Material for organic light-emitting device and organic light-emitting device

Abstract

The present invention provides a material for an organic electroluminescent device, an organic electroluminescent device, and provides a compound of formula (1): # imgabs0 # formula (1), exhibiting a reduced driving voltage and a longer service life as an organic electroluminescent material, particularly a charge generating layer material.

Description

Technical Field

[0001] The present invention belongs to the technical field of photoelectric materials, and in particular relates to a material for an organic electroluminescent device and an organic electroluminescent device. Background Art

[0002] Over the past decade, OLED, as a new display technology, has made significant progress. In terms of brightness, luminous efficiency, and lifespan, OLED devices have essentially reached practical requirements. However, to better meet customer needs, significant improvements are needed in driving voltage, lifespan, and other performance characteristics.

[0003] Therefore, there is an urgent need to develop new materials to improve the driving voltage and life of the device. Summary of the Invention

[0004] The present invention provides a material for an organic electroluminescent device and an organic electroluminescent device comprising the material. The organic electroluminescent device prepared using the material has a reduced driving voltage and a durable service life.

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

[0006] A material for an organic electroluminescent device having a structure shown in formula (1)

[0007] Y is selected from O or S, X is selected from O or S,

[0008] L 1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0009] L 2 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0010] R 1 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0011] R 2 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0012] The heteroatoms in the heteroarylene group and the heteroaryl group are selected from one or more of N, O, and S.

[0013] As a preference, L 1 , L 2Each 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 phenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranylene group, and a substituted or unsubstituted dibenzothiophenylene group.

[0014] More preferably, L 1 , L 2 Each independently selected from a single bond, a substituted or unsubstituted group

[0015]

[0016]

[0017] Represents a replacement position.

[0018] As a preference, -L 1 -L 2 - a single bond, a substituted or unsubstituted group

[0019]

[0020]

[0021] As a preference, R 1 、R 2 Each is independently selected from phenyl, naphthyl, and pyridyl.

[0022] More preferably, R 1 、R 2 Each independently selected

[0023] Preferably, the substituents in the above-mentioned substituted or unsubstituted C3-C30 heteroarylene group, substituted or unsubstituted C3-C30 heteroaryl group, substituted or unsubstituted C6-C30 arylene group, and substituted or unsubstituted C6-C30 aryl group are each independently selected from the group consisting of one or more combinations of deuterium, halogen, cyano, C1-C4 alkyl, C3-C10 cycloalkyl, C3-C30 heteroaryl, and C6-C30 aryl groups.

[0024] Preferably, the substituents in the substituted or unsubstituted C3-C30 heteroarylene group, substituted or unsubstituted C3-C30 heteroaryl group, substituted or unsubstituted C6-C30 arylene group, and substituted or unsubstituted C6-C30 aryl group are selected from deuterium, and the number of deuterium can be one hydrogen substituted by deuteration, part of the hydrogen substituted by deuteration, or all the hydrogen substituted by deuteration.

[0025] Preferably, the C3-C30 heteroaryl group is selected from pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, furyl, thienyl, pyrrolyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, and indolyl.

[0026] Preferably, the C3-C30 heteroarylene group is selected from pyridylene, pyrimidylene, pyrazinylene, pyridazinylene, triazinylene, quinolylene, isoquinolylene, quinoxalylene, quinazolinylene, furylene, thienylene, pyrrolylene, benzofuranylene, dibenzofuranylene, benzothienylene, dibenzothienylene and indolylene.

[0027] Preferably, the C6-C30 aryl group is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, phenyl, pyrenyl, triphenylene, fluoranthenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, biphenyl, terphenyl, phenylnaphthyl.

[0028] Preferably, the C6-C30 arylene group is selected from phenylene, naphthylene, anthrylene, phenanthrenyl, phenylene, pyrenyl, triphenylene, fluoranthenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, biphenylene, terphenylene, phenylene naphthyl.

[0029] In one embodiment, X is selected from O.

[0030] In one embodiment, Y is selected from O.

[0031] Preferably, formula (1) is selected from any of the following deuterated or undeuterated compounds:

[0032]

[0033]

[0034]

[0035]

[0036] The present invention provides an organic electroluminescent device comprising the material for an organic electroluminescent device according to the present invention. Preferably, the organic electroluminescent device comprises an anode, a cathode, and an organic layer positioned between the anode and the cathode, wherein the organic layer comprises multiple layers, at least one of which comprises the material for an organic electroluminescent device according to the present invention.

[0037] Preferably, at least two light-emitting units are included between the anode and the cathode, and the material for the organic electroluminescent device of the present invention is included between the light-emitting units.

[0038] Preferably, at least two light-emitting units are included between the anode and the cathode, an N-type charge generation layer and a P-type charge generation layer are included between the light-emitting units, and the N-type charge generation layer includes the material for the organic electroluminescent device described in the present invention.

[0039] The N-type charge generation layer contains the material for organic electroluminescent devices described in the present invention, which means that it includes one N-type charge generation layer containing the material for organic electroluminescent devices described in the present invention; or multiple N-type charge generation layers contain the material for organic electroluminescent devices described in the present invention. When there are more than or equal to 2 N-type charge generation layers containing the material for organic electroluminescent devices described in the present invention, the materials for organic electroluminescent devices are the same or different.

[0040] The stacked structure of the present invention refers to n light-emitting units, where n is greater than or equal to 2, and the number of N-type charge generation layers is n-1.

[0041] The material for an organic electroluminescent device of the present invention is used in combination with a metal as an N-type charge generation layer.

[0042] Preferably, the N-type charge generation layer further comprises metal.

[0043] Preferably, the N-type charge generation layer further comprises one or more of alkali metals, alkaline earth metals or rare earth metals.

[0044] The alkali metal may be Li, the alkaline earth metal may be Mg, and the rare earth metal may be Sm, Eu, or Yb.

[0045] Compared with the prior art, the present invention has the following beneficial effects: and connection), and ( and Compared with the organic electroluminescent device prepared by the method of FIG, the driving voltage is lower and the life span is longer. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a schematic structural diagram of the organic electroluminescent device described in Application Example 1, wherein: a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a second hole transport layer 4, a light-emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an N-type charge generation layer 8, a P-type charge generation layer 9, a hole transport layer 10, a second hole transport layer 11, a light-emitting layer 12, a hole blocking layer 13, an electron transport layer 14, and a second electrode layer 15, wherein 100 is a first light-emitting unit and 200 is a second light-emitting unit. DETAILED DESCRIPTION

[0047] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present application belongs.

[0048] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "include" and / or "including" are used in this specification, they indicate that they are not limited to the contents disclosed in this specification.

[0049] The present invention will now be further described in conjunction with specific examples. The following examples are only intended to explain the present invention but do not limit the present invention. The test samples and test procedures used in the following examples include the following (if the specific experimental conditions are not specified in the examples, they are usually based on conventional conditions or the conditions recommended by the reagent company; the reagents, consumables, etc. used in the following examples, unless otherwise specified, can be obtained from commercial sources).

[0050] 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 concept of the present invention to those skilled in the art.

[0051] As used herein, the term "C1-C4 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 4 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, and tert-butyl.

[0052] As used herein, 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 groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0053] 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. The C6-C30 refers to the number of carbon atoms in the ring constituting the aryl, excluding the number of carbon atoms in the substituent. Further, the 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, perylene, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl, etc.

[0054] As used herein, the term "arylene" refers to a divalent aromatic group derived from an "aryl" group by removing a hydrogen atom. For example, a phenyl group can be converted to a phenylene group by removing a hydrogen atom, and a naphthyl group can be converted to a naphthylene group by removing a hydrogen atom.

[0055] As used herein, the term "C3-C30 heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic heterocyclic aromatic hydrocarbon having 3 to 30 carbon atoms. The C6-C30 refers to the number of carbon atoms in the ring that constitutes the heteroaryl group and does not include the number of carbon atoms in the substituent. In this connection, at least one carbon atom, preferably 1-3 carbon atoms, in the ring is substituted with a heteroatom such as N, O, or S. Furthermore, such heteroaryl groups may have a form in which two or more rings are simply attached to each other or fused to each other or to an aryl group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, azacarbazolyl, diazacarbazolyl, dibenzofuranyl, dibenzothienyl, and the like, but the present invention is not limited thereto.

[0056] As used herein, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl" by removing a hydrogen atom. For example, a pyridyl group can be converted into a pyridylene group by removing a hydrogen atom from a pyridyl group.

[0057] As used in the present invention, the term "substituted" refers to a group in which one or more hydrogen atoms in a compound are 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, unless otherwise specified in this specification, is specifically any of the following groups:

[0058]

[0059] The number of substitutions may be one or more. When two or more substituents are present, the two or more substituents may be the same or different.

[0060] As used herein, the term "single bond" refers to a direct bond, such as L 1 is selected from single bonds, then formula (1) is

[0061] As used in the present invention, hydrogen atoms include protium, deuterium, and tritium. The compounds of the present invention may contain deuterium atoms from natural sources, or deuterium atoms may be introduced 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 less than 100%, or less than 95%, or less than 90%, or less than 80%. The deuteration rate may also be greater than 1%, or greater than 5%, or greater than 10%. If the deuteration rate is not 100%, it represents a mixture of deuterated and undeuterated compounds, or a mixture of a fully deuterated and incompletely deuterated compound, or a mixture of a fully deuterated and undeuterated compound and an incompletely deuterated compound.

[0062] As used in the present invention, for example, in expressions such as “a substituted or unsubstituted aryl group having 6 to 30 carbon atoms”, “the number of carbon atoms is 6-30” means the number of carbon atoms when the aryl group is unsubstituted, and does not include the number of carbon atoms of the substituent when substituted. The number of carbon atoms in the aryl group can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15...30.

[0063] As used in the present invention, terms such as first, second, A, and B 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.

[0064] organic electroluminescent elements

[0065] 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. The organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0066] The organic layer further includes one or more of a hole injection layer, a hole transport layer, a second hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0067] 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 the form of a series of multiple light-emitting units.

[0068] As simple light emitting elements, the following may be mentioned, but are not limited to these:

[0069] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0070] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0071] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0072] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0073] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0074] (6) hole transport layer / second hole transport layer / fluorescent light emitting layer / electron transport layer;

[0075] (7) hole transport layer / second hole transport layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0076] (8) hole transport layer / second hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0077] (9) hole transport layer / second hole transport layer / phosphorescent light emitting layer / hole blocking layer / electron transport layer;

[0078] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0079] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0080] (12) hole injection layer / hole transport layer / second hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0081] (13) hole injection layer / hole transport layer / second hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0082] The phosphorescent / fluorescent light-emitting layers may each emit light of a different color.

[0083] As a tandem organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also generally be 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.

[0084] 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.

[0085] 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 material layers comprises the compound of the present invention.

[0086] Anode materials can be materials with relatively large work functions, including transparent conductive oxides, metals, and conductive polymers. Specific examples of anode materials include, but are not limited to, 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; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

[0087] Cathode materials typically use materials with a low work function to facilitate electron injection into the organic layer. Examples of cathode materials include metals, metal oxides, and conductive polymers. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; and multilayer structures such as LiF / Al or LiO2 / Al.

[0088] The hole injection layer (HIL) is a layer that injects holes from the electrodes and has the ability to transport holes. To reduce the energy level difference between the electrodes, the HIL is primarily based on aromatic amine compounds. Other materials used include copper phthalocyanine, HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene), α,α',α"-1,2,3-cycloalkyltriylidene tris[4-cyano-2,3,5,6-tetrafluorophenylacetonitrile], α,α',α"-1,2,3-cyclopropyltriylidene tris[2,6-dichloro-3,5-difluoro-4-(trifluoromethyl)phenylacetonitrile], and α,α',α"-1,2,3-cycloalkyltriylidene tris[2,3,4,5,6-pentafluorophenylacetonitrile].

[0089] 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 weight or high molecular weight materials can also be used.

[0090] 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.

[0091] A luminescent material is a material that receives holes and electrons from the hole transport layer and 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 dopant material. Red, green, or blue luminescent materials can be used, and two or more luminescent materials can be mixed as needed. Both fluorescent and phosphorescent materials can be used as luminescent materials. The luminescent material can be a single-component material or a multi-component material.

[0092] 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. It is a material with high electron mobility. 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. Metal complexes, and polymer materials and small molecule materials can also be used.

[0093] The hole blocking layer material can be used to block holes from escaping from the light emitting layer.

[0094] Depending on the materials used, the organic light-emitting device of the present specification can be a top-emitting device, a bottom-emitting device, or a dual-emission device.

[0095] The charge generation layer refers to the intermediate layer between the anode and cathode in a tandem structure device, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, which can effectively separate charges and effectively transport carriers. The P-type layer material can be a quinone derivative or an axial compound, and the hole injection layer material can be used. The N-type layer can be a compound containing formula (1) as a main body and a metal dopant, and the metal can be selected from Li, Mg, and Yb.

[0096] In one embodiment of the present invention, the method for forming each layer is not particularly limited. Conventionally known methods such as vacuum evaporation and spin coating can be used. Each layer, such as the light-emitting layer, can be formed by vacuum evaporation, molecular beam evaporation (MBE), or by a known coating method such as dipping, spin coating, casting, rod coating, or roller coating of a solution dissolved in a solvent.

[0097] Test instrument model

[0098] LC-MS brand: Waters, model: SQ Detector 2

[0099] NMR brand: Bruker, model: AVANCE NEO 400

[0100] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and known synthesis methods. There are many synthesis methods for the compounds of the present invention, and the following general formula is only one of the synthesis methods.

[0101]

[0102] K is independently selected from F, Cl, Br, and I; the rest of the definitions are the same as above.

[0103] Bpin is To replace the position.

[0104] The following are specific examples of the synthesis of the compounds of the present invention, but are not limited to the compounds exemplified below.

[0105] Synthesis Example 1: Synthesis of Compound 4

[0106]

[0107] Dissolve diphenylphosphine oxide (20 g, 98.92 mmol), 1-bromo-4-iodonaphthalene (42.8 g, 128.59 mmol), potassium carbonate (41 g, 596.75 mmol), palladium acetate (672 mg, 2.9 mmol), and bis(2-diphenylphosphinophenyl) ether (1.598 g, 2.9 mmol) in 1,4-dioxane solution and reflux under nitrogen for 5 hours. After completion of the reaction, pass through a silica gel funnel, concentrate, and slurry with n-hexane to obtain 21 g of intermediate 4-1.

[0108] LC-MS: [M+H] + =407.13

[0109]

[0110]

[0111] Dissolve intermediate 4-1 (21 g, 51.60 mmol), pinacol diboron (15.72 g, 61.90 mmol), potassium acetate (15 g, 0.15 mmol), and 1,1-bis(diphenylphosphino)diphenylferric palladium chloride (1.13 g, 1.57 mmol) in 1,4-dioxane solution and reflux under nitrogen for 4 hours. After the reaction, pass through a silica gel funnel, concentrate, and slurry with n-hexane to obtain 26 g of intermediate 4-2.

[0112] LC-MS: [M+H] + =455.19

[0113]

[0114] Intermediate 4-2 (26 g, 57.27 mmol), 8-bromophenanthrene〔4,5-bcd〕furan (11.1 g, 40.05 mmol), potassium carbonate (31.62 g, 229.13 mmol), and tetrakis(triphenylphosphine)palladium (1.98 mg, 1.71 mmol) were dissolved in a solution of tetrahydrofuran:water (4:1 by volume) and refluxed under nitrogen for 3 hours. After completion of the reaction, the mixture was separated, passed through a silica gel funnel, concentrated, and crystallized from ethyl acetate to obtain 13.5 g of compound 4.

[0115] LC-MS: [M+H] + =519.30

[0116] 1H NMR(400MHz,Methylene Chloride-d2)δ8.79(d,1H),8.11(s,1H),7.98–7.90(m,2H),7.87–7.78(m,6H),7.77 –7.71(m,2H),7.65(dddd,2H),7.62–7.55(m,5H),7.54–7.47(m,2H),7.37(ddd,2H).

[0117] Synthesis Example 2: Synthesis of Compound 11

[0118]

[0119] Under an N2 atmosphere, 20 g of 4-bromo-1-chlorodibenzo[b,d]furan, 16 g of diphenylphosphine oxide, 20 g of potassium carbonate, 0.8 g of palladium acetate, and 1.9 g of bis(2-diphenylphosphinophenyl)ether were added to a four-necked reaction flask. 200 ml of anhydrous dioxane was then added and the mixture was heated to reflux. After completion of the reaction, the mixture was cooled to room temperature, filtered, and slurried with water and then ethanol to obtain 23.8 g of intermediate 11-1, a yield of 82.9%.

[0120] LC-MS (APCI): 403.17 (M+H + ).

[0121]

[0122] Under a nitrogen atmosphere, 15g of intermediate 11-1, 12.3g of pinacol diboronate, 9.2g of potassium acetate, and 1.4g of 1,1'-bis(diphenylphosphinoferrocene)palladium dichloride were added to a four-necked reaction flask. 250ml of anhydrous dioxane was then added and the mixture was heated to reflux. After the reaction was complete, the mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The mixture was dried over anhydrous sodium sulfate and then mixed with silica gel. Column chromatography (n-hexane:dichloromethane = volume ratio 3:1) afforded 16.8g of intermediate 11-2 as a solid, with a yield of 91.3%. LC-MS (APCI) results: 495.35 (M+H + ).

[0123]

[0124] Under N2 atmosphere, 9.2 g of 8-bromophenanthro[4,5-bcd]furan, 16.8 g of intermediate 11-2, 2 g of tetrakis(triphenylphosphine palladium), and 9.4 g of potassium carbonate were added to a four-necked reaction flask, followed by 300 ml of tetrahydrofuran and 100 ml of water. The mixture was heated to 75°C for reaction. After completion of the reaction, the reaction solution was cooled to room temperature and purified by column chromatography (n-hexane: dichloromethane = volume ratio 3:1) to obtain 10 g of compound 11 as a solid, with a yield of 52.7%.

[0125] LC-MS (APCI): 559.33 (M+H + ).

[0126] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.11(s,1H),7.92–7.87(m,1H),7.86-7.78(m,6H),7.68–7.66(d,1H),7.64–7.59(m,2H),7.58 –7.50(m,3H),7.47–7.42(m,4H),7.40–7.38(m,1H),7.33–7.32(d,1H),7.22–7.18(m,1H),6.75–6.68(m,2H).

[0127] Synthesis Example 3: Synthesis of Compound 13

[0128]

[0129]

[0130] The synthesis of intermediates 13-1 and 13-2 refers to the synthesis of intermediates 11-1 and 11-2, except that 4-bromo-1-chlorodibenzo[b,d]furan is replaced by 1-bromo-4-chlorodibenzo[b,d]furan.

[0131] Under a nitrogen atmosphere, 8-bromophenanthrene-[4,5-bcd]furan (8 g, 29.5 mmol), intermediate 13-2 (16 g, 32.17 mmol), potassium carbonate (8.2 g, 59.4 mmol), and bistriphenylphosphine palladium dichloride (0.414 g, 0.5 mmol) were added to a four-necked reaction flask. A 120 ml mixture of tetrahydrofuran and water was then added. The mixture was heated to 75°C for 4 hours, then the temperature was reduced to room temperature. 500 ml of water and 500 ml of ethyl acetate were added to extract the reaction solution. The organic phase was separated, washed three times with water, dried over anhydrous sodium sulfate, filtered, and partially removed by rotary evaporation. The remaining product was passed through a flash chromatography column to obtain 20 g of crude product. After column chromatography (n-hexane:dichloromethane = 3:1 by volume), 11.2 g of compound 13 was obtained, with a yield of 68.3%.

[0132] LC-MS (APCI): 559.22 (M+H + ).

[0133] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.50(d,1H),8.24(s,1H),7.88(d,1H),7.82(t,1H),7.76–7.68(m,5H),7.68– 7.62(m,3H),7.59(d,1H),7.53(td,2H),7.45(td,4H),7.38–7.30(m,2H),7.18–7.10(m,2H).

[0134] Synthesis Example 4:

[0135]

[0136] Under N2 atmosphere, (4-bromophenyl)diphenylphosphine oxide (20.00 g, 55.99 mmol), 4-chloro-1-naphthaleneboronic acid (11.56 g, 55.99 mmol), potassium carbonate (11.61 g, 83.99 mmol) and 1,1'-bis(diphenylphosphino)ferrocenedichloridopalladium (826 mg, 1.12 mmol) were added to a four-necked reaction flask. 300 ml of tetrahydrofuran and 30 ml of water were added, and the temperature was raised to reflux for reaction. The reaction was completed after 8 h. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with ethyl acetate to obtain the organic phase, which was dried over anhydrous sodium sulfate and concentrated to obtain intermediate 20-1 (15.00 g, 34.18 mmol).

[0137] LC-MS: [M+H] + =439.25

[0138] Under N2 atmosphere, intermediate 20-1 (15.00 g, 34.18 mmol), pinacol diboronate (9.11 g, 35.88 mmol), bis(dibenzylideneacetone) palladium (0) (626 mg, 0.684 mmol) and 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (1.31 g, 2.73 mmol) were added to a four-necked reaction flask, 250 ml of tetrahydrofuran was added, and potassium acetate (6.71 g, 68.36 mmol) was added under nitrogen atmosphere. The temperature was raised to reflux for reaction. The reaction was completed after 5 h. After the reaction was completed, the reaction solution was cooled to room temperature, cooled to room temperature, and then passed through a chromatography column with n-hexane: dichloromethane (volume ratio 1:1) to obtain intermediate 20-2 (11.20 g, 21.12 mmol).

[0139] LC-MS: [M+H] + =531.22

[0140] Under N2 atmosphere, intermediate 20-2 (11.2 g, 21.12 mmol), 8-bromophenanthro[4,5-BCD]furan (5.15 g, 19.01 mmol), potassium carbonate (5.84 g, 42.24 mmol) and tetrakistriphenylphosphine palladium (488 mg, 0.422 mmol) were added to a four-necked reaction flask. 200 ml of tetrahydrofuran and 20 ml of water were added, and the temperature was raised to reflux for reaction. The reaction was completed after 8 h. After the reaction was completed, the reaction solution was cooled to room temperature and passed through a chromatography column with dichloromethane:tetrahydrofuran (volume ratio 50:1) to obtain compound 20 (4.5 g, 7.56 mmol).

[0141] LC-MS: [M+H] + =595.36

[0142] 1H NMR(400MHz,Methylene Chloride-d2)δ8.01(s,1H),7.93(m,1H),7.87–7.80(m,2H),7.80–7.76(m,1H),7.76–7.73(m,1H),7.72(t,1H),7.71–7.68(m,2 H),7.68–7.64(m,5H),7.64(d,1H),7.63–7.58(m,2H),7.57–7.50(m,3H),7.46(m,4H),7.39(m,1H),7.30(dd,1H),7.25(m,1H).

[0143] The following application examples further illustrate the application of the OLED luminescent compound of the present invention in the preparation of organic electroluminescent elements.

[0144] Application Example 1

[0145] This embodiment provides an organic electroluminescent device, 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 second hole transport layer 4, a light-emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an N-type charge generation layer 8, a P-type charge generation layer 9, a hole transport layer 10, a second hole transport layer 11, a light-emitting layer 12, a hole blocking layer 13, an electron transport layer 14, and a second electrode layer 15, wherein 100 is a first light-emitting unit and 200 is a second light-emitting unit. The specific device structure is:

[0146] ITO / HT1:PD(3%)(10nm) / HT1(60nm) / HT2(5nm) / ADN:BD(3%)(20nm) /

[0147] HB(5nm) / ET-Liq(50%)(10nm) / REF-1:Li(2%)(10nm) / HT1:PD(10%)(10nm) / HT1(60nm) / HT2(5nm) / ADN:BD(3%)(20nm) / HB(5nm) / ET-Liq(50%)(20nm) / Mg:Ag 1:9(100nm).

[0148] Device preparation process:

[0149] The bottom-emitting glass substrate used in this example was purchased from Guangdong Truly Display Technology Co., Ltd., and ITO was used as the first electrode layer 1. First, the bottom-emitting glass substrate was cleaned using an ITO cleaner, deionized water, and isopropyl alcohol, in that order. The bottom-emitting glass substrate was then baked at 180 degrees Celsius for 30 minutes to dry it.

[0150] Then put the bottom luminescent glass substrate into the evaporation chamber and -8 Under the condition of support, 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, PD (3%) is doped into HT1 to form a thickness of 10nm as a hole injection layer. HT1 is formed to a thickness of 60nm as a hole transport layer, and a 5nm layer of HT2 material is evaporated thereon as a second hole transport layer. Then, 3% BD is doped on the anthracene main body ADN (9,10-di(naphtha-2-yl-) anthracene) to form a blue light-emitting layer with a thickness of 20nm, and 5nm HB is evaporated thereon as a hole blocking material. ET is doped with 50% Liq to form a thickness of 10nm as an electron transport layer. 2% Li is doped in REF-1 to form an N-type charge generation layer with a thickness of 10nm. 10% PD is doped in HT1 to form The device comprises a 10nm thick P-type charge generation layer, HT1 formed to a 60nm thickness as a hole transport layer, and a 5nm layer of HT2 evaporated on top as a second hole transport layer. A 20nm thick blue light-emitting layer is then formed by evaporating anthracene (ADN) doped with 3% BD as a host anthracene. 5nm of HB is evaporated on top as a hole-blocking material. ET doped with 50% Liq is formed to a thickness of 20nm as an electron transport layer, and Mg:Ag (1:9) is formed to a thickness of 100nm as the second electrode 15. In this device embodiment, different materials are co-evaporated in the same layer, with the layers existing in a certain volume ratio. For example, 50% Liq is a 50% ET:50% Liq volume ratio. The material of the present invention was used after sublimation purification, HPLC: 99.9%.

[0151] 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 designated as organic electronic element 1 (comparative example).

[0152]

[0153] REF-1 Synthesis:

[0154]

[0155] Under nitrogen atmosphere, 2,8-dibromodibenzofuran (30 g, 92.03 mmol), 9-phenanthreneboronic acid (10.7 g, 48.18 mmol), potassium carbonate (25.4 g, 184.05 mmol), and tetrakistriphenylphosphine palladium (2.12 g, 1.84 mmol) were added to a four-necked reaction flask. A mixed solvent of toluene, ethanol, and water (556 ml) was then added. The mixture was heated to 80°C and allowed to react overnight. The mixture was removed from the heat and cooled to room temperature. The reaction mixture was extracted with 500 ml of water and 500 ml of ethyl acetate. The organic phase was separated, washed three times with water, dried over anhydrous sodium sulfate, filtered, and the ethyl acetate was removed by rotary evaporation to yield 45 g of a crude product. Purification by column chromatography yielded 30 g of a white solid.

[0156] LC-MS (APCI): 424.32 (M+H + ).

[0157] Under N2 atmosphere, the above product (30 g), diphenylphosphine oxide (28.6 g, 105.53 mmol), potassium phosphate (30.1 g, 217.78 mmol) and 1,3-bis(diphenylpropane)nickel dichloride (2.3 g, 4.26 mmol) were added to a four-necked reaction flask, and then N,N-dimethylformamide (500 ml) was added. The mixture was heated to 150 ° C. and reacted for 3 hours, then cooled to room temperature. 500 ml of water and 500 ml of ethyl acetate were added to extract the reaction solution. The organic phase was separated, washed three times with water, dried over anhydrous sodium sulfate, and purified by column chromatography (n-hexane: dichloromethane = volume ratio 3:1) to obtain 20 g of REF-1.

[0158] LC-MS (APCI): 545.39 (M+H + ).

[0159] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.77–8.71(m,1H),8.70–8.65(m,1H),8.25(ddd,1H),8.03(dd,1H),7.83(ddd,2H),7.75–7.52(m,12H),7.51–7.34(m,7H).

[0160] The charge generation layer is prepared by using the compound 4 prepared in Example 1 of the present invention instead of the REF-1 material to prepare the N-type charge generation layer 8, and the rest remains unchanged to prepare the organic electronic element 2.

[0161] The charge generation layer was prepared by replacing the REF-1 material with the compound 11 prepared in Example 2 of the present invention to prepare the N-type charge generation layer 8, and the rest remained unchanged to prepare the organic electronic device 3.

[0162] The charge generation layer was prepared by replacing the REF-1 material with the compound 13 prepared in Example 3 of the present invention to prepare the N-type charge generation layer 8, and the rest remained unchanged to prepare the organic electronic element 4.

[0163] Organic electroluminescent device evaluation

[0164] IVL testing instrument: F STAR Optical Measurement Systems, model: FS-2000GA4.

[0165] F STAR, Model: FS-MP72-HC24.

[0166] Life test method: Apply voltage to the obtained organic electroluminescent device 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.

[0167] The driving voltage is at a current density of 15 mA / cm 2 Next test.

[0168] See Table 1 for details.

[0169] Table 1

[0170] product Driving voltage / v LT95 / hour Electronic devices 1 (comparison) 7.99 137 Electronic devices 2 7.47 150 Electronic devices 3 7.51 142 Electronic devices 4 7.46 153

[0171] Compared to REF-1, the organic electroluminescent device prepared from the compound of the present invention not only has a significantly lower driving voltage but also has a longer service life. Compared to the structure of REF-1, the compound of the present invention has a phosphorus-oxygen group linked to phenanthrofuran, and its charge generation and transfer capabilities are superior to materials in which the phosphorus-oxygen group is linked to dibenzofuran.

[0172] The charge generation layer uses the compound 4 prepared in Example 1 of the present invention instead of the REF-1 material, and uses 1% Li instead of 2% Li to prepare an N-type charge generation layer 8. The rest remains unchanged to prepare the organic electronic element 5.

[0173] The charge generation layer uses the compound 4 prepared in Example 1 of the present invention to replace the REF-1 material, and uses 1% Yb to replace 2% Li to prepare an N-type charge generation layer 8. The rest remains unchanged to prepare the organic electronic element 6.

[0174] The charge generation layer is replaced with the compound 20 prepared in Example 4 of the present invention in place of the REF-1 material, and 1% of Yb is used to replace 2% of Li to prepare an N-type charge generation layer 8. The rest remains unchanged to prepare the organic electronic element 7.

[0175] The charge generation layer uses the compound 13 prepared in Example 3 of the present invention instead of the REF-1 material, and uses 1% Yb to replace 2% Li to prepare an N-type charge generation layer 8. The rest remains unchanged to prepare an organic electronic element 8.

[0176] Current efficiency at current density 15mA / cm 2 The following test is shown in Table 2.

[0177] Table 2

[0178] product Current efficiency / cd / A Electronic devices 5 (comparison) 12.6 Electronic devices 6 12.9 Electronic devices 7 12.9 Electronic devices 8 13.1

[0179] Replacing Li with Yb results in a device with higher current efficiency. This may be because Yb has a larger molecular weight and Li has a smaller molecular weight, making it easier to diffuse to adjacent layers, causing crosstalk and affecting the current efficiency of the device. Using rare earth metal Yb can effectively suppress crosstalk.

[0180] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from the other embodiments. Reference can be made to the descriptions of the identical or similar parts between the various embodiments. For the devices disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the descriptions are relatively simple, and the relevant parts can be referred to the descriptions of the methods.

[0181] The above is a detailed introduction to a material for an organic electroluminescent device and an organic electroluminescent device 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 intended to help understand the method and core concept of the present invention. It should be noted that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A material for an organic electroluminescent device, characterized in that Having the structure shown in formula (1), Formula (1), wherein Y is selected from O or S, X is selected from O or S, L 1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, L 2 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, R 1 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R 2 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, The heteroatoms in the heteroarylene group and the heteroaryl group are selected from one or more of N, O, and S.

2. The material for an organic electroluminescent device according to claim 1, characterized in that L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenylene group.

3. The material for an organic electroluminescent device according to claim 1, characterized in that L 1 , L 2 Each independently selected from a single bond, a substituted or unsubstituted group 4. The material for an organic electroluminescent device according to claim 1, characterized in that -L 1 -L 2 - a single bond, a substituted or unsubstituted group 5. The material for an organic electroluminescent device according to claim 1, characterized in that R 1 、R 2 Each is independently selected from phenyl, naphthyl, and pyridyl.

6. The material for an organic electroluminescent device according to claim 1, characterized in that R 1 、R 2 Each independently selected 7. The material for an organic electroluminescent device according to claim 1, characterized in that Formula (1) is selected from any of the following compounds, deuterated or not deuterated 8. An organic electroluminescent device, characterized in that The organic electroluminescent device comprises an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer comprises multiple layers, at least one of which comprises the material for an organic electroluminescent device according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that A light-emitting layer is contained between the anode and the cathode, and the material for an organic electroluminescent device according to any one of claims 1 to 7 is contained between the light-emitting layer and the cathode.

10. The organic electroluminescent device according to claim 8, characterized in that At least two light-emitting units are contained between the anode and the cathode, and an N-type charge generation layer and a P-type charge generation layer are contained between the light-emitting units. The N-type charge generation layer comprises the material for an organic electroluminescent device according to any one of claims 1 to 7; preferably, the N-type charge generation layer also includes a metal.

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