Nitrogen heterocyclic derivative, organic electroluminescent element and electronic equipment

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to a nitrogen heterocyclic derivative, an organic electroluminescence element and electronic equipment. The invention relates to a nitrogen heterocyclic derivative, which has a structure shown in a formula (1), # imgabs0 #, and Ar1 is selected from substituted or unsubstituted C6-C30 aryl. According to the nitrogen heterocyclic derivative, the current efficiency of an OLED device can be improved, the driving voltage of the device is reduced, and the service life of the device is effectively prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and in particular relates to a nitrogen heterocyclic derivative, an organic electroluminescent element and an electronic device. Background Art

[0002] Organic light emitting diode is a self-luminous display element based on organic electroluminescent materials. Unlike existing liquid crystal display elements, it does not require a backlight source and is thin, making it a technology suitable for flexible element devices (flexible light-emitting display devices). Organic semiconductor materials are diverse in synthesis, have relatively low manufacturing costs, and have excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential for application in optoelectronic devices (such as flat panel displays and lighting).

[0003] From the perspective of device structure, OLED device structures are classified into various types according to the structure of the light-emitting layer, such as single light-emitting layer, multi-doped light-emitting layer, multiple light-emitting layer, stacked structure, etc. In stacked devices, the performance of the device is improved by adding a charge generation layer to the light-emitting unit. However, there is a lack of high-performance materials that can be used for the charge generation layer of stacked devices, and the choice space is limited when designing devices. In addition, the number of device layers is large, and different compounds are often used for each layer, which increases the complexity of device manufacturing. Summary of the invention

[0004] The object of the present invention is to provide a nitrogen heterocyclic derivative, which can be used for the preparation of an organic electroluminescent element, thereby prolonging the service life of the organic electroluminescent element.

[0005] The technical solution adopted by the present invention to solve its technical problem is:

[0006] A nitrogen heterocyclic derivative, the compound having a structure shown in formula (1),

[0007] in,

[0008] Ar1 is selected from substituted or unsubstituted C6-C30 aryl;

[0009] R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl,

[0010] R1, R2, R3, and R4 are not hydrogen at the same time;

[0011] The substituent in the "substituted or unsubstituted" is selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group,

[0012] The heteroatom in the heterocyclic group and heteroaryl group is selected from N, O, S, Si, and P.

[0013] Preferably, R1, R2, R3, and R4 are each independently selected from hydrogen, substituted or unsubstituted C6-C60 aryl, and R1, R2, R3, and R4 are not hydrogen at the same time; further preferably, R1, R2, R3, and R4 are each independently selected from hydrogen, substituted or unsubstituted phenyl.

[0014] Preferably, Ar1 is selected from substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, and substituted or unsubstituted perylenyl.

[0015] Preferably, Ar1 is selected from one of the following structures:

[0016]

[0017] Wherein, * indicates connection with N in formula (1),

[0018] R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Each is independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl.

[0019] Preferably, R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted iso ...tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isocyanate ... quinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl, and

[0020] At least one of R1, R2, R3 and R4 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indene substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

[0021] Preferably, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl , substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted substituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted substituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

[0022] Preferably, the nitrogen heterocyclic derivative is selected from any one of the compounds shown in numbers 1 to 65 below:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] The present invention also provides a preparation, which comprises at least one of the above-mentioned nitrogen heterocyclic derivatives and at least one solvent.

[0031] The present invention also provides an organic electroluminescent element, which comprises:

[0032] a first electrode;

[0033] a second electrode disposed to face the first electrode; and

[0034] one or more organic material layers disposed between the first electrode and the second electrode and including a light-emitting layer,

[0035] One or more layers of the organic material layer contain the nitrogen heterocyclic derivative described in the present invention.

[0036] Preferably, the organic material layer comprises an electron transport layer and a hole blocking layer, and at least one of the electron transport layer and the hole blocking layer comprises the nitrogen heterocyclic derivative described in the present invention.

[0037] Preferably, the organic material layer comprises at least two light-emitting units, an N-type charge generation layer is disposed between the two light-emitting units, and the N-type charge generation layer comprises the nitrogen heterocyclic derivative described in the present invention.

[0038] The present invention also provides an electronic device, wherein the electronic device is provided with the organic electroluminescent element.

[0039] In general, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following

[0040] Beneficial effects:

[0041] 1. The nitrogen heterocyclic derivatives of the present invention can improve the current efficiency of OLED devices, reduce the driving voltage of the devices and effectively extend the service life of the devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1, wherein a first electrode layer 12, a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, an electron transport layer 8, an N-type charge generation layer 7, a P-type charge generation layer 6, a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, an electron injection layer 2, a second electrode layer 1, a first light-emitting unit 200, and a second light-emitting unit 100. DETAILED DESCRIPTION

[0043] The technical solution of the present invention is further described in detail below through specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any form of modification and / or change made to the present invention will fall within the protection scope of the present invention.

[0044] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0045] The reagents used in the following examples, unless otherwise specified, can be purchased from conventional biochemical reagent stores.

[0046] Explanation of terms

[0047] As used in the present invention, the term "halogen group" may include fluorine, chlorine, bromine or iodine.

[0048] As used in the present invention, 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.

[0049] As used in the present invention, 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 include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0050] As used in the present invention, the term "C2-C10 heterocyclic group (heterocycloalkyl)" refers to a monovalent substituent derived from a monocyclic or polycyclic ring having 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, Si.

[0051] As used in the present invention, the term "alkoxy" refers to a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited herein, but the alkoxy group preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentyloxy, n-hexyloxy, and benzyloxy.

[0052] As used herein, the term "cycloalkenyl" refers to an unsaturated carbon ring and does not have aromatic character.

[0053] As used herein, the term "heterocycloalkenyl" refers to an unsaturated heterocyclic ring, and does not have aromaticity.

[0054] As used in the present invention, the term "C6-C60 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 60 carbon atoms. Further, such an aryl may have a form in which two or more rings are simply lateral or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0055] As used herein, the term "arylene group" refers to a divalent aromatic group derived from an "aryl group" by removing a hydrogen atom. For example, a phenyl group is substituted by removing a hydrogen atom to form a phenylene group, and a naphthyl group is substituted by removing a hydrogen atom to form a naphthylene group.

[0056] As used in the present invention, the term "C3-C60 heteroaryl group" refers to a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S, P, B or Si. In addition, this heteroaryl group may have a form in which two or more rings are simply lateral to each other or fused to each other or fused 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.

[0057] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl" by removing a hydrogen atom. For example, a pyridyl group is derived from a pyridylene group by removing a hydrogen atom.

[0058] As used in the present invention, the term "silyl group" refers to a trisubstituted silyl group, such as trimethylsilyl, triphenylsilyl, and the like.

[0059] As used in the present invention, the "carbon number is XY" in the expression "Z group having carbon number XY" or "Z group of C(XY)" 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-C60 aromatic group means that when it is unsubstituted, the carbon number of the aromatic group is any integer between 6 and 60, that is, the carbon number when unsubstituted can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20...60.

[0060] 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, as long as it is not otherwise described in this specification,

[0061] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0062] When two or more substituents are present, the two or more substituents may be the same or different.

[0063] As used herein, the term "naphthyridine" includes

[0064] As used herein, the term "terphenyl" includes

[0065] As used herein, the term "benzoquinoline" includes

[0066] As used in the present invention, hydrogen atoms include protium, deuterium and tritium. The compounds of the present invention may contain deuterium atoms of natural origin, or may introduce deuterium atoms 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 may be less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be more than 1%, or more than 5%, or more than 10%. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and undeuterated compounds, or a mixture of completely deuterated compounds and incompletely deuterated compounds, or a mixture of completely deuterated compounds and undeuterated compounds and incompletely deuterated compounds.

[0067] As used in the present invention, terms such as first, second, A, B, etc. 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.

[0068] Organic electroluminescent element

[0069] 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, wherein the organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0070] The organic layer may further include 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.

[0071] The light-emitting element of the present invention may emit fluorescence or phosphorescence or a combination thereof. The light-emitting element may emit light alone or in series with multiple light-emitting units.

[0072] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0073] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0074] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0075] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0076] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0077] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0078] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0079] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0080] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0081] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0082] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0083] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0084] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0085] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0086] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0087] As a tandem type organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also be generally 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.

[0088] When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

[0089] The organic electroluminescent element of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers is prepared by using a compound comprising the formula (1).

[0090] As the cathode material, a material having a low work function is generally used to facilitate electron injection into the organic material layer.

[0091] The hole injection layer is a layer that injects holes from the electrode and has a capability of transporting holes.

[0092] The hole transport material is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and is suitably a material having high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0093] The light emitting material may be a material that receives holes and electrons from the hole transport layer and the electron transport layer, respectively, and combines the holes and electrons to emit light in the visible light region. The light emitting layer material includes a host material and a doping material.

[0094] 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 is a material having high electron mobility that can receive electrons from the cathode and transfer the electrons to the light emitting layer.

[0095] The electron injection layer is a layer that injects electrons from the electrode.

[0096] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0097] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0098] The organic light emitting device of the present specification may be a top-emitting device, a bottom-emitting device, or a dual-emission type device according to the materials used.

[0099] The charge generation layer refers to the middle layer between the anode and cathode in a tandem structure device, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, which can effectively separate charges and effectively transport carriers.

[0100] 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.

[0101] Synthesis Example

[0102] Example 1: Synthesis of Compound 1

[0103]

[0104] Under nitrogen atmosphere, 9-bromophenanthrene (27g, 105.01mmol), 2,3,4,5-tetraphenyl-1H-pyrrole (20g, 47.73mmol), bis(trimethylsilyl) lithium amide (15.9g, 95.46mmol), tridibenzylideneacetone palladium (1.4g, 1.43mmol) and tri-tert-butylphosphine (2.89g, 14.31mmol) were put into a four-necked bottle, 300mL of xylene was added, and the temperature was raised to reflux of the reaction system, and then the mixture was stirred for 12h, and tridibenzylideneacetone palladium (1.4g, 1.43mmol) was added to continue the reaction for 24h. When the reaction was completed, the heating was stopped. After cooling, ethyl acetate and H2O were used for extraction, and the organic phases were combined and dried. The sample was purified by column chromatography with n-hexane: dichloromethane (volume ratio) = 15:1-6:1 to obtain 4.9g of the product.

[0105] LC-MS (APCI): 548.70 (M+H + ).Calcd for:C 42 H 29 N

[0106] 1H NMR (400MHz, CD2Cl2) δ8.69-8.60 (m, 2H), 7.85 (s, 1H), 7.74 (dd, 1.5Hz, 1H), 7.63-7.51 (m, 4H), 7.48-7.3 7(m, 3H), 7.35-7.29(m, 2H), 7.28-7.22(m, 1H), 7.00-6.92(m, 6H), 6.87-6.72(m, 7H), 6.35-6.24(m, 2H).

[0107] The following application examples further illustrate the application of a nitrogen heterocyclic derivative described in the present invention in the preparation of an organic electroluminescent element.

[0108] Application Example 1:

[0109] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes a first electrode layer 12, a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, an electron transport layer 8, an N-type charge generation layer 7, a P-type charge generation layer 6, a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, an electron injection layer 2 and a second electrode layer 1 stacked from bottom to top, wherein 200 is a first light-emitting unit, 100 is a second light-emitting unit, the first light-emitting unit 200 includes a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, and an electron transport layer 8, and the second light-emitting unit 100 includes a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, and an electron injection layer 2.

[0110] The specific device structure is:

[0111] 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).

[0112] Device preparation process:

[0113] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 12. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0114] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10-8 In the case of torr, each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second. 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 the anthracene main body ADN (9,10-di(naphtha-2-yl-) anthracene) is doped with a 3% mass content of pyrene dopant 1,6-bis(diphenylamino)pyrene 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% mass content of Li to form an N-type charge generation layer 7 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 20nm is formed, NPD with a thickness of 20nm is formed as a hole transport layer, 1,6-bis(diphenylamino)pyrene with a mass content of 3% of pyrene dopant 1,6-bis(diphenylamino)pyrene is doped on the anthracene main body ADN(9,10-di(naphtha-2-yl-)anthracene) to form a blue light-emitting layer with a thickness of 20nm, Alq3(Tris-(8-hydroxyquinolinato)aluminum) is formed with a thickness of 10nm as a second electron transport layer, LiF is formed with a thickness of 0.5nm as an electron injection layer, and Al is formed with a thickness of 200nm as a cathode.

[0115] Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic component 1.

[0116]

[0117] Examples and Comparative Examples

[0118] Comparative Example 1 Bphen (4,7-Diphenyl-1,10-phenanthroline)

[0119] Comparative Example 2 uses the structural formula The N-type charge generation layer 7 is prepared by replacing the Bphen material with a compound, and the organic electronic element 2 is prepared by the same method.

[0120] The preparation method is:

[0121]

[0122] Under nitrogen atmosphere, 2,3,4,5-tetraphenyl-pyrrole (30.0 g, 80.8 mmol) was put into a four-necked bottle, and about 300 mL of THF was added to dissolve. The temperature in the system was lowered to below -78°C with liquid nitrogen, and then n-butyl lithium was slowly dripped in, and stirred at low temperature for 1 hour after the dripping was completed. Diphenylphosphine chloride was then slowly dripped in, and stirred at low temperature for 1 hour after the dripping was completed, and then the cold bath was removed and stirred at room temperature for 2 hours. Extracted with DCM and H2O, the organic phases were combined and spin-dried. The crude product obtained above was purified by silica gel column chromatography (developing solvent was n-hexane: dichloromethane = 1:3), and then recrystallized from chlorobenzene to obtain a white comparative compound 1 (12.7 g, yield 28%).

[0123] 1 H NMR (400MHz, CD2Cl2) δ7.42-7.32(m, 4H), 7.13-7.08(m, 2H), 7.07-7.00(m, 8H), 6.99-6.89(m, 10H), 6.86-6.77(m, 6H).

[0124] LC-MS (APCI): 572.46 (M+H+).

[0125] Example

[0126] The N-type charge generation layer 7 was prepared by using the compound prepared in Example 1 of the present invention instead of the Bphen material, and the organic electronic element 3 was prepared by the same method.

[0127] Organic electroluminescent element evaluation

[0128] 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.

[0129] Current efficiency at current density 15mA / cm 2 The following test is performed and the test results are shown in Table 1.

[0130] Table 1

[0131]

[0132] The organic electroluminescent element 3 prepared by the compound of the present invention has higher current efficiency and longer service life than the organic electronic elements 1 and 2. Therefore, the compound of the present invention is suitable for preparing high-performance organic electroluminescent elements.

[0133] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nitrogen heterocyclic derivative, characterized in that: The compound has a structure shown in formula (1), in, Ar1 is selected from substituted or unsubstituted C6-C30 aryl; R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl, R1, R2, R3, and R4 are not hydrogen at the same time; In the "substituted or unsubstituted" mentioned above, the substituent when substituted is selected from hydrogen, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C2-C10 alkenyl, C2-C10 alkynyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 carbocyclic group, C3-C60 heterocyclic group, The heteroatom in the heterocyclic group and heteroaryl group is selected from N, O, S, Si, and P.

2. A nitrogen heterocyclic derivative according to claim 1, characterized in that: Ar1 is selected from substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, and substituted or unsubstituted perylenyl.

3. A nitrogen heterocyclic derivative according to claim 1, characterized in that: Ar1 is selected from one of the following structures: Wherein, * indicates connection with N in formula (1), R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Each is independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl.

4. A nitrogen heterocyclic derivative according to claim 1, characterized in that: R1, R2, R3, and R4 are each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl, and At least one of R1, R2, R3 and R4 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indene substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

5. A nitrogen heterocyclic derivative according to claim 3, characterized in that: R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 each independently selected from hydrogen, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl , substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted substituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted substituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

6. A nitrogen heterocyclic derivative according to claim 1, characterized in that: The nitrogen heterocyclic derivative is selected from any one of the compounds shown in numbers 1 to 65 below:

7. A preparation, characterized in that The preparation comprises at least one nitrogen heterocyclic derivative according to any one of claims 1 to 6 and at least one solvent.

8. An organic electroluminescent element, characterized in that: The organic electroluminescent element comprises: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode and including a light-emitting layer, One or more layers of the organic material layer contain the nitrogen heterocyclic derivative according to any one of claims 1 to 6.

9. The organic electroluminescent element according to claim 8, characterized in that: The organic material layer comprises at least two light-emitting units, an N-type charge generation layer is disposed between the two light-emitting units, and the N-type charge generation layer comprises the nitrogen heterocyclic derivative according to any one of claims 1 to 6.

10. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent element according to claim 8 or 9.

Images