Compound and organic electroluminescent element and electronic device made of same

Abstract

The invention relates to a compound as well as an organic electroluminescent element and electronic equipment prepared from the compound. The compound has a structure shown in a formula (1), # imgabs0 # L1, L2, L3 and L4 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group, at least one of L1 and L2 is # imgabs1 # X is selected from O, S and CR9R10, R9 and R10 are selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C1-C10 alkyl groups or are connected into a ring B, and when the ring B is formed, the formula (2) is a substituted or unsubstituted spirobifluorenyl group; r1 to R8 are respectively and independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C60, substituted or unsubstituted alkyl of C1-C10, and substituted or unsubstituted cycloalkyl of C3-C10.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials, and particularly relates to a compound and an organic electroluminescent element and electronic equipment made thereof. Background Art

[0002] An organic light emitting diode (OLED) 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).

[0003] The organic light-emitting device has an anode and a cathode, and a structure in which an organic thin film is placed between the two electrodes. It can be a simple element including a single light-emitting unit or a tandem element including multiple light-emitting units.

[0004] Simple elements usually include a hole transport layer, a light-emitting layer, and an electron transport layer. The reason for making organic electroluminescent elements into multiple layers is to stabilize the interface between the electrode and the organic matter and to improve the luminous efficiency. The characteristics of the organic compound components contained in each layer have a great influence on the driving voltage, luminous efficiency, etc. of the element. Therefore, it is crucial to use suitable organic materials. Summary of the invention

[0005] The object of the present invention is to provide a compound which can be used as an organic electroluminescent material in an organic electroluminescent element, especially as an organic electroluminescent material in a hole transport region, so that the compound has a better current efficiency.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] A compound having a structure shown in formula (1),

[0008]

[0009] L 1 , L 2 , L 3 , L 4 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0010] L 1 , L 2 At least one of

[0011] X is selected from O, S, CR 9 R 10 , R 9, R 10 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C10 alkyl group, or connected to form ring B. When ring B is formed, formula (2) is a substituted or unsubstituted spirobifluorenyl group;

[0012] R 1 -R 8 Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl,

[0013] R 1 -R 8 Each exists independently or adjacent groups are connected to form a ring C, and the ring C is selected from an aromatic ring, a heteroaromatic ring, and an alkyl ring;

[0014] Ar 1 ,Ar 2 Each is independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C12-C60 diarylamine, substituted or unsubstituted C9-C60 arylheteroarylamine, substituted or unsubstituted C6-C60 diheteroarylamine, substituted or unsubstituted C3-C30 trialkylsilyl, substituted or unsubstituted C18-C60 triarylsilyl. Preferably, the compound has the structure shown in formula (1-1) or formula (1-2):

[0015]

[0016] L 1 , L 2 , L 3 , L 4 When each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group, the heteroatoms of the heteroarylene group are independently selected from O or S;

[0017] Preferably, L 1 , L 2 One of The other is a single bond, a substituted or unsubstituted phenylene group,

[0018] Preferably, ring C is selected from a benzene ring,

[0019] Preferably, the substituted substituents are each independently selected from one or more combinations of deuterium, halogen, C1-C10 alkyl, C2-C10 alkenyl, C6-C30 aryl, C3-C10 cycloalkyl, C3-C30 heteroaryl.

[0020] As a preference, L 1 , L 2 At least one is selected from a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, and a substituted or unsubstituted spirobifluorenylene group.

[0021] As a preference, L 1 , L 2 One of them is selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthrylene, and a substituted or unsubstituted phenanthrylene, and the other is selected from a substituted or unsubstituted dibenzofuranylene, a substituted or unsubstituted dibenzothiophenylene, a substituted or unsubstituted dimethylfluorenylene, a substituted or unsubstituted diphenylfluorenylene, and a substituted or unsubstituted spirobifluorenylene.

[0022] As a preference, -L 1 L 2 -Selected from one of the following groups:

[0023]

[0024] Preferably, -L 1 L 2 -Selected from one of the following groups:

[0025]

[0026]

[0027] As a preference, L 3 , L 4 each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted benzonaphthofuranylene group, a substituted or unsubstituted benzonaphthothiophenylene group,

[0028] Ar 1 ,Ar 2Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted carbazolyl.

[0029] As a preference, -L 3 -Ar 1 , -L 4 -Ar 2 Each is independently selected from one of the following groups:

[0030]

[0031]

[0032] Preferably, -L 3 -Ar 1 , -L 4 -Ar 2 Each is independently selected from one of the following groups:

[0033]

[0034]

[0035] Preferably, the compound of formula (1) is selected from one of the following compounds numbered O1-O424:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] And one of the compounds S1-S424 formed by replacing O in the compounds numbered O1-O424 with S.

[0065] A use of the compound of the invention as an organic electroluminescent material.

[0066] An organic electroluminescent element comprises a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode, wherein the light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, the electron transport region is located between the light-emitting layer and the cathode, and the hole transport region contains the compound described in the present invention.

[0067] Preferably, the hole transport region comprises a hole injection layer, a first hole transport layer, and a second hole transport layer, wherein the first hole transport layer is located between the hole injection layer and the light-emitting layer, the second hole transport layer is located between the first hole transport layer and the light-emitting layer, and the second hole transport layer comprises the compound described in the present invention.

[0068] An electronic device comprises the organic electroluminescent element of the present invention.

[0069] The beneficial effects of the present invention are:

[0070] 1. The compounds of the present invention have triphenylene-linked It can be used as an organic electroluminescent material in an organic electroluminescent element, especially as an organic electroluminescent material in a hole transport region, so that it has a better current efficiency. In more detail, it can be used as an organic electroluminescent material in a second hole transport layer, and at this time, the organic electroluminescent element has an improved current efficiency.

[0071] 2. The compound of the present invention has a relatively high glass transition temperature and is easy to form a pinhole-free film during vacuum evaporation, which is beneficial to improving device performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1,

[0073] Explanation of reference numerals: 1. substrate, 2. anode, 3. hole injection layer, 4. first hole transport layer, 5. second hole transport layer, 6. light-emitting layer, 7. hole blocking layer, 8. electron transport layer, 9. cathode. DETAILED DESCRIPTION

[0074] 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.

[0075] 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.

[0076] The reagents used in the following examples, unless otherwise specified, can be purchased from conventional biochemical reagent stores.

[0077] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0078] 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.

[0079] 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.

[0080] As used in the present invention, the term "C2-C10 heterocycloalkyl" is a monovalent substituent having a monocyclic or polycyclic ring of 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, and Si.

[0081] 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, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentyloxy, n-hexyloxy, and benzyloxy.

[0082] 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.

[0083] 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.

[0084] As used in the present invention, the term "C3-C60 heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon in the ring, preferably 1-3 carbons, is substituted by a heteroatom, such as N, O, S, P, B or Si. In addition, this heteroaryl can have a form in which two or more rings are simply lateral to each other or fused to each other or fused to an aryl. Examples of this heteroaryl include pyridyl, indolyl, indolopyridyl, purinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl, etc., and the present invention is not limited thereto.

[0085] 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.

[0086] 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.

[0087] As used in the present invention, the term "substituted or unsubstituted" means that the hydrogen atoms in the compound are replaced by non-hydrogen groups or are not replaced by non-hydrogen groups. The number of substituents is not limited, as long as they can be obtained through chemical reactions. It 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,

[0088]

[0089] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0090] When two or more substituents are present, the two or more substituents may be the same or different.

[0091] Refers to the replacement position.

[0092] 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.

[0093] 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.

[0094] Organic electroluminescent element

[0095] 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.

[0096] 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.

[0097] 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.

[0098] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0099] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0100] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0101] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0102] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0103] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0104] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0105] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0106] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0107] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0108] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0109] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0110] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0111] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0112] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0113] 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.

[0114] When the organic light emitting element includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0115] 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 layers are prepared by using a compound comprising formula (1).

[0116] As the anode material, a material having a relatively large work function may be used, and a transparent conductive oxide, a metal, a conductive polymer, etc. may be used. Specific examples of the anode material include: 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; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, etc., but are not limited thereto.

[0117] As the cathode material, a material with a low work function is generally used to facilitate electron injection into the organic layer, and metals, metal oxides, conductive polymers, etc. can be used. Specific examples of cathode materials include: metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; multilayer structure materials, such as LiF / Al or LiO2 / Al, etc., but are not limited thereto.

[0118] The hole injection layer is a layer that injects holes from the electrode and has the ability to transport holes. In order to reduce the energy level difference between the electrodes, the hole injection layer is mainly prepared based on aromatic amine compounds, and can also be prepared using the following materials, such as copper phthalocyanine in the metal complex, and HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene) with a phenylene structure in the material with the lowest unoccupied molecular orbital energy level. When used as a light-emitting host and dopant, F4-TCNQ (2 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone) inducer with the lowest unoccupied molecular orbital energy level can be doped in the aromatic amine compound.

[0119] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and 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 or high molecular materials can also be used.

[0120] The second hole transport layer can adjust the energy difference between the hole transport region and the light-emitting layer, which is beneficial for holes to enter the light-emitting layer, while reducing the probability of electrons entering the hole transport region from the light-emitting layer. Aromatic amine derivatives are commonly used.

[0121] The luminescent material is 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 luminescent layer material includes a host material and a doping material. Red, green or blue luminescent materials can be used, and two or more luminescent materials can be mixed as needed. As the luminescent material, a fluorescent material can be used, and a phosphorescent material can also be used. As the luminescent material, a single component material can be used, and a multi-component material can also be used.

[0122] The electron transport layer 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. The metal complexes of 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, and polymer materials and small molecule materials can also be used.

[0123] The electron injection layer is a layer that injects electrons from the electrode.

[0124] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0125] 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.

[0126] 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. There are many synthesis methods for the compounds of the present invention, and the following methods are only illustrative.

[0127] LC-MS brand model: Waters SQ Detector 2;

[0128] NMR brand: Bruker, model: AVANCE NEO 400.

[0129] DSC25 brand: TA, nitrogen atmosphere.

[0130] Synthesis formula: The following general formula is only one method for synthesizing the compounds of the present invention. The compounds of the present invention can also be synthesized by other methods.

[0131]

[0132]

[0133] Bpin refers to Br / Cl represents bromine or chlorine.

[0134] Synthesis Example 1 (Compound O291)

[0135] 1. Synthesis of Intermediate 1

[0136]

[0137] Add raw material 1-a (40.0g, 175.4mmol), m-bromoiodobenzene (59.5g, 210.5mmol) into a 1L four-necked flask, then add cuprous bromide (2.5g, 17.5mmol), palladium acetate (1.9g, 8.7mmol) and XPhos (8.3g, 17.5mmol), and 400ml triethylamine. Turn on magnetic stirring, replace nitrogen with vacuum, add nitrogen balloon, stir and react at room temperature for 1.5h. The final system is a brown turbid liquid. After the reaction is completed, pour into 500ml water, extract with ethyl acetate, mix the organic phase and pass through a column (n-hexane: dichloromethane = volume ratio 100:5), and obtain 148g of the intermediate with a yield of 72%.

[0138] LC-MS (APCI): 383.80 (M+H + ).Calcd for:C24H15Br

[0139] 2. Synthesis of Intermediate 2

[0140]

[0141] Add intermediate 1 (45g, 117.8mmol) and 675ml of dehydrated dichloromethane to a 2L four-necked flask, install a nitrogen balloon after vacuum replacement of nitrogen, and place the reaction device in an ice-water bath. Slowly drip trifluoromethanesulfonic acid (0.6ml, 4%) into the reaction bottle. After dripping, the system is a brown-yellow turbid liquid. Remove the ice-water bath, place the reaction bottle in a heating module, and stir the reaction at room temperature. The system gradually turns black. After reacting for 4h, add trifluoromethanesulfonic acid (0.4ml, 3%). After reacting for another 2h, the reaction is complete. Add 25ml of saturated sodium bicarbonate aqueous solution to the reaction bottle. Dilute with tap water and extract the liquid, and collect the organic phase. The organic phase is dried over anhydrous sodium sulfate, and the organic phase is finally spin-dried to obtain 38g of brown-yellow solid with a yield of 84%.

[0142] LC-MS (APCI): 383.09 (M+H + ).Calcd for:C24H15Br

[0143] 3. Synthesis of Intermediate 3

[0144]

[0145] Under nitrogen atmosphere, raw material 3-a (20g, 35.4mmol), biboric acid pinacol ester (10.7g, 42.4mmol), potassium acetate (6.9g, 70.8mmol), Pd (dppf) Cl2 (0.76g, 1mmol), 200mL 1,4-dioxane were added and the temperature was raised to 100°C for reaction. After the reaction was completed, the reaction solution was cooled to room temperature, 200mL water was added, and it was extracted twice with ethyl acetate. The organic phases were combined, concentrated to dryness, and the residue was purified by reflux beating with 300mL ethyl acetate. 17g of intermediate 3 was obtained with a yield of 78.3%.

[0146] LC-MS (APCI): 614.17 (M+H + ).Calcd for:C42H36BNO3

[0147] 4. Synthesis of the final product compound O291

[0148]

[0149] Under nitrogen atmosphere, intermediate 2 (7 g, 18.3 mmol), intermediate 3 (11.2 g, 18.3 mmol), K2CO3 (5 g, 36.6 mmol), Pd(PPh3)4 (0.63 g, 0.54 mmol) were added to a four-necked reaction bottle, and then 100 mL of THF:H2O (3:1) was added, and the temperature was raised to reflux reaction. After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of white solid precipitated and was directly filtered. Purification was performed by reflux beating with 70 mL of toluene to obtain 8.3 g of the final product with a yield of 60%.

[0150] LC-MS (APCI): 790.78 (M+H + ).Calcd for:C60H39NO

[0151] 1 H NMR(400MHz,Methylene Chloride-d2)δ9.23–9.01(m,1H),8.87–8.68(m,1H),8.30–8.10(m,2H),8.08–7.79(m,5H), 7.74–7.53(m,7H),7.51–7.38(m,10H),7.36–7.25(m,5H),7.23–7.10(m,7H),7.00(ddd,1H).

[0152] Glass transition temperature Tg: 159℃.

[0153] Synthesis Example 2 (Compound O219)

[0154] 1. Synthesis of Intermediate 1

[0155]

[0156] Under nitrogen atmosphere, raw material a (28 g, 48.7 mmol), m-chlorophenylboronic acid (26 g, 78 mmol), potassium carbonate (25 g, 97.4 mmol), Pd (dppf) Cl2 (1.1 g, 0.97 mmol) were added to a four-necked reaction bottle, and THF:H2O (3:1) was added for a total of 300 mL, and the temperature was raised to reflux reaction. After the reaction was completed, the reaction solution was cooled to room temperature and filtered directly. Purification was performed by reflux beating with 160 mL of ethanol to obtain 30 g of intermediate 1 with a yield of 90%. LC-MS (APCI): 339.80 (M+H + ).Calcd for:C24H15Cl

[0157] 2. Synthesis of Intermediate 2

[0158]

[0159] Under nitrogen atmosphere, intermediate 1 (28 g, 48.7 mmol), biboric acid pinacol ester (26 g, 78 mmol), potassium acetate (25 g, 97.4 mmol), Pd (dppf) Cl2 (1.1 g, 0.97 mmol) were added to a four-necked reaction bottle, and 300 mL of 1,4-dioxane was added, and the temperature was raised to reflux reaction. After the reaction was completed, the reaction solution was cooled to room temperature and filtered directly. Purification was performed by reflux beating with 160 mL of ethanol to obtain 30 g of intermediate 2 with a yield of 90%. LC-MS (APCI): 431.40 (M+H + ).Calcd for:C30H27BO2

[0160] 3. Synthesis of Intermediate 3

[0161]

[0162] Under nitrogen atmosphere, intermediate 2 (20 g, 25.4 mmol), 4-bromo-1-chlorobenzofuran (16 g, 24.1 mmol), K2CO3 (12 g, 50.8 mmol), Pd(dppf)Cl2 (1.5 g, 0.5 mmol) were added to a four-mouth reaction bottle, and THF:H2O (3:1) was added for a total of 200 mL, and the temperature was raised to reflux reaction. After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of white solid was precipitated and directly filtered. Purification was performed with 160 mL of chlorobenzene reflux pulping to obtain 15 g of intermediate 3 with a yield of 81%.

[0163] LC-MS (APCI): 505.40 (M+H+ ).Calcd for:C36H21ClO

[0164] 4. Synthesis of the final product compound O219

[0165]

[0166] Under nitrogen atmosphere, intermediate 3 (20 g, 25.4 mmol), di(4-biphenyl)amine (16 g, 24.1 mmol), K2CO3 (12 g, 50.8 mmol), Pd2(dba)3 (1.5 g, 0.5 mmol) and Xphos (1.5 g, 0.5 mmol) were added to a four-mouth reaction bottle, and 200 mL of toluene was added, and the temperature was raised to reflux reaction. After completion of the reaction, the reaction solution was cooled to room temperature, and a large amount of white solid was precipitated and directly filtered. Purification was performed by reflux pulping with 160 mL of chlorobenzene to obtain 15 g of the final product with a yield of 81%.

[0167] LC-MS (APCI): 790.31 (M+H + ).Calcd for:C60H39NO

[0168] 1 H NMR(400MHz,Methylene Chloride-d2)δ9.16–9.05(m,2H),8.21(dd,1H),8.13(t,1H),7.98(ddd,2H),7.90–7.79(m,3 H),7.57(dddd,2H),7.52–7.41(m,12H),7.34–7.28(m,6H),7.23–7.09(m,9H),7.01(td,1H).

[0169] Glass transition temperature Tg: 152℃.

[0170] The following application examples further illustrate the application of the compound of the present invention and the organic electroluminescent element containing the compound.

[0171] Application Example 1

[0172] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes a substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8 and a cathode 9 stacked from bottom to top. The hole injection layer 3, the first hole transport layer 4 and the second hole transport layer 5 are hole transport regions, and the hole blocking layer 7 and the electron transport layer 8 are electron transport regions.

[0173] The specific device structure is:

[0174] ITO / HT1-PD3%(10nm) / HT1(60nm) / HT2(5nm) / BH-BD3%(20nm) / HB(5nm) / ET-LiQ50%(30nm) / Mg:Ag 1:9(100nm)

[0175] Device preparation process:

[0176] The bottom emitting glass substrate 1 used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and ITO was used as the anode 2. 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.

[0177] 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 a 100 nm-thick PD doped on the ITO anode, each organic layer is deposited sequentially by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second. Among them, 3% PD is doped on HT1 to form a thickness of 10 nm as a hole injection layer 3, HT1 is formed to a thickness of 60 nm as a first hole transport layer 4, HT2 is evaporated on HT1 to a thickness of 5 nm as a second hole transport layer 5, 3% BD is doped on the anthracene main body BH to form a blue light-emitting layer 6 with a thickness of 20 nm, HB is formed to a thickness of 5 nm as a hole blocking layer 7, ET is doped with 50% Liq to form an electron transport layer 8 with a thickness of 30 nm, and Mg:Ag (1:9) is formed to a thickness of 100 nm as a cathode 9. In the present device embodiment, the same layer is co-evaporated with different materials, and exists in the layer in a certain volume ratio, for example, 50% Liq is a volume ratio of ET50% and Liq50%. Finally, the device was transferred back to the glove box and packaged with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic element 1 (Comparative Example 1).

[0178] The compound (No. O219) in Synthesis Example 2 was substituted for the material HT2 of the second hole transport layer to prepare an organic electronic device 2 (Application Example 1).

[0179] The above abbreviated compounds are specifically:

[0180]

[0181]

[0182] Test Results

[0183] The organic electronic component obtained by the above method was tested under the following test conditions:

[0184] IVL test equipment: F STAR Optical Measurement Systems, model: FS-2000GA4;

[0185] Atmospheric environment, room temperature,

[0186] Current efficiency and EQE external quantum efficiency are both at a current density of 15mA / cm 2 The following test is performed and the test results are shown in Table 1.

[0187] Table 1

[0188] Detection object Current efficiency, cd / A EQE, % Organic electronic component 1 (Comparative example HT2) 4.78 6.49 Organic electronic element 2 (compound of synthesis example 2) 5.87 8.22

[0189] According to Table 1, the compound of the present invention (compound No. 219) is used to replace the material HT2 of the second hole transport layer to prepare an organic electronic component, which has higher current efficiency and external quantum efficiency.

[0190] The glass transition temperature of the compound of the present invention is much higher than the glass transition temperature of HT2 (95 degrees Celsius). The compound of the present invention has a relatively high glass transition temperature and is easy to form a pinhole-free film during vacuum evaporation, which is beneficial to improving device performance.

[0191] The above is a detailed introduction to a compound provided by the present invention and its application as an organic electroluminescent material. Specific examples are used herein to illustrate the principles and implementation methods of the present invention, and 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 principle of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A compound characterized in that The compound has a structure shown in formula (1), L 1 , L 2 , L 3 , L 4 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group, L 1 , L 2 At least one of X is selected from O, S, CR 9 R 10 , R 9 , R 10 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C10 alkyl group, or connected to form ring B. When ring B is formed, formula (2) is a substituted or unsubstituted spirobifluorenyl group; R 1 -R 8 Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, R 1 -R 8 Each exists independently or adjacent groups are connected to form a ring C, and the ring C is selected from an aromatic ring, a heteroaromatic ring, and an alkyl ring; Ar 1 ,Ar 2 Each is independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C12-C60 diarylamine, substituted or unsubstituted C9-C60 arylheteroarylamine, substituted or unsubstituted C6-C60 diheteroarylamine, substituted or unsubstituted C3-C30 trialkylsilyl, substituted or unsubstituted C18-C60 triarylsilyl.

2. The compound according to claim 1, characterized in that: The compound has a structure shown in formula (1-1) or formula (1-2): L 1 , L 2 , L 3 , L 4 When each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group, the heteroatoms of the heteroarylene group are independently selected from O or S, The substituted substituents are each independently selected from one or more combinations of deuterium, halogen, C1-C10 alkyl, C2-C10 alkenyl, C6-C30 aryl, C3-C10 cycloalkyl, and C3-C30 heteroaryl.

3. The compound according to claim 1, characterized in that: L 1 , L 2 At least one is selected from a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, and a substituted or unsubstituted spirobifluorenylene group.

4. The compound according to claim 3, characterized in that -L 1 L 2 -Selected from one of the following groups:

5. The compound according to claim 1, characterized in that: L 3 , L 4 each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted benzonaphthofuranylene group, a substituted or unsubstituted benzonaphthothiophenylene group, Ar 1 ,Ar 2 Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted carbazolyl.

6. The compound according to claim 5, characterized in that -L 3 -Ar 1 , -L 4 -Ar 2 Each is independently selected from one of the following groups:

7. The compound according to claim 1, characterized in that The compound is selected from one of the following compounds numbered O1-O424: And one of the compounds S1-S424 formed by replacing O in the compounds numbered O1-O424 with S.

8. Use of the compound according to claims 1 to 7 as an organic electroluminescent material.

9. An organic electroluminescent element, comprising a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode, wherein the light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, and the electron transport region is located between the light-emitting layer and the cathode, characterized in that: The hole transport region comprises the compound according to claims 1-7. 10 . An electronic device comprising the organic electroluminescent element according to claim 9 .

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