmol), and another 70 mL of DME. Then, an aqueous solution of sodium carbonate (2.0 mmol) (100 mL) was added. The reaction mixture was heated to 130 °C and stirred vigorously for 6 hours. The reaction mixture was then concentrated, and dichloromethane (100 mL) was added to disperse the solid. The mixture was filtered, and the filtrate was collected and washed with brine (3 × 100 mL). The organic phase was separated, dried over sodium sulfate, and concentrated to dryness. The crude product was dissolved in toluene by heating, and excess magnesium chloride was added with stirring. The complex of triphenylphosphine oxide and magnesium chloride was removed by hot filtration to obtain intermediate B-2 (yield: 65.2%).

[0129] Synthesis of intermediate B-3: In a 500 mL three-necked flask, intermediate B-2 (46.4 mmol) and methanol (200 mL) were added. While stirring, Zn (92.8 mmol) and hydrazine formate solution (119.3 mL; prepared by slowly neutralizing an equal volume of hydrazine hydrate (110 mL) with 85 wt% formic acid in an ice-water bath) were added. The reaction mixture was heated to 60 °C and stirred vigorously overnight. The resulting green suspension was cooled to room temperature, filtered through diatomaceous earth, and the filtrate was concentrated. The residue was dissolved in dichloromethane (100 mL) and washed with brine (3 × 60 mL). The organic layer was separated, dried over sodium sulfate, and concentrated to obtain a brown solid crude product. This crude product was purified by silica gel column chromatography to obtain intermediate B-3 (yield: 73.7%).

[0130] Synthesis of intermediate B: In a 500 mL three-necked flask, intermediate B-3 (7.32 mmol), con. H2SO4 (73.2 mmol, 98%), and H2O (1 mL) were added. The reaction mixture was heated to 100 °C, and glycerol (36.6 mmol) was slowly added until the temperature did not exceed 140 °C. The mixture was then stirred for 2 h. The reaction mixture was cooled to room temperature, poured into water, and a solid precipitated. The solid was filtered, the filter cake was washed with water, and dried to obtain intermediate B (yield: 66.5%).

[0131] Mass spectrometry: C16H9BrN2, theoretical value: 307.99, measured value: 307.93. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.36~7.41(1H, m), 7.54~7.59(1H, m), 7.62~7.68(1H, m), 7.76~7.81(1H, m), 7.95~8.00(1H, m), 8.12~8.17(2H, m), 8.47~8.51(1H, m), 8.78~8.82(1H, m).

[0132] Preparation Example 1:

[0133]

[0134] Synthesis of Intermediate 1-1: In a 200 mL three-necked flask under nitrogen protection, intermediate A (20 mmol), 1,4-diboronobenzene (20 mmol), isopropanol, water (mixed in a 3:1 volume ratio) (52.8 mL), anhydrous potassium carbonate (50 mmol), and bis(triphenylphosphine)palladium dichloride (0.2 mmol) were added sequentially. The mixture was stirred and refluxed at 80 °C for 4 h. Deionized water (80 mL) was added to the reaction mixture, and the mixture was stirred for 10 min. The organic phase was washed three times with water, and the two phases were combined and dried over anhydrous magnesium sulfate. The drying agent was filtered off, the organic solvent was evaporated, and the residue was separated by silica gel column chromatography to obtain intermediate 1-1 (yield: 65.8%).

[0135] Synthesis of Compound 1: The synthesis method was the same as that for intermediate 1-1, yielding Compound 1 (yield: 78.3%).

[0136] Mass spectrometry: C34H20N4, theoretical value: 484.17, measured value: 484.21. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.31~7.36 (1H, d), 7.52~7.69 (6H, m), 7.76~7.80 (1H, m), 7.86~7.90 (2H, m), 7.91~7.96 (1H, m), 8.37~8.48 (3H, m), 8.67~8.71 (4H, s), 8.77~8.82 (2H, m).

[0137] Preparation Example 2:

[0138]

[0139] Synthesis of intermediate 10-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 10-1 (yield: 66.4%).

[0140] Synthesis of intermediate 10-2: In a 500 ml three-necked flask, under nitrogen protection, 1,4-dioxane solvent (153 ml), intermediate 10-1 (30 mmol), boron pinacol ester (30 mmol), potassium acetate (75 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.3 mmol) were added sequentially with stirring. The mixture was heated to reflux for 4 h. HPLC analysis confirmed the reaction was complete. After cooling the reaction solution to room temperature, the solution was evaporated under reduced pressure to obtain a crude product. The crude product was dissolved in toluene solvent, heated with stirring, and refluxed. The solution was then decolorized by hot silica gel column chromatography. The filtrate was evaporated under reduced pressure to a small amount of solvent remaining. Ethanol (230 ml) was added and the mixture was stirred. Recrystallized from toluene / ethanol to obtain intermediate 10-2 (yield: 87.9%).

[0141] Synthesis of compound 10: The synthesis method was the same as that for intermediate 1-1, yielding compound 10 (yield: 77.6%).

[0142] Mass spectrometry: C44H26N4, theoretical value: 610.22, measured value: 610.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.21~7.28(2H, m), 7.29~7.44(3H, m), 7.52~7.69(7H, m), 7.75~7.81(1H, m), 7.85~7.97(3H, m), 8.15~8.19(1H, m), 8.36~8.49(3H, m), 8.66~8.72(2H, m), 8.77~8.83(2H, m), 8.92~9.04(2H, m).

[0143] Preparation Example 3:

[0144]

[0145] Synthesis of intermediate 17-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 17-1 (yield: 65.3%).

[0146] Synthesis of compound 17: The synthesis method was the same as that for intermediate 1-1, yielding compound 17 (yield: 76.9%).

[0147] Mass spectrometry: C34H20N4, theoretical value: 484.17, measured value: 484.23. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.22~7.28(2H, m), 7.32~7.43(2H, m), 7.52~7.69(4H, m), 7.75~7.81(1H, m), 7.85~7.91(1H, m), 7.95~8.01(1H, m), 8.11~8.17(1H, m), 8.25~8.29(1H, m), 8.36~8.48(2H, m), 8.55~8.58(1H, m), 8.66~8.72(2H, m), 8.77~8.83(2H, m).

[0148] Preparation Example 4:

[0149]

[0150] Synthesis of intermediate 30-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 30-1 (yield: 67.5%).

[0151] Synthesis of compound 30: The synthesis method was the same as that for intermediate 1-1, yielding compound 30 (yield: 75.7%).

[0152] Mass spectrometry: C42H26N4, theoretical value: 586.22, measured value: 586.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.22~7.28 (2H, m), 7.45~7.69 (8H, m), 7.75~7.98 (11H, m), 8.10~8.16 (1H, m), 8.42~8.48 (1H, m), 8.66~8.72 (2H, m), 8.77~8.83 (1H, m).

[0153] Preparation Example 5:

[0154]

[0155] Synthesis of intermediate 42-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 42-1 (yield: 66.8%).

[0156] Synthesis of compound 42: The synthesis method was the same as that for intermediate 1-1, yielding compound 42 (yield: 75.9%).

[0157] Mass spectrometry: C40H24N4, theoretical value: 560.20, measured value: 560.18. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.29~7.42(4H, m), 7.53~7.70(6H, m), 7.76~7.83(3H, m), 7.93~8.05(5H, m), 8.12~8.16(1H, m), 8.25~8.28(1H, m), 8.54~8.59(2H, m), 8.78~8.82(1H, m), 9.06~9.09(1H, m).

[0158] Preparation Example 6:

[0159]

[0160] Synthesis of intermediate 99-1: The synthesis method is the same as that of intermediate 1-1, yielding intermediate 99-1 (yield: 67.2%).

[0161] Synthesis of compound 99: The synthesis method was the same as that for intermediate 1-1, yielding compound 99 (yield: 76.3%).

[0162] Mass spectrometry: C36H22N2, theoretical value: 482.18, measured value: 482.20. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.31~7.42 (3H, m), 7.53~7.67 (8H, m), 7.76~7.80 (1H, m), 7.86~7.90 (1H, m), 7.92~8.01 (2H, m), 8.04~8.11 (2H, m), 8.15~8.19 (1H, m), 8.42~8.47 (1H, m), 8.77~8.82 (1H, m), 8.93~9.04 (2H, m).

[0163] Preparation Example 7:

[0164]

[0165] Synthesis of compound 110: The synthesis method was the same as that for intermediate 1-1, yielding compound 110 (yield: 75.8%).

[0166] Mass spectrometry: C34H20N2O, theoretical value: 472.16, measured value: 472.13. 1H-NMR (400MHz, CDCl3) (ppm) δ=7.22~7.45(5H, m), 7.52~7.69(5H, m), 7.75~7.81(1H, m), 7.86~8.11(5H, m), 8.42~8.48(1H, m), 8.66~8.72(2H, m), 8.78~8.83(1H, m).

[0167] Device Example 1

[0168] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0169] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5Pa, a first hole injection layer is vacuum-deposited on the aforementioned anolyte film using a multi-source co-evaporation method. The deposition rate of compound HT is adjusted to 0.1 nm / s, and the deposition rate of compound NPD-9 is set to 5%, resulting in a total film thickness of 10 nm. Next, compound HT is deposited as the first hole transport layer at a deposition rate of 0.1 nm / s, with a thickness of 60 nm. A first light-emitting layer, comprising a red light host material and a red light guest material, is then deposited on the hole transport layer using a multi-source co-evaporation method. The deposition rate of the red light host material (RH) was adjusted to 0.1 nm / s, and the deposition rate of the red light guest material (RD) was set to 3%, with a total deposition thickness of 30 nm. ET was vacuum-deposited on top of the emitting layer as the first electron transport layer at a deposition rate of 0.1 nm / s, with a total deposition thickness of 30 nm. An n-type charge generation layer was then vacuum-deposited on top of the electron transport layer using a multi-source co-evaporation method. The deposition rate of compound 1 was adjusted to 0.1 nm / s, and the deposition rate of Yb was set to 1%, with a total deposition thickness of 30 nm. The film thickness is 10 nm. A p-type charge-generating layer is then vacuum-deposited on top of this layer using a multi-source co-evaporation method. The deposition rate of compound HT is adjusted to 0.1 nm / s, and the deposition rate of compound NPD-9 is set to 5%, resulting in a total film thickness of 10 nm. Then, compound HT is deposited as a second hole transport layer at a deposition rate of 0.1 nm / s, with a thickness of 60 nm. A second light-emitting layer, comprising a red light host material and a red light guest material, is then deposited on the hole transport layer using a multi-source co-evaporation method. The method involves adjusting the evaporation rate of the red light host material (RH) to 0.1 nm / s, setting the evaporation rate of the red light guest material (RD) to 3%, and the total evaporation film thickness to 30 nm. ET is then vacuum-deposited on top of the light-emitting layer as a second electron transport layer at a rate of 0.1 nm / s, with the Liq evaporation rate set to 50%, resulting in a total evaporation film thickness of 30 nm. A 2 nm thick Liq layer is then vacuum-deposited on the electron transport layer as an electron injection layer, and a 100 nm thick Al layer is deposited as the cathode of the device.

[0170] The molecular structure of the material is as follows:

[0171]

[0172] Device Examples 2 to 7

[0173] Organic light-emitting devices of Device Examples 2 to 7 were prepared using a method similar to that of Device Example 1, except that compound 1 in Device Example 1 was replaced with the same mass of the corresponding compound in Table 1.

[0174] Device Comparison Example 1 to Device Comparison Example 2

[0175] Organic electroluminescent devices of Device Comparative Examples 1 to 2 were prepared using a method similar to that of Device Example 1, except that compound 1 in Device Example 1 was replaced with the same mass of Ref1 and Ref2.

[0176]

[0177] Test case

[0178] At a current density of 10 mA / cm 2 The driving voltage and current efficiency of the organic electroluminescent devices prepared in Device Examples 1 to 10 and Comparative Examples 1 to 2 were measured at a current density of 50 mA / cm². 2 The lifespan of the organic electroluminescent devices T95 prepared in Device Examples 1 to 10 and Device Comparative Examples 1 to 2 is shown in Table 1.

[0179] Table 1

[0180] serial number n-type main body Drive voltage (V) Current efficiency (cd / A) T95(h)@J50 Light color Example 1 Compound 1 6.53 28.37 213 Red light Example 2 Compound 10 6.70 28.15 198 Red light Example 3 Compound 17 6.58 28.32 215 Red light Example 4 Compound 30 6.71 28.04 194 Red light Example 5 Compound 42 6.55 28.20 196 Red light Example 6 Compound 99 6.62 27.96 186 Red light Example 7 Compound 110 6.57 27.99 189 Red light Comparative Example 1 Ref1 6.90 25.53 129 Red light Comparative Example 2 Ref2 6.88 25.76 157 Red light

[0181] The results above show that when the organic compounds of the present invention are used in organic electroluminescent devices, they exhibit significantly lower driving voltage and higher luminous efficiency compared to the comparative examples.

[0182] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A nitrogen-containing heterocyclic organic compound, characterized in that, This compound has the structure shown in ALB; A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-30 Aromatic groups; combination B contains C 1-20 Alkyl, C 1-20 Alkoxy, phenyl, diphenyl, triphenyl, naphthyl, anthraceneyl, and phenanthrene; L is composed of C, which may or may not contain type A heteroatoms. 3-30 An aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave; The type A heteroatoms include at least one of N, O, and S; 2. The nitrogen-containing heterocyclic organic compound according to claim 1, characterized in that, In the structure shown in ALB A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-12 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-24 Aromatic groups; combination B contains C 1-12 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; L is composed of C, which may or may not contain type A heteroatoms. 3-24 An aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave; The type A heteroatoms include at least one of N, O, and S; Preferably, in the structure shown in ALB, A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-8 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is an unsubstituted or substituted group of combination B, containing or not containing heteroatoms of type A. 6-20 Aromatic groups; combination B contains C 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; the class A heteroatoms include at least one of N, O, and S; L is one or two of the following linkage groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyridine, dibenzothiophene, dibenzofuran, fluorene, or carbazole: Preferably, B is any one of the following: a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; a group of formula (II-2) that is unsubstituted or substituted by at least one group in combination B; or a group of formula (II-3) that is unsubstituted or substituted by at least one group in combination B; wherein combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; X1, X2, and X3 are each independently N or CH; In formula (II-3), X4 is -N(R1)-, O, S or -C(R1)(R2)-; R1 and R2 are each independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

3. The nitrogen-containing heterocyclic organic compound according to claim 1 or 2, characterized in that, In the structure shown in ALB A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; In equation (II-1), X1 and X2 are each independently N or CH; L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine; Preferably, X1 and X2 in formula (II-1) are both N; More preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

4. The nitrogen-containing heterocyclic organic compound according to claim 1 or 2, characterized in that, In the structure shown in ALB A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is a group of formula (II-1) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; In equation (II-1), both X1 and X2 are CH; L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine; Preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of the following; 5. The nitrogen-containing heterocyclic organic compound according to claim 1 or 2, characterized in that, In the structure shown in ALB A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is a group of formula (II-2) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; In equation (II-2), X1, X2, and X3 are each independently N or CH; L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine; Preferably, in formula (II-2), X2 is N; one of X1 and X3 is H, and the other is CH; More preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

6. The nitrogen-containing heterocyclic organic compound according to claim 5, characterized in that, In the structure shown in ALB, X1, X2 and X3 are all CH in equation (II-2); Preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

7. The nitrogen-containing heterocyclic organic compound according to claim 1 or 2, characterized in that, In the structure shown in ALB A is a group of formula (I-1) that is unsubstituted or substituted by at least one group in combination A; said combination A contains C. 1-6 Alkyl, phenyl, diphenyl, naphthyl, anthraceneyl, phenanthrene; B is a group of formula (II-3) that is unsubstituted or substituted by at least one group in combination B; said combination B contains C. 1-8 Alkyl, phenyl, diphenyl, p-terphenyl, naphthyl, anthraceneyl, and phenanthrene; In formula (II-3), X4 is -N(R1)-, O, S or -C(R1)(R2)-; R1 and R2 are each independently phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl; L is one or two of the linking groups formed by removing any two H atoms from benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyridine; Preferably, the nitrogen-containing heterocyclic organic compound with the structure shown in ALB is selected from any one of the following:

8. The nitrogen-containing heterocyclic organic compound according to claim 1 or 2, characterized in that, The nitrogen-containing heterocyclic organic compounds with the structure shown in ALB are selected from any of the following:

9. The use of the nitrogen heterocyclic organic compound according to any one of claims 1-8 in organic electroluminescent devices and / or perovskite solar cells.

10. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode; a second electrode disposed opposite to the first electrode; and at least one organic material layer between the first electrode and the second electrode. The organic electroluminescent device contains at least one of the nitrogen heterocyclic organic compounds according to any one of claims 1-8.

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