Nitrogen-containing heterocyclic compound and organic light-emitting element comprising same

Abstract

The present invention relates to the technical field of photoelectric materials, and provides a nitrogen-containing heterocyclic compound and an organic light-emitting element comprising same. The nitrogen-containing heterocyclic compound has a structure represented by formula (1), wherein X is selected from O or S, R1-R16 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, and R1-R16 are each independently present or two adjacent ones are linked to form a ring. The organic light-emitting element prepared by using the compound can have reduced driving voltage and durable service life, and the organic light-emitting element has better performance.

Description

Nitrogen-containing heterocyclic compound and organic electroluminescent device containing the same

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of the following Chinese patent applications filed with the State Intellectual Property Office of China, the entire contents of which are incorporated herein by reference:

[0003] A Chinese patent application with application number CN202310894693.2 and application name “Nitrogen-containing heterocyclic compounds and organic electroluminescent elements containing the same” submitted on July 20, 2023. Technical Field

[0004] The present invention belongs to the technical field of optoelectronic materials, and in particular relates to a nitrogen-containing heterocyclic compound and an organic electroluminescent element containing the same. Background Art

[0005] Organic light emitting devices (OLEDs) have the advantages of surface light source, cold light, energy saving, fast response, flexibility, ultra-lightness and low cost, and their mass production technology is becoming increasingly mature. OLEDs are injection-type light-emitting devices, and their basic structure is a sandwich structure in which an organic light-emitting thin film layer is sandwiched between two electrodes with at least one transparent electrode. On this basis, people have developed more complex device structures, especially the introduction of more organic subdivided functional layers; these "functional layers" play a very important role in improving the device's luminous efficiency and device life. The main organic functional layers in organic electroluminescent devices include: hole transport layer (HTL), electron transport layer (ETL), light-emitting layer, hole injection layer, electron injection layer, hole blocking layer, etc.

[0006] Since the electron mobility of the electron transport layer material is much lower than the hole mobility of the hole transport layer material, an imbalance of holes and electrons entering the light-emitting layer occurs, affecting the luminous efficiency and life of the component.

[0007] Tandem devices typically incorporate a charge generation layer between the light-emitting units to ensure efficient charge distribution across the stacked light-emitting layers while also improving current efficiency within each individual light-emitting layer. Typically, the charge generation layer comprises a PN junction, with an N-type charge generation layer and a P-type charge generation layer stacked in sequence. The injection barrier for electrons from the N-type charge generation layer to the adjacent electron transport layer is relatively high. Consequently, electrons accumulate at the interface between the N-type charge generation layer and the adjacent electron transport layer, which can easily degrade this interface and shorten the device's lifespan.

[0008] Therefore, there is an urgent need to develop new materials for the preparation of charge generation layers to improve the performance of components.

[0009] Summary of the Invention

[0010] The object of the present invention is to provide a nitrogen-containing heterocyclic compound, wherein an organic electroluminescent element prepared using the compound can achieve a reduced driving voltage and a durable service life.

[0011] The technical solution adopted by the present invention to solve its technical problem is:

[0012] A nitrogen-containing heterocyclic compound having a structure shown in formula (1)

[0013] in

[0014] X is selected from O or S,

[0015] R 1 -R 16 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0016] R 1 -R 16 Each exists independently, or two adjacent ones are connected to form a ring.

[0017] Preferably, the compound is selected from any one of formula (1-1), (1-2), (1-3), and (1-4).

[0018] Preferably, the compound is selected from any one of formulas (1-5), (1-6), (1-7), and (1-8),

[0019] As a preference, R 1 -R 16 Each is independently selected from one of hydrogen, deuterium, halogen, phenyl, biphenyl, naphthyl, pyridyl, bipyridyl or a combination thereof. A combination of substituents refers to a combination of hydrogen, deuterium, halogen and phenyl, biphenyl, naphthyl, pyridyl, bipyridyl, wherein the combination refers to a group connected by a single bond, such as R 1 Phenyl or deuterated phenyl can be selected.

[0020] Preferably, R in the compounds represented by formula (1), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8) 4 , R 5 Linked into a ring, and / or R 12 , R13 are connected to form ring C. Preferably, the ring C is a six-membered ring; preferably, the ring C is an unsaturated six-membered ring. More preferably, the ring C is a benzene ring.

[0021] Preferably, R in the compounds represented by formula (1), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8) 4 and R 5 The phenyl groups are connected to form a benzene ring, and the remaining groups are independently selected from one of hydrogen, deuterium, halogen, phenyl, biphenyl, naphthyl, pyridyl, bipyridyl or a combination of multiple thereof.

[0022] Preferably, R in the compounds represented by formula (1), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8) 12 and R 13 The phenyl groups are connected to form a benzene ring, and the remaining groups are independently selected from one of hydrogen, deuterium, halogen, phenyl, biphenyl, naphthyl, pyridyl, bipyridyl or a combination of multiple thereof.

[0023] Preferably, in formula (1-5), X is selected from O or S, R 8 It is selected from pyridyl or deuterated pyridyl, and the number of deuterations is 1-4.

[0024] Preferably, in formula (1-6), X is selected from O or S, R 16 It is selected from pyridyl or deuterated pyridyl, and the number of deuterated pyridyl is 1-4.

[0025] Preferably, in formula (1-6), X is selected from O or S, R 16 is selected from pyridyl or deuterated pyridyl, wherein the number of deuterated groups is 1-4; R 4 and R 5 Connected to form a benzene ring; R 1 is selected from hydrogen, phenyl or deuterated phenyl, wherein the number of deuterations is 1-5; and the remaining groups are selected from hydrogen or deuterium.

[0026] Preferably, in formula (1-7), X is selected from O or S, R 8 It is selected from pyridyl or deuterated pyridyl, and the number of deuterations is 1-4.

[0027] Preferably, in formula (1-7), X is selected from O or S, R 8 is selected from pyridyl or deuterated pyridyl, wherein the number of deuterated groups is 1-4; R 12 and R 13 Connected to form a benzene ring; R 9 is selected from hydrogen, phenyl or deuterated phenyl, wherein the number of deuterations is 1-5; and the remaining groups are selected from hydrogen or deuterium.

[0028] Preferably, in formula (1-8), X is selected from O or S, R 4 and R 5 Connected to form a benzene ring, R 12 and R 13 Connected to form a benzene ring, R 1 is selected from hydrogen, phenyl or deuterated phenyl, R 9 is selected from hydrogen, phenyl or deuterated phenyl, and the remaining groups are selected from hydrogen or deuterium.

[0029] Preferably, the compound is selected from any one of the following compounds No. 1-36

[0030] The invention discloses an application of the nitrogen-containing heterocyclic compound as an organic electroluminescent element material.

[0031] An organic electroluminescent element comprises an anode, a cathode, and an organic layer located between the anode and the cathode, wherein the organic layer comprises the nitrogen-containing heterocyclic compound of the present invention.

[0032] Preferably, the organic layer comprises an electron transport layer and a light-emitting layer, and the electron transport layer comprises the nitrogen-containing heterocyclic compound described in the present invention.

[0033] Preferably, the organic layer comprises two or more light-emitting units, a charge generation layer is contained between the light-emitting units, the light-emitting units comprise an electron transport layer, and the at least one charge generation layer and / or at least one electron transport layer comprises the nitrogen-containing heterocyclic compound described in the present invention.

[0034] Preferably, the organic layer comprises two or more light-emitting units, a charge generation layer is included between the light-emitting units, the light-emitting unit comprises an electron transport layer, the charge generation layer comprises an N-type charge generation layer and a P-type charge generation layer, and at least one of the N-type charge generation layer and the electron transport layer comprises the nitrogen-containing heterocyclic compound described in the present invention.

[0035] The electron transport layer comprises the electron transport layer of each light-emitting unit, and at least one of the N-type charge generation layer and the electron transport layer comprises the nitrogen-containing heterocyclic compound of the present invention, which means that one N-type charge generation layer comprises the nitrogen-containing heterocyclic compound of the present invention; or multiple N-type charge generation layers comprise the nitrogen-containing heterocyclic compound of the present invention; or one electron transport layer in a light-emitting unit comprises the nitrogen-containing heterocyclic compound of the present invention; or one N-type charge generation layer and one electron transport layer in a light-emitting unit comprise the nitrogen-containing heterocyclic compound of the present invention; or one N-type charge generation layer and each electron transport layer in multiple light-emitting units comprise the nitrogen-containing heterocyclic compound of the present invention; or multiple N-type charge generation layers and each electron transport layer in multiple light-emitting units comprise the nitrogen-containing heterocyclic compound of the present invention, etc. When two or more layers comprise the nitrogen-containing heterocyclic compound of the present invention, the nitrogen-containing heterocyclic compounds may be the same or different.

[0036] An electronic device comprises the organic electroluminescent element of the present invention.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. The organic electroluminescent compound of the present invention has a benzofuran-substituted phenyl structure, and the phenyl group has an N-containing heteroaryl group at the para position, which can effectively improve the electron injection and transmission capabilities; the organic electroluminescent element prepared using the compound can achieve a reduced driving voltage and a long service life.

[0039] 2. Organic electroluminescent elements have a better lifespan. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is a schematic structural diagram of the organic electroluminescent element described in Application Example 1, wherein the first electrode layer 1, the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4, the electron transport layer 5, the N-type charge generation layer 6, the P-type charge generation layer 7, the hole transport layer 8, the light-emitting layer 9, the electron transport layer 10, the electron injection layer 11 and the second electrode layer 12, wherein 100 is the first light-emitting unit and 200 is the second light-emitting unit. DETAILED DESCRIPTION

[0041] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present application belongs.

[0042] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "include" and / or "including" are used in this specification, they indicate that they are not limited to the contents disclosed in this specification.

[0043] In order to more fully describe the present invention to those skilled in the art, embodiments of the present invention are provided. The scope of the present invention is not limited to the following embodiments. These embodiments can make the present invention more thorough and complete, and fully convey the concept of the present invention to those skilled in the art.

[0044] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0045] As used herein, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0046] As used herein, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0047] As used in the present invention, the term "C6-C30 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a monocyclic ring or a combination of two or more rings and having 6 to 30 carbon atoms. Further, such an aryl group may have a form in which two or more rings are simply lateral to each other or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0048] As used herein, the term "C3-C30 heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic heterocyclic aromatic hydrocarbon having 3 to 30 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbon atoms, in the ring is substituted with a heteroatom such as N, O, S, P, B, or Si. In addition, such a heteroaryl group may have a form in which two or more rings are simply attached to each other or fused to each other or to an aromatic group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl, and the like, but the present invention is not limited thereto.

[0049] As used herein, the term "C2-C10 alkenyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and 2 to 10 carbon atoms. Examples include, but are not limited to, ethenyl, propenyl, allyl, isopropenyl, 2-butenyl, and the like.

[0050] As used in the present invention, the "carbon number of AA-BB" in the expression "Z group having AA-BB carbon atoms" or "Z group having C(AA-BB)" means the carbon number of the Z group when it is unsubstituted, and does not include the carbon number of the substituent when it is substituted. For example, a C6-C30 aryl group means that when it is unsubstituted, the number of carbon atoms in the aryl group is any integer between 6 and 30, that is, the number of carbon atoms when it is unsubstituted can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20...30.

[0051] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where the substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, unless otherwise specified in this specification: "Unsubstituted" means that hydrogen atoms remain, and in this case, hydrogen atoms include protium, deuterium, and tritium.

[0052] When two or more substituents are present, the two or more substituents may be the same or different.

[0053] Unsaturated six-membered ring refers to R 4 With R 5 、R12 With R 13 pass Link, as shown in the figure Represents the connection location.

[0054] As used in the present invention, hydrogen atoms include protium, deuterium, and tritium. The compounds of the present invention may contain deuterium atoms from natural sources, or deuterium atoms may be introduced by deuterating a portion or all of the raw material compounds. If deuterium atoms are introduced from the raw materials, the deuteration rate may be 100%, or less than 100%, or less than 95%, or less than 90%, or less than 80%. The deuteration rate may also be greater than 1%, or greater than 5%, or greater than 10%. If the deuteration rate is not 100%, it represents a mixture of deuterated and undeuterated compounds, or a mixture of a fully deuterated and incompletely deuterated compound, or a mixture of a fully deuterated and undeuterated compound and an incompletely deuterated compound.

[0055] As used in the present invention, terms such as first, second, A, and B are used. The above terms are only used to distinguish components and do not limit the nature or order of the components to which the terms correspond.

[0056] organic electroluminescent elements

[0057] The structure of the organic electroluminescent element of the present invention is a disclosed structure, comprising an anode, a cathode and an organic layer located between the anode and the cathode. The organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0058] The organic layer further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0059] The light-emitting element of the present invention may emit fluorescence, phosphorescence, or a combination thereof. The light-emitting element may emit light alone or in the form of a series connection of multiple light-emitting units.

[0060] As simple light emitting elements, the following may be mentioned, but are not limited to these:

[0061] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0062] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0063] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0064] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0065] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0066] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0067] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0068] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0069] (9) hole transport layer / electron blocking layer / phosphorescent light emitting layer / hole blocking layer / electron transport layer;

[0070] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0071] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0072] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0073] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0074] The phosphorescent / fluorescent light-emitting layers may each emit light of a different color.

[0075] As a tandem organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also generally be called a charge generation layer, an electron extraction layer, a connecting layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer in order to prevent the excitons generated by the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to adjust the balance of carriers.

[0076] When the organic light emitting element includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

[0077] The organic electroluminescent element of the present specification can be manufactured by using materials and methods known in the art, except that one or more of the organic material layers is prepared by using a compound comprising Formula I.

[0078] Anode materials may include materials with relatively large work functions, such as transparent conductive oxides, metals, and conductive polymers. Specific examples of anode materials include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

[0079] Cathode materials typically use materials with a low work function to facilitate electron injection into the organic material layer. Examples of cathode materials include metals, metal oxides, and conductive polymers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; and multilayered structures such as LiF / Al or LiO2 / Al.

[0080] The hole injection layer (HIL) injects holes from the electrodes and has the ability to transport them. To reduce the energy level difference between the electrodes, the HIL is primarily based on aromatic amine compounds. Other materials include copper phthalocyanine for metal complexes and HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene) with a phenylene structure for the lowest unoccupied molecular orbital (LUMO) energy level. When used as a luminescent host and dopant, F4-TCNQ (2,2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone) derivatives with the lowest unoccupied molecular orbital (LUMO) energy level can be doped into aromatic amine compounds.

[0081] The hole transport material is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The hole transport material can appropriately receive holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer. Aromatic amine derivatives, triphenyldiamine derivatives, etc. can be used, and low molecular weight or high molecular weight materials can also be used.

[0082] A luminescent material is a material that receives holes and electrons from the hole transport layer and electron transport layer, respectively, and combines the holes and electrons to emit light in the visible light region. The luminescent layer material includes a host material and a dopant material. Red, green, or blue luminescent materials can be used, and two or more luminescent materials can be mixed as needed. Both fluorescent and phosphorescent materials can be used as luminescent materials. The luminescent material can be a single-component material or a multi-component material.

[0083] The electron transport material is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material can receive electrons from the cathode and transfer the electrons to the light-emitting layer. It is a material with high electron mobility. Triazine derivatives, oxadiazole derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, 8-hydroxyquinoline and its derivatives, etc. can be used. Metal complexes, and polymer materials and small molecule materials can also be used.

[0084] The electron injection layer is a layer that injects electrons from the electrode. This application uses LiF, however, this application is not limited thereto.

[0085] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0086] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0087] The organic light-emitting element of the present specification may be a top-emitting element, a bottom-emitting element, or a dual-emission element depending on the materials used.

[0088] The charge generation layer (CGL) is the intermediate layer between the anode and cathode in a tandem-structured device. It generates holes and electrons through charge separation. The CGL typically consists of a P-type layer on the cathode side and an N-type layer on the anode side, enabling efficient charge separation and carrier transport.

[0089] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and known synthesis methods.

[0090] The following are specific examples of the synthesis of the compounds of the present invention, but are not limited to the compounds exemplified below. Synthesis Example 1: Synthesis of Compound 15

[0091] Step 1: To a 500 ml reaction flask, add starting material 1 (20 g, 71.04 mmol), potassium acetate (20.92 g, 213.12 mmol), bis(triphenylphosphine)palladium dichloride (0.99 g, 1.42 mmol), and diboronic acid pinacol ester (23.36 g, 92.35 mmol) in sequence, using 200 ml of anhydrous dioxane as the solvent. After nitrogen substitution, heat to 100°C and stir for 2 hours. Monitor the reaction by TLC. Purify by column chromatography (eluting with pure n-hexane) to obtain intermediate 15-1 (21 g, 63.9 mmol).

[0092] LC-MS: [M+H] + =329.60

[0093] Step 2: To a 500 mL reaction flask were added starting material 2 (10 g, 32.01 mmol), intermediate 15-1 (10.52 g, 32.01 mmol), sodium carbonate (5.1 g, 48.015 mmol), tetrakis(triphenylphosphine)palladium (0.74 g, 0.64 mmol), 100 mL of tetrahydrofuran, and 30 mL of water as solvent. After nitrogen substitution, the mixture was stirred at 80°C for 12 hours, then terminated. The reaction was cooled to room temperature, and the aqueous phase was separated and discarded. Anhydrous sodium sulfate was added to the organic layer, the mixture was stirred, filtered through a pad of silica gel, concentrated under reduced pressure, and slurried with 100 mL of ethanol to afford intermediate 15-2 (11 g, 25.35 mmol).

[0094] LC-MS: [M+H] + =434.90

[0095] Step 3: To a 500ml reaction flask, add Intermediate 15-2 (11g, 25.35mmol), potassium acetate (7.46g, 76.06mmol), DPPF palladium dichloride (0.37g, 0.507mmol), and bis(pinacolato) borate (7.73g, 30.42mmol) in sequence, using 150ml of anhydrous dioxane as the solvent. After nitrogen substitution, heat to 100°C and stir for 2 hours. After completion of the reaction, filter, and concentrate the filtrate to dryness. Add 100ml of n-hexane and slurry to obtain Intermediate 15-3 (11.31g, 21.53mmol).

[0096] LC-MS: [M+H] + =526.42

[0097] Step 4: To a 500ml reaction flask were added starting material 3 (7.58g, 22.6mmol), intermediate 15-3 (11.53g, 21.53mmol), sodium carbonate (3.42g, 32.29mmol), and tetrakis(triphenylphosphine)palladium (0.52g, 0.451mmol), followed by 100ml of tetrahydrofuran and 30ml of water as solvent. After nitrogen substitution, the mixture was stirred at 80°C for 6 hours, then the reaction was terminated, cooled to room temperature, and the layers were separated. The organic layer was concentrated to dryness under reduced pressure and recrystallized from toluene to yield the final product, compound 15 (11.96g, 18.29mmol).

[0098] LC-MS: [M+H] + =654.75

[0099] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.91(dd,2H),8.81(s,2H),8.71(dt,2H),8.62(ddd,2H),8.46–8.38(m,3H),8.30(d,1H),8.13 (d,1H),7.91–7.77(m,4H),7.74–7.65(m,3H),7.58–7.50(m,2H),7.43(ddt,2H),7.31(ddd,2H),7.10(td,1H).

[0100] The following application examples further illustrate the application of the nitrogen-containing heterocyclic compound of the present invention and the organic electroluminescent device containing the same.

[0101] Application Example 1

[0102] This embodiment provides an organic electroluminescent element, as shown in Figure 1, including a stacked first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, an N-type charge generation layer 6, a P-type charge generation layer 7, a hole transport layer 8, a light-emitting layer 9, an electron transport layer 10, an electron injection layer 11 and a second electrode layer 12, wherein 100 is a first light-emitting unit and 200 is a second light-emitting unit.

[0103] The specific component structure is:

[0104] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / TmPyPB(10nm) / Bphen:Li(2%)( 10nm) / NPD:F4-TCNQ(10%)(20nm) / NPD(20nm) / BH:BD(3%)(20nm) / Alq3(10nm) / LiF(0.5nm) / Al(200nm).

[0105] Component preparation process:

[0106] The bottom-emitting glass substrate used in this example was purchased from Guangdong Truly Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 1. First, the bottom-emitting glass substrate was cleaned using an ITO cleaner, deionized water, and isopropyl alcohol, in that order. The bottom-emitting glass substrate was then baked at 180 degrees Celsius for 30 minutes to dry it.

[0107] Then put the bottom luminescent glass substrate into the evaporation chamber and -8 Each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of torr. Among them, F4-TCNQ (mass content 10%) is doped into NPD to form a thickness of 10nm as a hole injection layer. NPD is formed to a thickness of 120nm as a hole transport layer, and a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% is doped on the anthracene host ADN (9,10-di(naphtha-2-yl-)anthracene) to form a blue light-emitting layer with a thickness of 20nm. TmPyPB is formed to a thickness of 10nm as the first electron transport layer, and BPhen (4,7-Diphenyl-1,10-phenanthroline) is doped with 2% Li by mass to form an N-type charge generation layer 6 with a thickness of 10nm. F4-TCNQ with a mass content of 10% is doped on NPD. A P-type charge generation layer with a thickness of 20 nm is formed, NPD is formed with a thickness of 20 nm as a hole transport layer, the anthracene main body ADN (9,10-di(naphtha-2-yl-)anthracene) is doped with a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% to form a blue light-emitting layer with a thickness of 20 nm, Alq3 (Tris-(8-hydroxyquinolinato)aluminum) is formed with a thickness of 10 nm as a second electron transport layer, LiF is formed with a thickness of 0.5 nm as an electron injection layer, and Al is formed with a thickness of 200 nm as a cathode.

[0108] Finally, the element was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the element, which was recorded as organic electroluminescent element 1.

[0109] Contrast structure

[0110] Bphen(4,7-Diphenyl-1,10-phenanthroline)

[0111] Examples and Comparative Examples

[0112] Charge Generation Layer: The compound prepared in Example 1 of the present invention was used instead of Bphen material to prepare the N-type charge generation layer 6, and the organic electroluminescent element 2 was prepared using the same method.

[0113] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0114] The driving voltage is at a current density of 15 mA / cm 2 The following test results are shown in Table 1.

[0115] Table 1

[0116] The organic electroluminescent element 2 prepared using the compound of the present invention has a lower driving voltage and a longer service life than the organic electronic element 1 (using the BPHEN material). Therefore, the compound of the present invention is suitable for preparing high-performance organic electroluminescent elements.

[0117] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from the other embodiments. Reference can be made to the descriptions of the identical or similar parts between the various embodiments. For the devices disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the descriptions are relatively simple, and the relevant parts can be referred to the descriptions of the methods.

[0118] The above is a detailed introduction to a nitrogen-containing heterocyclic compound and an organic electroluminescent element containing the same provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, the present invention can also be improved and modified in several ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A nitrogen-containing heterocyclic compound, characterized in that The compound has the structure shown in formula (1): in X is selected from O or S, R 1 -R 16 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R 1 -R 16 They exist independently, or two adjacent ones are connected to form a ring.

2. The nitrogen-containing heterocyclic compound according to claim 1, characterized in that The compound is selected from any one of formula (1-1), (1-2), (1-3) and (1-4), 3. The nitrogen-containing heterocyclic compound according to claim 1, characterized in that: R 1 -R 16 Each independently selected from hydrogen, deuterium, halogen, phenyl, biphenyl, naphthyl, pyridyl, bipyridyl A combination of one or more of .

4. The nitrogen-containing heterocyclic compound according to claim 2, characterized in that: In the compounds represented by formula (1), (1-1), (1-2), (1-3), and (1-4), R 4 , R 5 Linked into a ring, and / or R 12 , R 13 Connect into ring C.

5. The nitrogen-containing heterocyclic compound according to claim 1, characterized in that The compound is selected from any of the following compounds No. 1-36 6. Use of the nitrogen-containing heterocyclic compound according to any one of claims 1 to 5 as an organic electroluminescent element material. 7 . An organic electroluminescent element, comprising an anode, a cathode, and an organic layer located between the anode and the cathode, wherein the organic layer comprises the nitrogen-containing heterocyclic compound according to claim 1 . 8 . The organic electroluminescent element according to claim 7 , wherein the organic layer comprises an electron transport layer and a light emitting layer, and the electron transport layer comprises the nitrogen-containing heterocyclic compound according to claim 1 .

9. The organic electroluminescent element according to claim 7, wherein the organic layer comprises two or more light-emitting units, a charge generation layer is comprised between the light-emitting units, and the light-emitting units comprise an electron transport layer, wherein: The at least one charge generation layer and / or the at least one electron transport layer comprises the nitrogen-containing heterocyclic compound according to any one of claims 1 to 5.

10. An electronic device comprising the organic electroluminescent element according to any one of claims 7 to 9.

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