Benzophenanthrene derivative and organic electroluminescent element containing same

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to a benzophenanthrene derivative and an organic electroluminescence element containing the benzophenanthrene derivative. The benzophenanthrene derivative has a structure # imgabs0 # as shown in a formula (1) or a formula (2), not only can be used as a high-performance charge generation layer material, but also can be used for one or more layers of single-layer or laminated devices such as an electron transport layer and a hole blocking layer, and can prolong the service life of an organic electroluminescent element when being applied to the organic electroluminescent element.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and particularly relates to a triphenylene derivative and an organic electroluminescent element containing the same. Background Art

[0002] Organic semiconductor materials are versatile 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, due to the different transmission rates of electrons and holes in OLED devices, the number of carriers in the light-emitting area is unbalanced, which limits the improvement of the exciton recombination rate, resulting in low device efficiency and high driving voltage. Adding a charge generation layer between the light-emitting units can effectively improve the problem of unbalanced number of carriers in the device. However, there is currently 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. Summary of the invention

[0004] The purpose of the present invention is to provide a triphenylene derivative, which can not only be used as a high-performance charge generation layer material, but also can be used in one or more layers of single-layer or stacked devices such as electron transport layers and hole blocking layers, and can be used in organic electroluminescent elements to extend their service life.

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

[0006] A triphenylene derivative having a structure shown in formula (1) or formula (2)

[0007]

[0008] L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C4-C60 nitrogen-free heteroarylene group,

[0009] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0010] R 1’ , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ , R 7’ , R 8’ , R 9’ , R 10’ , R 11’ , R 12’ are each independently selected from hydrogen or deuterium;

[0011] The substitution in the substituted C1-C10 alkyl, substituted C3-C10 cycloalkyl, substituted C4-C60 nitrogen-free heteroarylene group means that one or more substitutable positions are substituted, and the substituent is deuterium;

[0012] The substitution in the substituted C6-C60 arylene group, substituted C6-C60 aryl group and substituted C3-C60 heteroaryl group refers to that one or more substitutable positions are substituted, and the substituent is selected from one or more combinations of deuterium, halogen, cyano, C6-C30 aryl group and C3-C30 heteroaryl group.

[0013] As a preference, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each is independently selected from hydrogen and deuterium.

[0014] As a preference, R 1 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl;

[0015] Preferably, R 1 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0016] The substituent in the substituted C6-C30 aryl group or the substituted C3-C30 heteroaryl group means that one or more hydrogen atoms therein are independently selected from one or a combination of deuterium, halogen, cyano, C6-C30 aryl group, and C3-C30 heteroaryl group;

[0017] Preferably, R 1is selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl;

[0018] Preferably, the substitution in the substituted phenyl, substituted naphthyl, substituted pyridyl, substituted anthracenyl and substituted phenanthryl means that one or more substitutable positions are substituted, and the substituent is deuterium.

[0019] As a preference, L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group;

[0020] Preferably, the substitution in the substituted phenylene, substituted biphenylene, substituted naphthylene, substituted anthrylene, substituted phenanthrylene, substituted pyrene, substituted fluoranthenylene, substituted dibenzofuranyl and substituted dibenzothiophenylene means that one or more substitutable positions are substituted, and the substituent is deuterium.

[0021] Preferably, the triphenylene derivative is selected from any of the following compounds:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

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[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] A use of the triphenylene derivative of the present invention in preparing an organic electroluminescent element.

[0057] 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 triphenylene derivative of the present invention.

[0058] Preferably, the organic layer comprises an electron transport layer and a light-emitting layer, and the electron transport layer comprises the triphenylene derivative described in the present invention.

[0059] Preferably, a hole blocking layer is further included between the electron transport layer and the light-emitting layer, and the hole blocking layer material includes the triphenylene derivative described in the present invention.

[0060] Preferably, the organic layer comprises two or more light-emitting units, a charge generation layer is comprised between the light-emitting units, the light-emitting units comprise an electron transport layer, and the charge generation layer and / or the electron transport layer comprise the triphenylene derivative described in the present invention.

[0061] An electronic device comprises the organic electroluminescent element of the present invention.

[0062] The beneficial effects of the present invention are:

[0063] 1. The triphenylene derivatives of the present invention can reduce the driving voltage of the device and effectively extend the service life of the device while ensuring the current efficiency.

[0064] 2. The triphenylene derivatives of the present invention can be used not only for the N-type charge generation layer of the stacked OLED device, but also for the hole blocking layer and the charge transport layer, thereby reducing the types of materials of the stacked device. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent element described in the application example, wherein, a 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. DETAILED DESCRIPTION

[0066] 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 viewpoints of the present invention to those skilled in the art.

[0067] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0068] Explanation of terms

[0069] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0070] 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.

[0071] 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.

[0072] 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, this aryl can have a form in which two or more rings are simply lateral or fused to each other. Examples of this aryl include, but are not limited to, phenyl, biphenyl, terphenyl, phenyl substituted naphthyl, naphthyl substituted phenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] As used in the present invention, the "carbon number is AA-BB" in the expression "Z group having carbon atoms AA-BB" 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.

[0077] 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. The number of substitutions, if not explicitly defined, includes all the possible substitutions. For example, carbazolyl includes any of the following groups, but is not limited thereto, unless otherwise specified in this specification,

[0078]

[0079] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0080] When two or more substituents are present, the two or more substituents may be the same or different.

[0081] 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.

[0082] 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.

[0083] Organic electroluminescent element

[0084] 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.

[0085] 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.

[0086] 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.

[0087] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0088] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0089] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0090] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0091] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0092] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0093] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0094] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0095] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0096] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0097] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0098] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0099] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0100] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0101] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0102] 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.

[0103] 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.

[0104] 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).

[0105] As the cathode material, a material having a low work function is generally used to facilitate electron injection into the organic material layer.

[0106] The hole injection layer is a layer that injects holes from the electrode and has a capability of transporting holes.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] The electron injection layer is a layer that injects electrons from the electrode.

[0111] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0112] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0113] 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.

[0114] 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.

[0115] Those skilled in the art can synthesize the compounds of the present invention with reference to the synthesis of the following compounds and known synthesis methods. Two reference synthesis routes are given below, but other synthesis routes are not excluded.

[0116]

[0117] The preparation method of the intermediate 2-1 in the following examples is based on the synthesis example 2: Synthesis of Compound 2 (1) Synthesis of Intermediate 2-1.

[0118] Synthesis Example 1: Synthesis of Compound 1

[0119] (1) Synthesis of intermediate 1-1

[0120]

[0121] N 2 Under the atmosphere, 30g of raw material 1 was dissolved in 450ml of dimethylformamide, and the temperature was raised to 60°C, and 24.42g of N-bromosuccinimide (dissolved in dimethylformamide) was added dropwise. After the addition was completed, the temperature was kept at 60°C until the raw material was no longer reduced. After stopping the reaction, the temperature was lowered to room temperature and water was added. Filtered and washed with ethanol to obtain a crude product. After column chromatography (dichloromethane as the developing solvent), 28g of intermediate 1-1 was obtained, with a yield of 68.5%.

[0122] LC-MS (APCI): 309 (M+H + ).

[0123] (2) Synthesis of Compound 1

[0124]

[0125] Under nitrogen atmosphere, intermediate 1-1 (10 g, 32.5 mmol), 2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl]-1,10-phenanthroline (13.68 g, 35.8 mmol), tetrakis(triphenylphosphine)palladium (0.75 g, 0.65 mmol) and potassium carbonate (9.0 g, 65.1 mmol) were added to 90 ml of tetrahydrofuran and 30 ml of water, and the temperature was raised to reflux for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by column chromatography (dichloromethane as developing solvent) gave 13.2 g of compound 1 with a yield of 88%.

[0126] LC-MS (APCI): 483.37 (M+H + ).

[0127] 1H NMR (400MHz, CD 2 Cl 2 )δ9.22(dd,1H),8.97-8.75(m,4H),8.55(d,2H),8.41(d,1H),8.37-8.25(m ,2H),8.16(d,1H),8.12-8.01(m,2H),7.95-7.82(m,4H),7.82-7.60(m,5H).

[0128] Synthesis Example 2: Synthesis of Compound 2

[0129] (1) Synthesis of intermediate 2-1

[0130]

[0131] Under N2 atmosphere, 28g of intermediate 1-1, 16.7g of bipyraclostrobin, 18g of potassium acetate, and 2.6g of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride were added to a four-necked reaction bottle, and then 400ml of anhydrous dioxane was added, and the temperature was raised to reflux for reaction. After the reaction was completed, water was added after cooling to room temperature, and the mixture was extracted with dichloromethane, dried with anhydrous sodium sulfate, and then mixed with silica gel. After column chromatography (dichloromethane as the developing solvent), 21g of intermediate 2-1 was obtained, with a yield of 64.8%.

[0132] LC-MS (APCI): 355.18 (M+H + ).

[0133] (2) Synthesis of Compound 2

[0134]

[0135] N 2Under the atmosphere, 11.6g of 2-(4-bromonaphthalene-1-yl)-1,10-phenanthroline, 10.6g of intermediate 2, 1.8g of tetrakis(triphenylphosphine)palladium, and 8.34g of potassium carbonate were added to a four-necked reaction bottle, and then 260ml of tetrahydrofuran and 100ml of water were added, and the temperature was raised to 75°C for reaction. After the reaction was completed, the reaction solution was cooled to room temperature and filtered to obtain a crude product. Then, chlorobenzene was used to beat the product to obtain 6.3g of a white solid final product with a yield of 39%.

[0136] LC-MS (APCI): 533.42 (M+H + ).

[0137] 1 H NMR (400MHz, CD 2 Cl 2 )δ9.11-9.10(d,1H),8.88-8.86(d,1H),8.81-8.78(d,1H),8.78(s,1H),8.70-8 .68(d,1H),8.42-8.40(d,1H),8.28-8.26(d,1H),8.22-8.20(d,1H),8.06-7.97 (m,3H),7.90-7.88(d,2H),7.85-7.82(d,1H),7.74-7.72(d,1H),7.69-7.65(t, 1H),7.64-7.57(m,4H),7.50-7.48(d,1H),7.44-7.38(m,2H),7.26-7.22(t,1H).

[0138] Synthesis Example 3: Synthesis of Compound 47

[0139] (1) Synthesis of Intermediate 47-1

[0140]

[0141] Under nitrogen atmosphere, 2-bromo-9-phenyl-1,10-phenanthroline (19.17 g, 57.22 mmol), p-bromophenylboronic acid (11.5 g, 57.22 mmol), tetrakis(triphenylphosphine)palladium (1.98 g, 1.72 mmol) and sodium carbonate (12.13 g, 114.4 mmol) were added to 350 ml of toluene, 150 ml of ethanol and 150 ml of water, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (volume ratio of developing solvent: n-hexane: ethyl acetate = 50:50) gave 20 g of intermediate 47-1 with a yield of 85%.

[0142] LC-MS (APCI): 413.22 (M+H + ).

[0143] (2) Synthesis of Compound 47

[0144]

[0145] Under nitrogen atmosphere, intermediate 47-1 (10.0 g, 24.31 mmol), intermediate 2-1 (8.69 g, 24.55 mmol), tetrakis(triphenylphosphine)palladium (840 mg, 0.73 mmol) and potassium carbonate (10.0 g, 72.93 mmol) were added to 200 ml of tetrahydrofuran and 70 ml of water, and the temperature was raised to reflux for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (volume ratio of developing solvent: n-hexane: dichloromethane = 1:4) gave 8.5 g of compound 47 with a yield of 94%.

[0146] LC-MS (APCI): 559.43 (M+H + ).

[0147] 1H NMR (400MHz, CD 2 Cl 2 )δ8.93(d,1H),8.89-8.78(m,3H),8.67(d,2H),8.52-8.28(m,5H),8.20(dd ,2H),8.13-8.02(m,2H),7.95-7.83(m,4H),7.81-7.60(m,6H),7.51(t,1H)

[0148] Synthesis Example 4: Synthesis of Compound 6

[0149] (1) Synthesis of Intermediate 6-1

[0150]

[0151] 2-(4-bromophenyl)-1,10-phenanthroline (15 g, 44.75 mmol), 4-chloro-1-naphthaleneboric acid (9.7 g, 46.99 mmol), sodium bicarbonate (11.28 g, 134.25 mmol), 300 ml of tetrahydrofuran, 100 ml of water, and tetrakis(triphenylphosphine)palladium (1.0 g, 0.895 mmol) were added to a 1L four-necked bottle in sequence, and the mixture was refluxed for 3 hours after nitrogen replacement. After the reaction was completed, the mixture was separated and concentrated, and the intermediate 6-1 (15.86 g) was obtained by slurrying with 100 ml of ethanol.

[0152] LC-MS (APCI): =417.91 [M+H] +

[0153] (2) Synthesis of Compound 6

[0154]

[0155] Into a 1L four-necked bottle, add intermediate 6-1 (15.86g, 38.04mmol), intermediate 2-1 (14.15g, 39.94mmol), sodium carbonate (7.9g, 57.06mmol), 200ml toluene, 50ml ethanol, 50ml water, Pd-132 (0.54g, 0.76mmol), nitrogen replacement, reflux reaction for 6 hours. After the reaction is completed, water is separated, and after concentration, 100ml toluene is used for slurrying to obtain compound 6 (15g).

[0156] LC-MS (APCI): =609.74 [M+H] +

[0157] 1 H NMR(400MHz,Methylene Chloride-d 2 )δ9.14(dd,1H),8.87(d,1H),8.82–

[0158] 8.72(m,2H),8.71–8.63(m,1H),8.46(d,2H),8.34(d,1H),8.27–8.16(m,2H),8.12–7 .95(m,3H),7.85–7.74(m,4H),7.70–7.52(m,7H),7.50–7.37(m,3H),7.23(ddd,1H).

[0159] Synthesis Example 5: Synthesis of Compound 14

[0160] (1) Synthesis of Intermediate 14-1

[0161]

[0162] Under nitrogen atmosphere, 1,6-dibromopyrene (12.39 g, 34.41 mmol), intermediate 2-1 (13.4 g, 63.8 mmol), tetrakis(triphenylphosphine)palladium (1.2 g, 1.03 mmol) and potassium acetate (6.7 g, 68.82 mmol) were added to 350 ml of toluene, 150 ml of ethanol and 150 ml of water, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (developing solvent: n-hexane: ethyl acetate = volume ratio 4:1) gave intermediate 14-1 (8.0 g, yield 42%).

[0163] LC-MS (APCI): 507.26 (M+H + ).

[0164] (3) Synthesis of Intermediate 14-2

[0165]

[0166] Under nitrogen atmosphere, intermediate 14-1 (8.0 g, 15.78 mmol), biboronic acid pinacol ester (4.8 g, 18.93 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (346 mg, 0.473 mmol) and potassium acetate (3.1 g, 31.56 mmol) were added to 300 ml of 1,4-dioxane and heated to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (developing solvent: n-hexane: ethyl acetate volume ratio = 1:1) gave intermediate 14-2 (10.3 g, yield 85%).

[0167] LC-MS (APCI): 555.48 (M+H + ).

[0168] (4) Synthesis of Compound 14

[0169]

[0170] Under nitrogen atmosphere, intermediate 14-2 (7.3 g, 13.17 mmol), 2-bromo-1,10-phenanthroline (3.57 g, 13.57 mmol), tetrakis(triphenylphosphine)palladium (456 mg, 0.3951 mmol) and potassium carbonate (3.6 g, 26.34 mmol) were added to 210 ml of tetrahydrofuran and 70 ml of water, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Compound 14 (7.0 g, yield 88%) was obtained by purification by silica gel chromatography (developing solvent: ethyl acetate: dichloromethane = volume ratio 1:10).

[0171] LC-MS (APCI): 607.51 (M+H + ).Calcd for C 46 H 26 N 2

[0172] 1 H NMR(400MHz,Methylene Chloride-d 2 )δ9.19(dd,1H),9.00(d,1H),8.96–

[0173] 8.88(m,2H),8.82–8.74(m,1H),8.61(d,1H),8.52(d,1H),8.45–8.31(m,4H),8.34 –8.04(m,5H),8.04–7.90(m,3H),7.86–7.63(m,5H),7.58(d,1H),7.52–7.43(m,1H)

[0174] Synthesis Example 6: Synthesis of Compound 31

[0175] (1) Synthesis of Intermediate 31-1

[0176]

[0177] To N 2In a protected 1L four-necked flask, add 1-chloro-4-bromodibenzofuran (20g, 71.04mmol), 300ml of tetrahydrofuran, cool to -80℃ with liquid nitrogen, add n-butyl lithium (39ml (2mol / L), 78.14mmol), keep warm for 0.5h after the addition, add 1,10-phenanthroline (15.36g, 85.25mmol), naturally warm to room temperature for 1h, add 10ml of water to quench the reaction, separate the water phase, concentrate the organic phase, add 300ml of dichloromethane to dissolve, then add manganese dioxide (18.53g, 213.12mmol) and reflux for 2h. After the reaction is complete, pass through a silica gel funnel, concentrate the filtrate, and slurry with 100ml of ethanol to obtain intermediate 31-1 (23g).

[0178] LC-MS (APCI): =381.83 [M+H] +

[0179] (2) Synthesis of compound 31

[0180]

[0181] Into a 1L four-necked bottle, add intermediate 31-1 (23g, 60.39mmol), intermediate 2-1 (22.46g, 63.41mmol), sodium carbonate (9.6g, 90.58mmol), 200ml toluene, 50ml ethanol, 50ml water, Pd-132 (0.857g, 1.2mmol), nitrogen replacement, reflux reaction for 6 hours. After the reaction is completed, water is separated, and compound 31 (27.6g) is obtained after concentration and recrystallization from toluene.

[0182] LC-MS (APCI): =573.67 [M+H] +

[0183] 1 H NMR(400MHz,Methylene Chloride-d 2 )δ9.28(dd,1H),9.07–8.92(m,5H),8.86–8.78(m,1H),8.57(d,1H),8.37(dd,1H),8.20(dd,1H),8.14–8.09(m,1H),7.99(d, 1H),7.95–7.86(m,2H),7.85–7.78(m,2H),7.77–7.69(m,4H),7.54(ddd,1H),7.39(ddd,1H),6.87(ddd,1H),6.69(ddd,1H).

[0184] The following application examples further illustrate the application of the heterocyclic compound of the present invention in the preparation of organic electroluminescent elements.

[0185] Application Example 1

[0186] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes 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 the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4 and the electron transport layer 5 are a first light-emitting unit 100, and the hole transport layer 8, the light-emitting layer 9, the electron transport layer 10 and the electron injection layer 11 are a second light-emitting unit 200.

[0187] The specific device structure is:

[0188] 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) / Alq 3 (10nm) / LiF(0.5nm) / Al(200nm).

[0189] Device preparation process:

[0190] 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 1. 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.

[0191] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8Each organic layer was deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of 1000 Å / s. Among them, F4-TCNQ (mass content 10%) was doped into NPD to form a thickness of 10nm as a hole injection layer. NPD was formed to a thickness of 120nm as a hole transport layer, and the anthracene host ADN (9,10-di(naphtha-2-yl-)anthracene) was 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 was formed to a thickness of 10nm as the first electron transport layer, and BPhen (4,7-Diphenyl-1,10-phenanthroline) was doped with a mass content of 3%. The N-type charge generation layer 6 with a thickness of 10 nm is formed by doping NPD with a mass content of 2% Li, and a P-type charge generation layer with a thickness of 20 nm is formed by doping NPD with a mass content of 10% F4-TCNQ, and 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 mass content of 3% pyrene dopant 1,6-bis(diphenylamino)pyrene to form a blue light-emitting layer with a thickness of 20 nm. Alq 3 (Tris-(8-hydroxyquinolinato)aluminum) was formed to a thickness of 10 nm as a second electron transport layer, LiF was formed to a thickness of 0.5 nm as an electron injection layer, and Al was formed to a thickness of 200 nm as a cathode.

[0192] 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.

[0193]

[0194] Contrast structure

[0195] Bphen(4,7-Diphenyl-1,10-phenanthroline)

[0196]

[0197] Examples and Comparative Examples

[0198] The N-type charge generation layer was prepared by using the compound prepared in Example 1 of the present invention instead of the Bphen material, and the organic electroluminescent element 2 was prepared by the same method.

[0199] The N-type charge generation layer was prepared by using the compound prepared in Example 2 of the present invention instead of the Bphen material, and the organic electroluminescent element 3 was prepared by the same method.

[0200] The N-type charge generation layer was prepared by using the compound prepared in Example 3 of the present invention instead of the Bphen material, and the organic electroluminescent element 4 was prepared by the same method.

[0201] The N-type charge generation layer was prepared by using the compound prepared in Example 4 of the present invention instead of the Bphen material, and the organic electroluminescent element 5 was prepared by the same method.

[0202] The N-type charge generation layer was prepared by using the compound prepared in Example 5 of the present invention instead of the Bphen material, and the organic electroluminescent element 6 was prepared by the same method.

[0203] The N-type charge generation layer was prepared by using the compound prepared in Example 6 of the present invention instead of the Bphen material, and the organic electroluminescent element 7 was prepared by the same method.

[0204] 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.

[0205] Current efficiency at current density 15mA / cm 2 Next test.

[0206] The driving voltage is at a current density of 15 mA / cm 2 The following test is performed and the test results are shown in Table 1.

[0207] Table 1

[0208] Driving voltage, v Current efficiency, cd / A Life LT95, hours Organic electroluminescent element 1 7.07 17 58 Organic electroluminescent element 2 6.90 17 93 Organic electroluminescent element 3 6.91 17 94 Organic electroluminescent element 4 6.88 17 97 Organic electroluminescent element 5 6.90 18 95 Organic electroluminescent element 6 6.87 18 96 Organic electroluminescent element7 6.85 18 96

[0209] According to the results in Table 1, the organic electroluminescent element prepared from the triphenylene derivatives of the present invention has a lower driving voltage and a longer service life than the organic electronic element 1. The triphenylene derivatives of the present invention are suitable for preparing high-performance organic electroluminescent elements.

[0210] 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 triphenylene derivative, characterized in that The triphenylene derivative has a structure shown in formula (1) or formula (2): L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C4-C60 nitrogen-free heteroarylene group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 1’ , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ , R 7’ , R 8’ , R 9’ , R 10’ , R 11’ , R 12’ are each independently selected from hydrogen or deuterium; The substitution in the substituted C1-C10 alkyl, substituted C3-C10 cycloalkyl, substituted C4-C60 nitrogen-free heteroarylene group means that one or more substitutable positions are substituted, and the substituent is deuterium; The substitution in the substituted C6-C60 arylene group, substituted C6-C60 aryl group and substituted C3-C60 heteroaryl group refers to that one or more substitutable positions are substituted, and the substituent is selected from one or more combinations of deuterium, halogen, cyano, C6-C30 aryl group and C3-C30 heteroaryl group.

2. The triphenylene derivative according to claim 1, characterized in that R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Each is independently selected from hydrogen and deuterium.

3. The triphenylene derivative according to claim 1, characterized in that R 1 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.

4. The triphenylene derivative according to claim 1, characterized in that L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group.

5. The triphenylene derivative according to claim 1, characterized in that The triphenylene derivative is selected from any one of the following compounds, 6. Use of the triphenylene derivative according to any one of claims 1 to 5 in the preparation of an organic electroluminescent element.

7. An organic electroluminescent element comprising an anode, a cathode, and an organic layer located between the anode and the cathode, characterized in that The organic layer comprises the triphenylene derivative according to any one of claims 1 to 5.

8. The organic electroluminescent element according to claim 7, characterized in that The organic layer comprises an electron transport layer and a light emitting layer, and the electron transport layer comprises the triphenylene derivative according to any one of claims 1 to 5.

9. The organic electroluminescent element according to claim 7 or 8, characterized in that The organic layer comprises two or more light-emitting units, a charge generation layer is comprised between the light-emitting units, the light-emitting units comprise an electron transport layer, and the charge generation layer and / or the electron transport layer comprise the triphenylene derivative 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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