Thickened polycyclic heteroaryl compound and organic electroluminescent element containing same

Abstract

The invention belongs to the technical field of photoelectric materials, and particularly relates to a fused polycyclic heteroaryl compound and an organic electroluminescent element containing the fused polycyclic heteroaryl compound. The invention relates to a fused polycyclic heteroaryl compound, which has a structure as shown in a formula I, # imgabs0. The fused polycyclic heteroaryl compound disclosed by the invention improves the injection and transmission capabilities of electrons; the organic electroluminescent element prepared by using the compound can realize improved luminous efficiency, reduced driving voltage and durable service life. The organic electroluminescent element has better luminous efficiency and longer service life.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials, and particularly relates to a condensed polycyclic heteroaryl compound and an organic electroluminescent element containing the same. Background Art

[0002] OLEDs emit light by the cancellation of hole-electron pairs generated when holes and electrons are injected from a hole injection electrode (anode) and an electron injection electrode (cathode) into an emitting material layer (EML) disposed between the anode and the cathode. Such OLEDs can be formed on flexible transparent substrates such as plastics, can also operate at low voltages (below 10V), consume relatively low power, and provide excellent colors.

[0003] Generally, OLEDs can be divided into single-stack type and stacked type. In order to achieve a long-life OLED, a tandem OLED, that is, an OLED having a stacked structure of multiple light-emitting units, is mainly used. For example, a tandem white light OLED includes a first light-emitting stack including a blue light-emitting layer and a second light-emitting stack including a yellow-green light-emitting layer, wherein the first light-emitting stack and the second light-emitting stack are stacked vertically. This white light OLED emits white light by mixing the light emitted from the blue light-emitting layer and the light emitted from the yellow-green light-emitting layer. The stacked OLED includes a charge generation layer disposed between the first light-emitting stack and the second light-emitting stack to improve the current efficiency in each light-emitting layer while ensuring that the charge is effectively distributed to the light-emitting stack. Generally, the charge generation layer has a PN junction, in which an N-type charge generation layer and a P-type charge generation layer are stacked in sequence.

[0004] In such a charge generation layer used in a commonly used tandem OLED, due to the energy level difference between the N-type charge generation layer and the P-type charge generation layer, charges are generated at the interface between the P-type charge generation layer and the adjacent hole injection layer or hole transport layer, resulting in degradation of electron injection in the N-type charge generation layer.

[0005] When the N-type charge generation layer is doped with metal, the metal may diffuse into the P-type charge generation layer, resulting in a reduced lifespan of the OLED. In particular, common materials used for the charge generation layer do not have sufficient thermal / electrical stability. Therefore, long-term operation of the OLED leads to degradation or deterioration of the materials used for the charge generation layer. As a result, not only is the efficiency of electron injection from the interface between the P-type charge generation layer and the adjacent hole injection layer or hole transport layer to the N-type charge generation layer significantly reduced, but the efficiency of electron injection from the N-type charge generation layer to the adjacent electron transport layer is also significantly reduced, resulting in reduced performance and lifespan of the OLED.

[0006] Therefore, a compound is needed so that an organic electroluminescent element prepared by the compound can have a longer service life, a lower driving voltage and good current efficiency. Summary of the invention

[0007] The object of the present invention is to provide a condensed polycyclic heteroaryl compound, wherein an organic electroluminescent element prepared by using the compound can achieve a durable service life, a lower driving voltage and good current efficiency.

[0008] The technical solution adopted by the present invention to solve its technical problem is:

[0009] A condensed polycyclic heteroaromatic compound having a structure shown in formula I,

[0010]

[0011] R 1 , R 2 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0012] And R 1 , R 2 At least one selected from

[0013] L 1 , L 2 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] X is selected from O or S.

[0015] represents the attachment position of the substituent, Include Include Include

[0016] Preferably, R 1 , R 2 One of the selected

[0017] Preferably, L 1 It is selected from a single bond, and a substituted or unsubstituted C6-C30 arylene group.

[0018] Preferably, L 2 It is selected from a single bond, and a substituted or unsubstituted C6-C30 arylene group.

[0019] Preferably, L 1It is selected from a single bond, and a substituted or unsubstituted C6-C20 arylene group.

[0020] Preferably, L 2 It is selected from a single bond, and a substituted or unsubstituted C6-C20 arylene group.

[0021] Preferably, L 1 is selected from substituted or unsubstituted C6-C30 arylene groups.

[0022] Preferably, L 2 is selected from substituted or unsubstituted C6-C30 arylene groups.

[0023] Preferably, L 1 Selected from a single bond and a C6-C30 arylene group.

[0024] Preferably, L 2 Selected from a single bond and a C6-C30 arylene group.

[0025] Preferably, L 1 An arylene group selected from C6-C30.

[0026] Preferably, L 2 An arylene group selected from C6-C30.

[0027] Preferably, L 1 Select from single bonds.

[0028] Preferably, L 2 Select from single bonds.

[0029] The substituent of the substituted C1-C10 alkyl group or the substituted C3-C10 cycloalkyl group means that one or more H is replaced by D.

[0030] The substituent of the substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 arylene, substituted C3-C30 heteroarylene means that one or more H is replaced, and the substituents are independently selected from one or a combination of D, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl. The combination of D, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl means that two or more of them are connected by a single bond, such as deuterated C1-C10 alkyl, deuterated C6-C20 aryl, C1-C10 alkyl substituted C6-C20 aryl, but not limited thereto.

[0031] H refers to hydrogen and D refers to deuterium.

[0032] Preferably, the C1-C10 alkyl group is selected from methyl, ethyl and tert-butyl.

[0033] Preferably, the C3-C10 cycloalkyl group is selected from cyclohexyl group.

[0034] Preferably, the C6-C30 aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrene, fluoranthenyl, triphenylene, base.

[0035] Preferably, the C3-C30 heteroaryl group is selected from pyridyl, pyrimidinyl, triazine, phenazine, quinolyl and isoquinolyl.

[0036] Preferably, the C6-C30 arylene group is selected from phenylene, biphenylene, terphenylene, phenylene-substituted naphthylene, naphthylene, anthrylene, phenanthrenyl, pyrenyl, fluoranthenyl, triphenylene, ... base.

[0037] Preferably, the C3-C30 heteroarylene group is selected from pyridylene, pyrimidylene, triazinylene, phenazinylene, quinolylene and isoquinolylene.

[0038] Preferably, the C6-C20 aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrene, fluoranthenyl, triphenylene, base.

[0039] Preferably, the C3-C20 heteroaryl group is selected from pyridyl, pyrimidinyl, triazine, phenazine, quinolyl and isoquinolyl.

[0040] Preferably, the L 1 , L 2 Each independently selected from a single bond,

[0041]

[0042] As a preference, L 1 , L 2 Each independently selected from a single bond,

[0043]

[0044]

[0045] Preferably, the R 1 , R 2 At least one of

[0046]

[0047] As a preference, R 1 Selected from R 2Selected from hydrogen, phenyl, deuterated phenyl, methyl, deuterated methyl.

[0048] R 2 Selected from R 1 Selected from hydrogen, phenyl, deuterated phenyl, methyl, deuterated methyl.

[0049] Preferably, R 1 Selected from R 2 is selected from hydrogen, phenyl, deuterated phenyl, methyl, deuterated methyl; L 1 Selected from single bonds,

[0050]

[0051] L 2 Select from single bonds.

[0052] R 2 Selected from R 1 is selected from hydrogen, phenyl, deuterated phenyl, methyl, deuterated methyl; L 2 Selected from single bonds,

[0053]

[0054] L 1 Select from single bonds.

[0055] Preferably, the condensed polycyclic heteroaryl compound is selected from any one of the following compounds Nos. 1 to 114:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] The condensed polycyclic heteroaromatic compound of the present invention is used as an organic electroluminescent element material.

[0065] The invention provides an organic electroluminescent element, comprising an anode, a cathode and an organic layer between the anode and the cathode, wherein the organic layer comprises the condensed polycyclic heteroaryl compound of the invention.

[0066] Preferably, the organic layer comprises an electron transport layer and a light emitting layer, and the electron transport layer comprises the condensed polycyclic heteroaryl compound described in the present invention.

[0067] Preferably, the organic layer comprises more than or equal to two light-emitting units, a charge generation layer is included between the light-emitting units, the light-emitting units comprise an electron transport layer, and the at least one charge generation layer and / or at least one electron transport layer comprises the condensed polycyclic heteroaryl compound described in the present invention.

[0068] Preferably, the organic layer comprises more than or equal to two light-emitting units, a charge generation layer is comprised between the light-emitting units, the light-emitting units comprise an electron transport layer, the charge generation layer comprises an N-type charge generation layer and a P-type charge generation layer, and at least one of the N-type charge generation layer and the electron transport layer comprises the condensed polycyclic heteroaryl compound described in the present invention.

[0069] The electron transport layer comprises the electron transport layer of each light-emitting unit, and at least one of the N-type charge generation layer and the electron transport layer comprises the condensed polycyclic heteroaryl compound of the present invention, which means that one N-type charge generation layer comprises the condensed polycyclic heteroaryl compound of the present invention; or multiple N-type charge generation layers comprise the condensed polycyclic heteroaryl compound of the present invention; or one electron transport layer in one light-emitting unit comprises the condensed polycyclic heteroaryl compound of the present invention; or one N-type charge generation layer and one electron transport layer in one light-emitting unit comprise the condensed polycyclic heteroaryl compound of the present invention; or one N-type charge generation layer and each electron transport layer in multiple light-emitting units comprise the condensed polycyclic heteroaryl compound of the present invention; or multiple N-type charge generation layers and each electron transport layer in multiple light-emitting units comprise the condensed polycyclic heteroaryl compound of the present invention, etc. When more than or equal to 2 layers comprise the condensed polycyclic heteroaryl compound of the present invention, the condensed polycyclic heteroaryl compounds are the same or different.

[0070] An electronic device comprises the organic electroluminescent element of the present invention.

[0071] Compared with the prior art, the present invention has the following beneficial effects:

[0072] 1. The condensed polycyclic heteroaromatic compound of the present invention has a triphenylene furan or triphenylene thiophene structure and is linked to a N-containing heteroaromatic group, thereby improving the electron injection and transmission capabilities; the organic electroluminescent element prepared using the compound can achieve a long service life, and has a lower driving voltage and a higher current efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1, wherein the first electrode layer 1, the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4, the electron transport layer 5, the N-type charge generation layer 6, the P-type charge generation layer 7, the hole transport layer 8, the light-emitting layer 9, the electron transport layer 10, the electron injection layer 11 and the second electrode layer 12, wherein 100 is the first light-emitting unit and 200 is the second light-emitting unit. DETAILED DESCRIPTION

[0074] In order to more fully describe the present invention to those skilled in the art, embodiments of the present invention are provided. The scope of the present invention is not limited to the following embodiments. These embodiments can make the present invention more thorough and complete, and fully convey the viewpoints of the present invention to those skilled in the art.

[0075] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0076] 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.

[0077] 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.

[0078] As used in the present invention, the term "C6-C30 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a monocyclic ring or a combination of two or more rings and having 6 to 30 carbon atoms. Further, such an aryl may have a form in which two or more rings are simply lateral to each other or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0079] 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.

[0080] As used in the present invention, the term "C3-C30 heteroaryl group" refers to a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having 3 to 30 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S, P, B or Si. In addition, this heteroaryl group may have a form in which two or more rings are simply lateral to each other or fused to each other or fused to an aromatic group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl and the like, but the present invention is not limited thereto.

[0081] 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.

[0082] 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.

[0083] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where the substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, as long as it is not otherwise described in this specification,

[0084]

[0085] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0086] As used in the present invention, the term "phenylene-substituted naphthylene" refers to any of the following groups, but is not limited thereto,

[0087] When two or more substituents are present, the two or more substituents may be the same or different.

[0088] 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.

[0089] 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.

[0090] Organic electroluminescent element

[0091] 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.

[0092] 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.

[0093] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0094] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0095] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0096] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0097] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0098] (6) hole transport layer / electron blocking layer / fluorescent emitting layer / electron transport layer;

[0099] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0100] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0101] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0102] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0103] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0104] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0105] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0106] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0107] 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.

[0108] When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

[0109] The organic electroluminescent element of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers is prepared by using a compound comprising the formula (1).

[0110] 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.

[0111] As the cathode material, a material with a low work function is generally used to facilitate electron injection into the organic material 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.

[0112] 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.

[0113] The hole transport material is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and 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.

[0114] 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.

[0115] The electron transport material is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material can receive electrons from the cathode and transfer the electrons to the light-emitting layer. 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.

[0116] The electron injection layer is a layer that injects electrons from the electrode. The present application uses LiF, however, the present application is not limited thereto.

[0117] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0118] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0119] 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.

[0120] The charge generation layer is an intermediate layer between the anode and cathode in a tandem structure element, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, and can effectively separate charges and effectively transport carriers.

[0121] 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 general formula is only one of the synthesis methods,

[0122]

[0123] The same synthetic method can be used for different substitution positions.

[0124] Synthesis Example 1: Synthesis of Compound 1

[0125] (1) Synthesis of intermediate 1-1

[0126]

[0127] Under nitrogen atmosphere, 41.6g phenanthrenequinone, 69.2g 4-bromophenol, 6.8ml trifluoromethanesulfonic acid were added to a four-necked reaction bottle, and then 1000ml o-dichlorobenzene was added, and the temperature was raised to reflux reaction. After the reaction was completed, the reaction liquid system was desolventized until no solvent was distilled out, and water was added after cooling to room temperature, and extracted with dichloromethane. Insoluble impurities were filtered with diatomaceous earth, and the organic phase was dried with anhydrous sodium sulfate and then mixed with silica gel. After column chromatography (dichloromethane as the developing solvent), 20g of intermediate 1-1 was obtained, with a yield of 43.4%.

[0128] LC-MS (APCI): 348.11 (M+H) + .Calcd for C 20 H 11 BrO 347.21

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

[0130]

[0131] Under nitrogen atmosphere, 17.99g of intermediate 1-1, 15.8g of biboric acid pinacol ester, 10.2g of potassium acetate, and 1.5g of 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride were added to a four-necked reaction bottle, and then 400ml of anhydrous dioxane was added, and the temperature was raised to reflux reaction. After the reaction was completed, water was added after cooling to room temperature, extracted with dichloromethane, dried with anhydrous sodium sulfate, and mixed with silica gel. After column chromatography (dichloromethane as the developing solvent), 12g of intermediate 1-2 was obtained, with a yield of 58.5%.

[0132] GC-MS(EI):394.17(M + ).Calcd for C 26 H 23 BO3 394.28

[0133] (3) Synthesis of Compound 1

[0134]

[0135] Under nitrogen atmosphere, 10.97g 2-(4-bromophenyl)-1,10-phenanthroline, 12.94g intermediate 1-2, 0.76g tetrakis(triphenylphosphine palladium), 9.06g potassium carbonate were added to a four-necked reaction bottle, and then 180ml toluene, 60ml ethanol, and 60ml water were added, and the temperature was raised to 85°C for reaction. After the reaction was completed, the reaction solution was cooled to room temperature and filtered to obtain a crude product. Then, chlorobenzene was used to beat the white solid target compound 1 to obtain 9.05g, with a yield of 52.8%.

[0136] LC-MS (APCI): 523.37 (M+H+ ).Calcd for C 38 H 22 N2O 522.61

[0137] 1 H NMR (400MHz, CD2Cl2) δ9.15–9.14(d,1H),8.79–8.73(m,3H),8.65(s,1H),8.49–8.47(m,1H),8.45–8.43(d,2H),8.32–8.30(d,1H),8.25–8.23( d,1H),8.18–8.15(d,1H),7.95–7.93(d,2H),7.84–7.79(dd,2H),7.81– 7.75(q,3H),7.73–7.70(t,2H),7.68–7.64(t,1H),7.62–7.59(dd,1H).

[0138] Synthesis Example 2: Synthesis of Compound 11

[0139] (1) Synthesis of Intermediate 11-1

[0140]

[0141] Under nitrogen atmosphere, (4-bromonaphthalene-1-yl)boric acid (30.0 g, 0.120 mmol), 2-bromo-1,10-phenanthroline (31.0 g, 0.120 mmol), Na2CO3 (25.0 g, 0.24 mmol) and Pd(PPh3)4 (4.2 g, 0.004 mmol) were put into a four-necked bottle, 150 ml of toluene, 70 ml of ethanol and 70 ml of deionized water were added, and the temperature was raised to reflux of the reaction system, and then the mixture was stirred for 24 h. After cooling, 150 ml of water was added, concentrated and filtered, 1 L of water was added to the solid, stirred for 20 min, and filtered. Then toluene was slurried, and then ethyl acetate was used to slurry to obtain 28 g of white solid intermediate 11-1.

[0142] LC-MS (APCI): 385.03 (M+H) + .Calcd for:C22H13BrN2 384.03

[0143] (2) Synthesis of Compound 11

[0144]

[0145] Under nitrogen atmosphere, intermediate 1-2 (5.3 g, 13.44 mmol), intermediate 11-1 (5.8 g, 14.78 mmol), K2CO3 (3.8 g, 26.88 mmol) and Pd(PPh3)4 (0.47 g, 0.40 mmol) were placed in a four-necked bottle, 120 mL of tetrahydrofuran and 40 mL of deionized water were added, and the temperature was raised to reflux of the reaction system, and then the mixture was stirred for 24 h. The mixture was extracted with ethyl acetate and water, and the organic phases were combined and dried. The sample was purified by column chromatography with a volume ratio of n-hexane to dichloromethane of 1:20 to 5:1 to obtain 4.5 g of white solid compound 11.

[0146] LC-MS (APCI): 573.19 (M+H) + .Calcd for:C42H24N2O 572.19

[0147] 1 H NMR(400MHz,Methylene Chloride-d2)δ9.10(dd,1H),8.79(d,1H),8.78–8.76(m,1H),8.63(dd,1H),8.56– 8.52(m,2H),8.40(d,1H),8.27(dd,1H),8.21–8.17(m,1H),8.08–8.04(m,1H),7.96 (d,1H),7.90(d,1H),7.88(s,1H),7.85(d,1H),7.83(d,1H),7.78–7.72(m,2H),7. 71(dd,2H),7.68–7.66(m,1H),7.66–7.64(m,1H),7.61(dd,1H),7.47–7.43(m,2H).

[0148] The following application examples further illustrate the application of the heterocyclic compound of the present invention in the preparation of organic electroluminescent elements.

[0149] Application Example 1

[0150] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes a stacked first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, an N-type charge generation layer 6, a P-type charge generation layer 7, a hole transport layer 8, a light-emitting layer 9, an electron transport layer 10, an electron injection layer 11 and a second electrode layer 12, wherein 100 is a first light-emitting unit and 200 is a second light-emitting unit.

[0151] The specific device structure is:

[0152] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / TmPyPB(10nm) / Bphen:Li(2%)( 10nm) / NPD:F4-TCNQ(10%)(20nm) / NPD(20nm) / BH:BD(3%)(20nm) / Alq3(10nm) / LiF(0.5nm) / Al(200nm).

[0153] Device preparation process:

[0154] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 1. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0155] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8 In the case of torr, each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second. Among them, F4-TCNQ (mass content 10%) is doped into NPD to form a thickness of 10nm as a hole injection layer. NPD is formed to a thickness of 120nm as a hole transport layer, and the anthracene main body ADN (9,10-di(naphtha-2-yl-)anthracene) is doped with a 3% mass content of pyrene dopant 1,6-bis(diphenylamino)pyrene to form a blue light-emitting layer with a thickness of 20nm. TmPyPB is formed to a thickness of 10nm as the first electron transport layer, and BPhen (4,7-Diphenyl-1,10-phenanthroline) is doped with 2% mass content of Li to form an N-type charge generation layer 6 with a thickness of 10nm. F4-TCNQ with a mass content of 10% is doped on NPD. A P-type charge generation layer with a thickness of 20 nm is formed, NPD with a thickness of 20 nm is formed as a hole transport layer, an anthracene main body ADN (9,10-di(naphtha-2-yl-)anthracene) is doped with a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% to form a blue light-emitting layer with a thickness of 20 nm, Alq3 (Tris-(8-hydroxyquinolinato)aluminum) is formed with a thickness of 10 nm as a second electron transport layer, LiF is formed with a thickness of 0.5 nm as an electron injection layer, and Al is formed with a thickness of 200 nm as a cathode.

[0156] 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 electroluminescent element 1.

[0157]

[0158] Contrast structure

[0159] Bphen(4,7-Diphenyl-1,10-phenanthroline)

[0160]

[0161] Examples and Comparative Examples

[0162] Charge Generation Layer The N-type charge generation layer 6 is prepared by using the compound prepared in Example 1 of the present invention instead of the Bphen material, and the organic electroluminescent element 2 is prepared by the same method.

[0163] Charge Generation Layer The N-type charge generation layer 6 is prepared by using the compound prepared in Example 2 of the present invention instead of the Bphen material, and the organic electroluminescent element 3 is prepared by the same method.

[0164] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0165] Driving voltage and current efficiency at current density 15mA / cm 2 The following test results are shown in Table 1.

[0166] Table 1

[0167] Driving voltage(v) Current efficiency (cd / A) Lifespan LT95(h) Organic electroluminescent element 1 7.07 17.53 58 Organic electroluminescent element 2 6.90 17.76 88.38 Organic electroluminescent element 3 6.82 17.79 90.79

[0168] According to the results in Table 1, the organic electroluminescent element prepared by the compound of the present application has a lower driving voltage, a higher current efficiency and a longer service life than the organic electroluminescent element 1. The compound of the present invention is suitable for preparing a high-performance organic electroluminescent element.

[0169] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0170] The above is a detailed introduction to a condensed polycyclic heteroaromatic compound and an organic electroluminescent element containing the same provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A condensed polycyclic heteroaryl compound, characterized in that: The compound has a structure shown in formula I, R 1 , R 2 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, And R 1 , R 2 At least one selected from L 1 , L 2 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, X is selected from O or S.

2. The condensed polycyclic heteroaryl compound according to claim 1, characterized in that: The L 1 , L 2 Each independently selected from a single bond, 3. The condensed polycyclic heteroaryl compound according to claim 2, characterized in that: L 1 , L 2 Each independently selected from a single bond, 4. The condensed polycyclic heteroaryl compound according to claim 1, characterized in that: The R 1 , R 2 At least one of 5. The condensed polycyclic heteroaryl compound according to claim 1, characterized in that: R 1 Selected from R 2 is selected from hydrogen, phenyl, deuterated phenyl, methyl or deuterated methyl; or R 2 Selected from R 1 is selected from hydrogen, phenyl, deuterated phenyl, methyl or deuterated methyl.

6. The condensed polycyclic heteroaryl compound according to claim 1, characterized in that: The fused polycyclic heteroaryl compound is selected from any one of the following compounds Nos. 1 to 114:

7. Use of the condensed polycyclic heteroaryl compound according to any one of claims 1 to 6 as an organic electroluminescent element material.

8. An organic electroluminescent element comprising an anode, a cathode, and an organic layer located between the anode and the cathode, characterized in that: The organic layer comprises the condensed polycyclic heteroaryl compound according to any one of claims 1 to 6.

9. The organic electroluminescent element according to claim 8, characterized in that: The organic layer comprises an electron transport layer and a light emitting layer, and the electron transport layer comprises the condensed polycyclic heteroaryl compound according to any one of claims 1 to 6.

10. The organic electroluminescent element according to claim 9, characterized in that: The organic layer comprises two or more light-emitting units, a charge generation layer is comprised between the light-emitting units, the light-emitting units comprise an electron transport layer, and the at least one charge generation layer and / or at least one electron transport layer comprises the condensed polycyclic heteroaryl compound according to any one of claims 1 to 6.

Images