Compound and application thereof as organic electroluminescent material

Abstract

The invention belongs to the technical field of photoelectric materials, and particularly relates to a compound and application thereof as an organic electroluminescent material, the compound has a structure shown in a formula (1), and # imgabs0 # X is selected from O or S. According to the compound disclosed by the invention, due to the fact that phenanthrofuran (thiophene) and # imgabs 1 # jointly form a heteroarylamine compound in the structure, the stability, carrier mobility and the like of the compound are more suitable for being used as an organic electroluminescent material to be used in an organic electroluminescent element, and particularly, the compound can be used as an organic electroluminescent material in a hole transport region; and the current efficiency is better. In more detail, the organic electroluminescent element can be used as an organic electroluminescent material of the second hole transport layer, and at the time, the organic electroluminescent element has higher efficiency.

Description

Technical Field

[0001] The invention belongs to the technical field of photoelectric materials, and particularly relates to a compound and its application as an organic electroluminescent material. 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 components usually include a hole transport layer, a light-emitting layer, and an electron transport layer. Holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. The injected electrons and holes combine in the light-emitting region to form an excited state, and emit light when the excited state returns to the ground state. In order to promote the entry of holes into the light-emitting region and reduce the overflow of electrons into the hole transport region, new hole transport materials need to be developed to solve this problem. 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] X is selected from O or S,

[0010] 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,

[0011] Ar 1 ,Ar 2each 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;

[0012] Preferably, L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group, wherein the heteroatoms of the heteroarylene group are independently selected from O or S;

[0013] Preferably, 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,

[0014] Ar 1 ,Ar 2 each 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,

[0015] The heteroatoms in the heteroaryl and heterocycloalkyl groups are each independently selected from O, S, and N;

[0016] 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.

[0017] As a preference, L 1 , L 2each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dimethylfluorenylene, substituted or unsubstituted diphenylfluorenylene,

[0018] 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, a substituted or unsubstituted carbazolylene group,

[0019] Ar 1 ,Ar 2 each 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;

[0020] 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; further preferably, the substituted substituents are each independently selected from one or more combinations of deuterium, halogen, methyl, ethyl, tert-butyl, cyclohexanyl, adamantyl, phenyl, naphthyl, phenanthrenyl, anthracenyl, biphenyl.

[0021] As a preference, -L 3 -Ar 1 -、-L 4 -Ar 2 - Each independently selected from one of the following groups:

[0022]

[0023] Preferably, -L3 -Ar 1 -、-L 4 -Ar 2 - Each independently selected from one of the following groups:

[0024]

[0025]

[0026]

[0027] Preferably, Ar 1 ,Ar 2 At least one selected from in

[0028] Y is selected from O, S, CR 9 R 10 NR 11 ,

[0029] 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,

[0030] 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,

[0031] R 11 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0032] R 9 , R 10 Each is independently selected from substituted or unsubstituted C6-C30 aryl groups,

[0033] When Y is CR 9 R 10 When R 9 , R 10 Ring-forming, formula (2) is a substituted or unsubstituted spirobifluorenyl;

[0034] Preferably, ring C is selected from a benzene ring;

[0035] Preferably, Ar 1 ,Ar 2At least one is selected from substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirobifluorenyl;

[0036] Preferably, Ar 1 ,Ar 2 One of them is selected from substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirobifluorenyl; Ar 1 ,Ar 2 the other of which is selected from 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;

[0037] The substituted substituents are each independently selected from one or more combinations of deuterium, halogen, methyl, ethyl, tert-butyl, cyclohexyl, adamantyl, phenyl, naphthyl, phenanthrenyl, anthracenyl, and biphenyl.

[0038] As a preference, -L 3 -Ar 1 -Selected from one of the following groups:

[0039]

[0040]

[0041] -L 4 -Ar 2 -Selected from one of the following groups

[0042]

[0043] Preferably, -L 3 -Ar 1 -Selected from one of the following groups:

[0044]

[0045]

[0046]

[0047] -L 4 -Ar 2 -Selected from one of the following groups:

[0048]

[0049]

[0050] As a preference, L 1 , L 2 each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, a substituted or unsubstituted diphenylfluorenylene group,

[0051] Preferably, L 1 Selected from single bonds, L 2 Selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dimethylfluorenylene, substituted or unsubstituted diphenylfluorenylene;

[0052] Preferably, -L 1 L 2 -Selected from one of the following groups:

[0053]

[0054] Preferably, -L 1 L 2 -Selected from one of the following groups:

[0055]

[0056] Preferably, the compound is selected from one of the following compounds numbered O1-O468:

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] And the phenanthrofuran of the compounds shown in the above numbers O1-O468 Phenanthiophene One of the formed compounds S1-S468 was replaced.

[0086] A use of the compound of the invention as an organic electroluminescent material.

[0087] 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 according to claims 1 to 7.

[0088] 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.

[0089] An electronic device comprises the organic electroluminescent element of the present invention.

[0090] The beneficial effects of the present invention are:

[0091] The compound of the present invention has a structure of phenanthrofuran (thiophene) and The heteroaromatic amine compound is formed together, and its stability, carrier mobility, etc. are more suitable for use 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 of a second hole transport layer, and at this time, the organic electroluminescent element has a higher efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] Figure 1 is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1,

[0093] 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

[0094] 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.

[0095] 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.

[0096] The reagents used in the following examples, unless otherwise specified, can be purchased from conventional biochemical reagent stores.

[0097] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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 aromatic group means that when it is unsubstituted, the number of carbon atoms in the aromatic 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.

[0107] 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,

[0108] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0109] When two or more substituents are present, the two or more substituents may be the same or different.

[0110] Refers to the replacement position.

[0111] 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.

[0112] 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.

[0113] Organic electroluminescent element

[0114] 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.

[0115] 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.

[0116] 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.

[0117] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0118] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0119] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0120] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0121] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0122] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0123] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0124] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0125] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0126] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0127] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0128] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0129] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0130] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0131] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0132] 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.

[0133] 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.

[0134] The organic electroluminescent element of the present specification can be manufactured by using materials and methods known in the art, except that one or more of the organic layers is prepared by using the compound comprising Formula I.

[0135] 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.

[0136] 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.

[0137] 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 with 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 luminescent host and dopant, F4-TCNQ (22,3,5,6-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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] The electron injection layer is a layer that injects electrons from the electrode.

[0143] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0144] 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.

[0145] 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.

[0146] LC-MS brand: Waters, model: SQ Detector 2

[0147] NMR brand: Bruker, model: AVANCE NEO 400

[0148] DSC25 brand: TA, nitrogen atmosphere.

[0149] 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.

[0150]

[0151]

[0152] Bpin refers to

[0153] Synthesis Example 1 (Compound O50)

[0154] 1. Synthesis of Intermediate 1

[0155]

[0156] Under nitrogen atmosphere, raw material a (50g, 62mmol), o-bromoiodobenzene (51, 78mmol), sodium carbonate (14g, 142mmol), Pd (dppf) Cl2 (1.1g, 1.42mmol), CuBr (1.1g, 1.42mmol) were added to THF (500mL) and heated to reflux reaction. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, concentrated and dried, and purified with dichloromethane through a 200-300 mesh silica gel quick column. Concentration gave a solid, which was slurried with n-hexane to obtain 22g of intermediate 1 (white solid) with a yield of 72%.

[0157] LC-MS (APCI): 381.20 (M+H + ).Calcd for:C21H14BrFO

[0158] 2. Synthesis of Intermediate 2

[0159]

[0160] Under nitrogen atmosphere, intermediate 1 (50 g, 48.7 mmol) and trifluoromethanesulfonic acid (1.1 g, 0.97 mmol) were placed in a four-necked reaction bottle, and 300 mL of DCM was added, and the mixture was heated to reflux for reaction. After the reaction was completed, the reaction solution was cooled to room temperature and directly filtered. The mixture was purified by reflux beating with 160 mL of ethanol to obtain 20 g of intermediate 2 with a yield of 65%.

[0161] LC-MS (APCI): 381.20 (M+H + ).Calcd for:C21H14BrFO

[0162] 3. Synthesis of Intermediate 3

[0163]

[0164] Under nitrogen atmosphere, intermediate 2 (20 g, 25.4 mmol) was placed in a four-necked reaction bottle, and 200 mL of dichloromethane was added, followed by slow dropwise addition of BBr3 (5 g, 7.1 mmol) for reaction at room temperature. After the reaction was completed, the mixture was filtered through a silica gel column (n-hexane: dichloromethane volume = 3:1) to obtain 15 g of intermediate 3, with a yield of 81%.

[0165] LC-MS (APCI): 367.20 (M+H + ).Calcd for:C20H12BrFO

[0166] 4. Synthesis of Intermediate 4

[0167]

[0168] Under nitrogen atmosphere, intermediate 3 (15 g, 22.4 mmol) and sodium carbonate (14 g, 142 mmol) were placed in a four-necked reaction bottle, and 200 mL of DMF was added, and the mixture was heated under reflux for reaction. After the reaction was completed, the mixture was filtered through a silica gel column (pure hexane) to obtain 10 g of intermediate 4 with a yield of 71%.

[0169] LC-MS (APCI): 347.20 (M+H + ).Calcd for:C20H11BrO

[0170] 5. Synthesis of the final product compound O50

[0171]

[0172]

[0173] Under nitrogen atmosphere, intermediate 4 (10 g, 22 mmol), raw material b (11, 21 mmol), sodium carbonate (9 g, 50 mmol), Pd (dppf) Cl2 (0.5 g, 1.42 mmol), THF / H2O (3:1) (100 mL) were added and heated to reflux for reaction. After the reaction was completed, the reaction solution was cooled to room temperature and filtered to obtain a solid, which was refluxed with toluene to obtain the final product (white solid) with a yield of 91%.

[0174] LC-MS (APCI): 664.80 (M+H + ).Calcd for:C50H33NO

[0175] 1H NMR (400MHz, Methylene Chloride-d2) δ7.80 (s, 1H), 7.76-7.73 (m, 2H), 7.62-7.56 (m, 5H), 7.52 (td, 1H), 7.49-7.43 (m, 5H) ), 7.37-7.26(m, 9H), 7.26-7.19(m, 2H), 7.04-6.99(m, 2H), 6.76-6.71(m, 4H), 6.65-6.60(m, 2H).

[0176] Glass transition temperature Tg: 113°C.

[0177] Synthesis Example 2 (Compound O155)

[0178] 1. Synthesis of intermediates

[0179]

[0180] Under nitrogen atmosphere, 1-bromo-3-iodobenzene (89.2g, 315mmol), 2-ethyl-6-fluoro-2′-methoxy-1,1′-biphenyl (71.3g, 315mmol), tetrakis(triphenylphosphine)palladium (7.3g, 6.3mmol) and cuprous bromide (1.8g, 12.6mmol) were added to a 2000mL four-necked bottle, and 430mL triethylamine and 660mL tetrahydrofuran were added and stirred at room temperature for 4h. The sample point plate was taken and sent for inspection. After the test results were confirmed, the liquid was extracted with dichloromethane+water, and the organic phase was spin-dried and left for standby use. The intermediate 2-(3-bromophenyl)ethyl)-6-fluoro-2′-methoxy-1,1′-biphenyl was obtained.

[0181] LC-MS (APCI): 382.24 (M+H + ).Calcd for:C 21 H 14 BrF

[0182] 2. Synthesis of intermediates

[0183]

[0184] Under nitrogen atmosphere, 2-(3-bromophenyl)ethyl)-6-fluoro-2′-methoxy-1,1′-biphenyl (120.0g, 315mmol) was put into a 2000mL four-necked bottle, and 1000mL dichloromethane was added to dissolve. 3mL trifluoromethanesulfonic acid (15mmol) was slowly added dropwise, and the reaction was stirred at room temperature for 1h. The sample point plate was taken and sent for inspection. After the test results were confirmed, the liquid was extracted with dichloromethane+water, the organic phase was spin-dried, the solid product was precipitated, and the product was filtered to obtain the product, and pure n-hexane was used to beat the pulp to obtain the intermediate 9-(3-bromophenyl)-4-fluoro-5-methoxyphenanthrene 100.0g (wet weight), which was retained for standby use.

[0185] LC-MS (APCI): 382.24 (M+H + ).Calcd for:C 21 H 14 BrF

[0186] 3. Synthesis of intermediates

[0187]

[0188] Under nitrogen atmosphere, 9-(3-bromophenyl)-4-fluoro-5-methoxyphenanthrene (100.0g, 262mmol) was put into a 2000mL four-necked bottle, and 1000mL dichloromethane was added to dissolve. After lowering the temperature to 0°C, 65mL boron tribromide (2.5eq) was slowly added dropwise, and the reaction was stirred at room temperature for 2h. The sample point plate was taken and sent for inspection. After the test results were confirmed, the reaction solution was poured into 1500mL ice water and extracted with dichloromethane + water. The organic phase was combined and dried to obtain an intermediate oily brown product 10-(3-bromophenyl)-5-fluorophenanthrene-4-ol about 92.5g, which was retained for standby use.

[0189] LC-MS (APCI): 368.22 (M+H + ).Calcd for:C 20 H 12 BrF

[0190] 4. Synthesis of intermediates

[0191]

[0192] Under nitrogen atmosphere, 10-(3-bromophenyl)-5-fluorophenanthrene-4-ol (92.5g, 252mmol) was put into a 2000mL four-necked bottle, 900mLN,N-dimethylformamide was added and stirred for 3min, cesium carbonate (164.0g, 504mmol) was added, and after the system was stable, the temperature was raised to 120°C, and then kept warm and stirred for 4h. The sample point plate was taken and sent for inspection. After the test results were confirmed, the reaction was stopped and heating was stopped. After cooling, cesium carbonate was filtered to remove the cesium carbonate, and the filtrate was extracted with ethyl acetate + water. The sample was purified by column chromatography (pure hexane) to obtain about 30.0g of white solid 8-(3-bromophenyl)phenanthrene [4,5-bcd] furan, which was retained for standby use.

[0193] LC-MS (APCI): 348.21 (M+H + ).Calcd for:C 20 H 11 B O

[0194] 5. Synthesis of intermediates

[0195]

[0196] Under nitrogen atmosphere, N, N-di([1,1′-biphenyl]-4-yl)-4-bromodibenzo[b,d]furan-1-amine (10.0 g, 17.6 mmol), 4,4,4′,4′,5,5′,5′,5′-octamethyl-2,2′-bis(1,3,2-dioxaborane) (5.4 g, 21.2 mmol), potassium acetate (3.5 g, 35.30 mmol), bistriphenylphosphine palladium dichloride (247 mg, 0.35 mmol) were put into a four-necked bottle, 1,4-dioxane 100 mL was added, the temperature was raised to reflux of the reaction system, and then the temperature was kept and stirred for 4 hours. The sample point plate was taken and sent for inspection. After the test results were confirmed, the reaction was terminated and the heating was stopped. The mixture was extracted with dichloromethane + water, and the sample was passed through a chromatography column (n-hexane: dichloromethane volume = 5:1) to obtain about 8.8 g of solid N,N-di([1,1′-biphenyl]-4-yl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-1-amine.

[0197] LC-MS (APCI): 614.56 (M+H + ).Calcd for:C 42 H 36 BNO3

[0198] 6. Synthesis of the final product compound O155

[0199]

[0200] Under nitrogen atmosphere, 8-(3-bromophenyl)phenanthro[4,5-bcd]furan (5.0g, 14.4mmol), N,N-di([1,1′-biphenyl]-4-yl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)dibenzo[b,d]furan-1-amine (8.8g, 14.4mmol), potassium carbonate (4.0g, 28.8mmol) and tetrakis(triphenylphosphine)palladium (333mg, 0.28mmol) were put into a four-necked bottle, 90mL of tetrahydrofuran and 30mL of deionized water were added, and the temperature was heated to reflux of the reaction system, and then the temperature was kept and stirred for 4h. The sample point plate was taken and sent for inspection. After the test results were confirmed, the reaction was terminated and the heating was stopped. Extract with dichloromethane + water, mix the sample and pass it through a chromatography column (n-hexane: dichloromethane = 10:1 to 1:3) to obtain about 4.5 g of white solid N,N--([1,1′-biphenyl]-4-yl)-4-(3-(phenanthro[4,5-bcd]furan-8-yl)phenyl)dibenzo[b,d]furan-1-amine (compound O155).

[0201] LC-MS (APCI): 754.90 (M+H + ).Calcd for:C56 H 35 NO2

[0202] 1 H NMR (400MHz, Methylene Chloride-d2)δ8.47(t,1H),8.23(d,2H),8.10(dt,1H),7.99-7.94(m,2H),7.93-7.89(m,2H),7.85-7.77(m,3H),7.74(d,1H),7.6 6(dt, 1H), 7.64-7.61(m, 4H), 7.60-7.56(m, 4H), 7.54(dt, 1H), 7.47-7.42(m, 5H), 7.37-7.32(m, 2H), 7.30(dd, 5H), 7.15(ddd, 1H).

[0203] Glass transition temperature Tg: 145°C.

[0204] The following application examples further illustrate the application of the compound of the present invention and the organic electroluminescent element containing the compound.

[0205] Application Example 1

[0206] 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.

[0207] The specific device structure is:

[0208] ITO / HT1-PD3%(10nm) / HT1(60nm) / HT2(5nm) / BH-BD3%(20nm) / HB(5nm) / ET-LiQ50%(30nm) / Mg∶Ag 1∶9(100nm)

[0209] Device preparation process:

[0210] 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.

[0211] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8In 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 encapsulated with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic component 1.

[0212] The compound (No. O155) in Synthesis Example 2 was used to replace the material HT2 of the second hole transport layer to prepare an organic electronic device 2.

[0213] The above abbreviated compounds are specifically:

[0214]

[0215]

[0216] Test Results

[0217] The organic electronic component obtained by the above method was tested under the following test conditions:

[0218] IVL test instrument: F STAR Optical Measurement Systems, model: FS-2000GA4; atmospheric environment, room temperature, driving voltage, current efficiency, EQE external quantum efficiency are all at a current density of 15mA / cm 2 The following test is performed and the test results are shown in Table 1.

[0219] Table 1

[0220]

[0221] According to Table 1, the compound of the present invention (compound No. O155) is used to replace the material HT2 of the second hole transport layer to prepare an organic electronic device, which has a higher current efficiency and a higher external quantum efficiency.

[0222] 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 higher glass transition temperature of the compound of the present invention makes it easy to form a pinhole-free film during vacuum evaporation, which is beneficial to improving the performance of the device.

[0223] 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), X is selected from O or S, 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, 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: L 1 , L 2 each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dimethylfluorenylene, substituted or unsubstituted diphenylfluorenylene, 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, a substituted or unsubstituted carbazolylene 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.

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

4. The compound according to claim 1, characterized in that: Ar 1 ,Ar 2 At least one selected from in Y is selected from O, S, CR 9 R 10 NR 11 , 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, R 11 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 9 , R 10 Each is independently selected from substituted or unsubstituted C6-C30 aryl groups, When Y is CR 9 R 10 When R 9 , R 10 The formula (2) is a substituted or unsubstituted spirobifluorenyl.

5. The compound according to claim 4, characterized in that -L 3 -Ar 1 -Selected from one of the following groups: -L 4 -Ar 2 -Selected from one of the following groups 6. The compound according to claim 5, 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 naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, and a substituted or unsubstituted diphenylfluorenylene group.

7. The compound according to claim 1, characterized in that The compound is selected from one of the following compounds numbered O1-O468: And the phenanthrofuran of the compounds shown in the above numbers O1-O468 Phenanthiophene One of the formed compounds S1-S468 is replaced.

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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