Materials for organic electroluminescent elements, organic electroluminescent elements, and consumer products

Abstract

The present invention discloses a material for an organic electroluminescent element, an organic electroluminescent element, and a consumer product. The organic electroluminescent element comprises: an anode, a cathode, and a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by the general formula (I). The hole injection layer and the charge generation layer disclosed in the present invention comprise a naphthyridine-based compound or consist of a naphthyridine-based compound, which can reduce the voltage of an OLED element and improve the efficiency and life of the element.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochromic technology, and in particular to a material for an organic electroluminescent element, an organic electroluminescent element, and a consumer product. Background Art

[0002] Generally speaking, organic luminescence refers to the phenomenon that light is emitted when electrical energy is applied to an organic substance. That is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light and heat are emitted.

[0003] As a method for effectively manufacturing organic electroluminescent elements, research has been conducted on replacing the organic layer in the single-layer manufacturing element with a multilayer structure. In 1987, Tang proposed an organic electroluminescent element with a stacked structure of functional layers of a hole layer and a light-emitting layer. Most of the organic electroluminescent elements currently used include: a substrate, an anode, a hole injection layer that receives holes from the anode, a hole transport layer that transports holes, a light-emitting layer that emits light by recombination of holes and electrons, an electron transport layer that transports electrons, an electron injection layer that receives electrons from the cathode, and a cathode. The reason for making organic electroluminescent elements with multiple layers is that since the movement speeds of holes and electrons are different, if appropriate hole injection layers and transport layers, electron transport layers, and electron injection layers are manufactured, holes and electrons can be effectively transmitted, holes and electrons can be balanced in the element, and the exciton utilization rate can be improved.

[0004] In OLED elements, the hole injection layer (HIL) facilitates hole injection from the ITO anode to the organic layer. In order to achieve a low element driving voltage, it is important to have a minimum charge injection barrier from the anode. Various HIL materials have been developed, such as triarylamine compounds with shallow HOMO energy levels, very electron-deficient heterocyclic compounds, and triarylamine compounds doped with P-type conductivity dopants. In order to improve OLED performance, such as longer element life, higher efficiency, and lower voltage, it is crucial to develop HIL materials with better performance.

[0005] Therefore, in order to overcome the above-mentioned problems of the prior art and further improve the characteristics of the organic electroluminescent element, there continues to be a demand for the development of more stable and effective substances that can be used as hole injecting and transporting substances in the organic electroluminescent element. Summary of the invention

[0006] The present invention aims to improve the voltage, efficiency and life of OLED by using a hole injection layer containing a naphthyridine-based compound. In addition, a charge injection layer containing a naphthyridine-based compound is provided, which can be used to connect a p-type charge generation layer in a tandem OLED structure to further improve the voltage, efficiency and life of the OLED.

[0007] According to one embodiment of the present invention, an organic electroluminescent element is disclosed, comprising: an anode, a cathode, and a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):

[0008]

[0009] Where: W 1 , W 2 , W 3 Each independently selected from CR 0 Or any two adjacent W 1 , W 2 , W 3 represents a group of the following formula (a), and W 1 , W 2 , W 3 Not CR at the same time 0 ;

[0010]

[0011] X is selected from S, Se, NR 1 or CR 2 R 3 ; G is selected from O, S, Se, SO or SO2; Z is selected from CR 4 Or N; and ^ indicates the corresponding adjacent W in formula (I) 1 , W 2 , W 3 ;

[0012] R 0 , R 4 In each occurrence, the same or different represents an electron withdrawing group;

[0013] R 1 , R 2 , R 3 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C3-C 40 branched alkyl or cycloalkyl, substituted or unsubstituted C1-C 40 heteroalkyl, substituted or unsubstituted C2-C 40 Alkenyl, substituted or unsubstituted C6-C60 Aryl, substituted or unsubstituted C6-C 60 Aryloxy, substituted or unsubstituted C7-C 60 Aralkyl, substituted or unsubstituted C3-C 40 Alkylsilyl, substituted or unsubstituted C6-C 60 Arylsilyl, substituted or unsubstituted C0-C 40 an amine group, or a substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, isonitrile groups, sulfenyl groups, sulfinyl groups, sulfonyl groups, phosphino groups, and phosphinooxy groups, wherein two or more adjacent groups may be optionally joined or fused to form another one or more substituted or unsubstituted rings, and the formed rings may or may not contain one or more heteroatoms N, P, B, O or S.

[0014] In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" means a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

[0015] According to another embodiment of the present invention, a material for an organic electroluminescent element is disclosed, comprising the compound represented by the above general formula (I).

[0016] According to another embodiment of the present invention, a tandem organic electroluminescent element is also disclosed, which includes an anode, a cathode, and a plurality of stacked layers arranged between the anode and the cathode, each stacked layer includes at least one light-emitting layer, and a charge generation layer is arranged between every two adjacent stacked layers, and the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer contains a compound represented by the general formula (I) as described above.

[0017] According to another embodiment of the present invention, a consumer product is also disclosed, comprising the above-mentioned organic electroluminescent element or the above-mentioned tandem organic electroluminescent element.

[0018] The hole injection layer and charge generation layer disclosed in the present invention include or consist of naphthyridine-based compounds, and can reduce the voltage of OLED elements and improve the efficiency and life of the elements. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a schematic diagram of an organic light-emitting device provided by the present invention;

[0020] Figure 2 is a schematic diagram of a tandem organic light-emitting device provided by the present invention;

[0021] Figure 3 It is a schematic diagram of another tandem organic light-emitting device provided by the present invention. DETAILED DESCRIPTION

[0022] The present invention is further described in detail below in conjunction with specific embodiments, but is not intended to limit the scope of the present invention.

[0023] OLEDs can be manufactured on a variety of substrates, such as glass, plastic, and metal. Figure 1 An organic light-emitting device 100 is shown schematically and non-limitingly. The figure is not necessarily drawn to scale, and some layer structures in the figure may be omitted as needed. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. The device 100 can be manufactured by depositing the described layers in sequence. The properties and functions of each layer and exemplary materials are described in more detail in columns 6-10 of U.S. Patent No. 7,279,704 B2, the entire contents of which are incorporated herein by reference.

[0024] There are more examples of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. An example of a host material is disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0025] The above layered structure is provided by way of non-limiting example. The functions of an OLED can be achieved by combining the various layers described above, or some layers can be omitted entirely. It can also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimal performance. Any functional layer can include several sublayers. For example, a light-emitting layer can have two layers of different light-emitting materials to achieve a desired light-emitting spectrum.

[0026] In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.

[0027] In one embodiment, two or more OLED units may be connected in series to form a series OLED, such as Figure 2 A tandem organic light-emitting device 500 is schematically and non-limitingly shown. The device 500 may include a substrate 101, an anode 110, a first unit 100, a charge generation layer 300, a second unit 200, and a cathode 290. The first unit 100 includes a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, and an electron transport layer 170, the second unit 200 includes a hole injection layer 220, a hole transport layer 230, an electron blocking layer 240, a light-emitting layer 250, a hole blocking layer 260, an electron transport layer 270, and an electron injection layer 280, and the charge generation layer 300 includes an N-type charge generation layer 310 and a P-type charge generation layer 320. The device 500 can be manufactured by depositing the described layers in sequence.

[0028] OLED can also be provided with an encapsulation layer, such as Figure 3 The organic light emitting device 600 is schematically and non-limitingly shown. Figure 2 The difference is that an encapsulation layer 102 may also be included on the cathode 290 to prevent harmful substances from the environment, such as moisture and oxygen. Any material that can provide an encapsulation function can be used as an encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly on the outside of the OLED element. Multilayer thin film encapsulation is described in U.S. Patent No. 7,968,146 B2, the entire contents of which are incorporated herein by reference.

[0029] The element manufactured according to the embodiment of the present invention can be incorporated into various consumer products of one or more electronic component modules (or units) with the element. Some examples of these consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro displays, 3-D displays, vehicle displays and taillights.

[0030] The materials and structures described herein may also be used in other organic electronic components listed above.

[0031] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed" "on" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, other layers may be present between the first and second layers. For example, a cathode may be described as being "disposed" "on" an anode even though various organic layers are present between the cathode and the anode.

[0032] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0033] A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive property of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive property of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.

[0034] Definition of Substituent Terms

[0035] Halogen or halide - as used herein includes fluorine, chlorine, bromine and iodine.

[0036] Alkyl includes straight chain and branched chain alkyl. Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, alkyl can be optionally substituted. The carbon in the alkyl chain can be substituted by other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.

[0037] Cycloalkyl as used herein includes cyclic alkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 3 to 40 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. In addition, the cycloalkyl group may be optionally substituted. The carbon in the ring may be substituted by other heteroatoms.

[0038] As used herein, alkenyl encompasses straight chain, branched chain and cyclic olefin groups. Preferred alkenyls are alkenyls containing 2 to 40 carbon atoms. Examples of alkenyls include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl and 3-phenyl-1-butenyl. In addition, alkenyl may be optionally substituted.

[0039] Aryl or aromatic groups as used herein contemplate both non-fused and fused systems. Preferred aryl groups are those containing 6 to 60 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, letrozole, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quaterphenyl.

[0040] Heterocyclyl or heterocycle as used herein contemplates both aromatic and non-aromatic cyclic groups. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclyls are those containing 3 to 7 ring atoms, including at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclyl may also be an aromatic heterocyclyl having at least one heteroatom selected from nitrogen, oxygen, sulfur and selenium atoms.

[0041] As used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms are contemplated. Preferred heteroaryls are heteroaryls containing 2 to 60 carbon atoms, more preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Suitable heteroaryls include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole, pyridineindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, In some embodiments, the heteroaryl group comprises an oxadiazole, an isocyanine ...

[0042] The alkoxy group is represented by -O-alkyl, and examples and preferred examples of the alkyl group are the same as those described above. Examples of the alkoxy group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

[0043] The aryloxy group is represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of the aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 60 carbon atoms include phenoxy and biphenyloxy.

[0044] Aralkyl is used herein to refer to an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally substituted. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthyl-ethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, , o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-2-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferred.

[0045] In the present specification, the term "substituted or unsubstituted" means a group selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidine group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C1-C 60 Alkyl, C2-C 60 Alkenyl, C2-C 60 Alkynyl, C1-C 60 Alkoxy, C3-C 60 Cycloalkyl, C3-C 60 Cycloalkenyl, C6-C 60 Aryl, C6-C 60 Aryloxy, C6-C 60 Aryl sulfide group and C2-C 60 The heterocyclic aryl group may be substituted or unsubstituted with one or more substituents, or may be substituted or unsubstituted with a substituent in which two or more substituents among the substituents exemplified above are linked together.

[0046] It should be understood that when describing a molecular fragment as a substituent or otherwise attached to another moiety, its name can be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying a substituent or attaching a fragment are considered equivalent.

[0047] In the compounds mentioned in this disclosure, hydrogen atoms can be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. Due to its enhanced efficiency and stability of the element, the replacement of other stable isotopes in the compound may be preferred.

[0048] In the compounds referred to in this disclosure, multiple substitutions are meant to include double substitutions up to the maximum number of available substitutions.

[0049] According to one embodiment of the present invention, an organic electroluminescent element is disclosed, comprising: an anode, a cathode, and a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by general formula (I):

[0050]

[0051] Where: W 1 , W 2 , W 3 Each independently selected from CR 0 Or any two adjacent W 1 , W 2 , W 3 represents a group of the following formula (a), and W 1 , W 2 , W 3 Not CR at the same time 0 ;

[0052]

[0053] X is selected from S, Se, NR 1 or CR 2 R 3 ; G is selected from O, S, Se, SO or SO2; Z is selected from CR 4 Or N; and ^ indicates the corresponding adjacent W in formula (I) 1 , W 2 , W 3 ;

[0054] R 0 , R 4 In each occurrence, the same or different represents an electron withdrawing group;

[0055] R 1 , R 2 , R 3 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C1-C 40 Alkyl, substituted or unsubstituted C3-C 40 branched alkyl or cycloalkyl, substituted or unsubstituted C1-C 40heteroalkyl, substituted or unsubstituted C2-C 40 Alkenyl, substituted or unsubstituted C6-C 60 Aryl, substituted or unsubstituted C6-C 60 Aryloxy, substituted or unsubstituted C7-C 60 Aralkyl, substituted or unsubstituted C3-C 40 Alkylsilyl, substituted or unsubstituted C6-C 60 Arylsilyl, substituted or unsubstituted C0-C 40 an amine group, or a substituted or unsubstituted C2-C 60 The group consisting of heterocyclic aromatic groups, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, isonitrile groups, sulfenyl groups, sulfinyl groups, sulfonyl groups, phosphino groups, and phosphinooxy groups, wherein two or more adjacent groups may be optionally joined or fused to form another one or more substituted or unsubstituted rings, and the formed rings may or may not contain one or more heteroatoms N, P, B, O or S.

[0056] According to an embodiment of the present invention, the hole injection layer comprises any one of the compounds represented by Formula 1 to Formula 4:

[0057]

[0058] Wherein, X is selected from NR 1 or CR 2 R 3 ; G is selected from O or S; Z is selected from CR 4 or N,

[0059] R 0 , R 4 each independently selected from the group consisting of hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, pentafluoroethyl, pentafluoroethoxy, cyano, nitro, methanesulfonyl, trifluoromethanesulfonyl, trifluoroacetyl, trifluoromethylthio, pentafluorothio, pyridyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, cyanophenyl, trifluoromethylphenyl, trifluoromethoxyphenyl, pentafluoroethylphenyl, pentafluoroethoxyphenyl, nitrophenyl, methanesulfonylphenyl, trifluoromethanesulfonylphenyl, trifluoromethylthiophenyl, pentafluorothiophenyl, cyanofluorophenyl, cyanodifluorophenyl, cyanotrifluorophenyl, cyanotetrafluorophenyl, pyrimidinyl, triazinyl, 2,6-dimethyl-1,3,5-triazinyl, 2,6-bis(trifluoromethyl)-1,3,5-triazinyl, and combinations thereof;

[0060] R 1 , R 2 , R 3 Each is independently selected from the group consisting of trifluoromethyl, cyano, pentafluorophenyl, pyridyl, and cyanotetrafluorophenyl.

[0061] According to another embodiment of the present invention, the hole injection layer comprises any one of the compounds represented by Formula 5 to Formula 12:

[0062]

[0063] Wherein, G is selected from O or S; Z is selected from CR 4 or N; R 0 , R 4 each independently selected from the group consisting of hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, pentafluoroethyl, pentafluoroethoxy, cyano, nitro, methanesulfonyl, trifluoromethanesulfonyl, trifluoroacetyl, trifluoromethylthio, pentafluorothio, pyridyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, cyanophenyl, trifluoromethylphenyl, trifluoromethoxyphenyl, pentafluoroethylphenyl, pentafluoroethoxyphenyl, nitrophenyl, methanesulfonylphenyl, trifluoromethanesulfonylphenyl, trifluoromethylthiophenyl, pentafluorothiophenyl, cyanofluorophenyl, cyanodifluorophenyl, cyanotrifluorophenyl, cyanotetrafluorophenyl, pyrimidinyl, triazinyl, 2,6-dimethyl-1,3,5-triazinyl, 2,6-bis(trifluoromethyl)-1,3,5-triazinyl, and combinations thereof;

[0064] R 1 , R 2 , R 3 Each is independently selected from the group consisting of trifluoromethyl, cyano, pentafluorophenyl, pyridyl, and cyanotetrafluorophenyl.

[0065] According to a preferred embodiment of the present invention, the hole injection layer comprises a group consisting of formulas CJHM383 to CJHM606:

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077] Among them, in the compounds represented by formula CJHM383 to CJHM606: G is O or S; Z is N or CR 4 , the R 4 is selected from hydrogen or a group represented by C1 to C70, and the structure of C1 to C70 is as follows:

[0078]

[0079]

[0080] According to one embodiment of the present invention, the hole injection layer is in contact with the anode.

[0081] According to one embodiment of the present invention, the hole injection layer is composed of the compound represented by the general formula (I) as a sole component.

[0082] According to one embodiment of the present invention, the hole injection layer further comprises an aromatic amine compound.

[0083] According to an embodiment of the present invention, the organic electroluminescent element further includes a light-emitting layer.

[0084] The present invention also provides an organic electroluminescent material, comprising the compound represented by the above general formula (I).

[0085] The materials for the specific layers in the organic light-emitting element described in the present invention can be used in combination with various other materials present in the element. The combination of these materials is described in detail in paragraphs 0132-0161 of U.S. Patent Application US2016 / 0359122A1, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0086] The materials described herein as being useful for specific layers in an organic light-emitting element can be used in combination with a variety of other materials present in the element. For example, the luminescent dopants disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of patent application US2015 / 0349273A1, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0087] The present invention also provides an organic electroluminescent element, which comprises a first electrode, a second electrode and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one layer of the organic layer comprises the naphthyridine-based compound of the above formula (I).

[0088] The organic electroluminescent element comprises a cathode, an anode and at least one luminescent layer. In addition to these layers, it may also comprise other layers, for example, in each case, comprising one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers. An intermediate layer having, for example, an exciton blocking function may also be introduced between two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent device described herein may comprise one luminescent layer, or it may comprise multiple luminescent layers. That is, a variety of luminescent compounds capable of luminescence are used in the luminescent layer. A system having three luminescent layers is particularly preferred, wherein the three layers can display blue, green and red luminescence. If there are more than one luminescent layer, then according to the present invention, at least one of these layers comprises a compound of the present invention.

[0089] Furthermore, the organic electroluminescent element according to the present invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, that is, the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.

[0090] In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner commonly used according to the prior art. A person skilled in the art will therefore be able to use all materials known about organic electroluminescent elements in combination with the emitting layer according to the invention without inventive effort.

[0091] Furthermore, preference is given to an organic electroluminescent component which is characterized in that one or more layers are applied by means of a sublimation process, wherein the sublimation reaction is carried out in a vacuum sublimation apparatus at temperatures below 10 -5 Pa, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa.

[0092] Preference is likewise given to an organic electroluminescent component, characterized in that one or more layers are applied by means of an organic vapor phase deposition method or by means of carrier gas sublimation, wherein at 10 -5The material is applied at a pressure of between 100 Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.

[0093] Furthermore, preference is given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example obtained by suitable substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0094] The present invention also provides a tandem organic electroluminescent element, which includes an anode, a cathode, and a plurality of stacked layers arranged between the anode and the cathode, each stacked layer includes at least one light-emitting layer, and a charge generation layer is arranged between each two adjacent stacked layers, and the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer contains a compound represented by the general formula (I) as described above.

[0095] These methods are generally known to those skilled in the art, and they can apply them to organic electroluminescent elements comprising the compounds according to the invention without inventive step.

[0096] The present invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, characterized in that at least one layer is applied by means of a sublimation method and / or characterized in that at least one layer is applied by means of an organic vapor deposition method or by means of carrier gas sublimation and / or characterized in that at least one layer is applied from a solution by spin coating or by means of a printing method.

[0097] In addition, the present invention relates to compounds of the present invention comprising at least one indicated above. The same preferred conditions as indicated above for organic electroluminescent elements apply to the compounds of the present invention. In particular, the compounds may also preferably comprise other compounds in addition. Processing the compounds according to the present invention from the liquid phase, for example by spin coating or by a printing method, requires preparations of the compounds according to the present invention. These preparations may, for example, be solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fennel, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpenes alcohol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0098] A consumer product comprising the organic electroluminescent element or the tandem organic electroluminescent element. In some embodiments, the consumer product may be one of the following: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a lamp for internal or external lighting and / or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a cellular phone, a tablet computer, a tablet phone, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0099] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained commercially, and any range recorded in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0100] The beneficial effects achieved by the present invention are:

[0101] The naphthyridine-based compound or the material composed of the naphthyridine-based compound shown in formula (I) provided by the present invention can reduce the voltage of the OLED element and improve the efficiency and life of the element.

[0102] In the description of the present invention, unless otherwise specified, “plurality” means two or more than two; the orientations or positional relationships indicated by the terms “upper”, “lower”, etc. are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0103] The experimental methods used in the following examples are all conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples are all commercially available unless otherwise specified, and the percentages are all mass percentages unless otherwise specified.

[0104] The test instruments and methods for testing the performance of OLED materials and components in the following embodiments are as follows:

[0105] OLED component performance testing conditions:

[0106] Brightness and chromaticity coordinates: tested using a spectral scanner PhotoResearch PR-715;

[0107] Current density and lighting voltage: tested using Keithley 2420 digital source meter;

[0108] Power efficiency: Tested using NEWPORT 1931-C.

[0109] Compound Synthesis Examples

[0110] The synthetic routes of the compounds represented by formula (I) including the compounds represented by formula 1 to formula 4 are as follows:

[0111] Synthesis of Formula 1 (Synthesis Route 1 and Synthesis Route 2):

[0112]

[0113]

[0114] Synthesis of Formula 2 (Synthesis Route 3 and Synthesis Route 4):

[0115]

[0116] Synthesis of Formula 3 (Synthesis Route 5 and Synthesis Route 6):

[0117]

[0118] Synthesis of Formula 4 (Synthesis Route 7 and Synthesis Route 8):

[0119]

[0120] Among them, X 1 is Cl, Br, I or OTf, and other symbols used are as defined above.

[0121] Example 1

[0122] The preparation method of the compound CJHM413 wherein G is O or S and Z is N comprises the following steps:

[0123] Step 1: Preparation of compound Int-1

[0124]

[0125] 40.0 mmol of the raw material SM was dissolved in 150 mL of ethanol, and then 201.0 mmol of stannous chloride dihydrate was added, the temperature was raised to reflux and stirred for reaction for 2 hours, and the mixture was concentrated under reduced pressure. 150 mL of saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with ethyl acetate. The organic phase was dried, concentrated under reduced pressure, and separated and purified by silica gel column to obtain compound Int-1 as a yellow solid with a yield of 80-88%.

[0126] Step 2: Preparation of compound Int-2

[0127]

[0128] 30.0 mmol of Int-1 was dissolved in 50 mL of dry DMSO. Under nitrogen protection, 150.0 mmol of triethyl orthoformate and 0.3 mmol of copper trifluoromethanesulfonate were added. The temperature was raised to 60°C and stirred for reaction for 12 hours. The reaction solution was poured into 150 mL of ice water and filtered. The filter cake was washed with ethanol and dried to obtain compound Int-2 as an off-white solid with a yield of 70-80%.

[0129] Step 3: Preparation of compound Int-3

[0130]

[0131] 20.0 mmol of Int-2 and 48.0 mmol of 3,5-difluoro-4-trifluoromethoxyphenylboronic acid were dispersed in 50 mL of toluene, 30 mL of ethanol and 30 mL of water, and then 80.0 mmol of anhydrous potassium carbonate and 0.01 mmol of Pd132 were added. The mixture was stirred under reflux and heated to react for 10 hours. The mixture was cooled to room temperature, 50 mL of water was added, and the mixture was extracted with dichloromethane. The organic phase was dried and concentrated under reduced pressure. The mixture was separated and purified by silica gel column to obtain compound Int-3 as a white solid with a yield of 86%.

[0132] Step 4: Preparation of compound Int-4

[0133]

[0134] 30.0 mmol of Int-3 was dissolved in 80 mL of dry THF. Under nitrogen protection, the temperature was lowered to -100 °C. 26.5 mL of 2.5 M n-butyllithium n-hexane solution was added dropwise. The reaction was stirred for 30 minutes. Then 66.0 mmol of iodine dissolved in THF was added dropwise. The temperature was raised to room temperature and stirred for 2 hours. 100 mL of saturated aqueous sodium bisulfite solution was added. The mixture was extracted with dichloromethane, dried, filtered, and the filtrate was concentrated under reduced pressure. The mixture was separated and purified on a silica gel column to obtain compound Int-4 as a white solid with a yield of 65-70%.

[0135] Step 5: Preparation of compound Int-5

[0136]

[0137] Under nitrogen protection, 60.0 mmol of malononitrile was dissolved in 80 mL of dry DMF, cooled to 0°C, 60.0 mmol of 65% sodium hydride solid was added in batches, the temperature was heated to room temperature and stirred for reaction for 1 hour, 10.0 mmol of Int-4 and 2.0 mmol of Pd(PPh3)4 catalyst were added, the temperature was raised to 90°C and stirred for reaction for 24 hours, cooled to room temperature, the reaction solution was poured into 200 mL of ice water, dilute hydrochloric acid was added dropwise to adjust to acidity, filtered, the filter cake was washed with water and acetone to obtain compound Int-5 as a yellow solid, yield: 90-95%.

[0138] Step 6: Preparation of compound CJHM413 in which G is O or S and Z is N

[0139]

[0140] Under nitrogen protection, 10.0 mmol of Int-5 and 200 mL of dichloromethane were mixed, cooled to 0°C, 30.0 mmol of bis(trifluoroacetyl)iodobenzene was added in batches, the mixture was heated to room temperature and stirred for reaction for 3 days, 500 mL of petroleum ether was added, filtered, the filter cake was washed with petroleum ether and dichloromethane-petroleum ether to obtain compound CJHM413, which was purified by sublimation to obtain a white solid with a yield of 75-80%, MS (TOF-SIMS) m / z: 730.0184 (G=O), 761.9723 (G=S), 1 HNMR (300MHz, CDCl3), G=O, δ=7.57~7.55 (d, 4H). G=S, δ=7.67~7.65(d,4H).

[0141] Example 2

[0142] In compound CJHM413, G is O or S, and Z is CR 4 The preparation method comprises the following steps:

[0143] Step 1: Preparation of compound Int-6

[0144]

[0145] 40.0 mmol of raw material SM1 was dissolved in 100 mL of DMF, and then 120.0 mmol of anhydrous potassium carbonate and 84.0 mmol of ethyl thioglycolate or ethyl glycolate were added, the temperature was raised to 65 °C and stirred for reaction for 5 hours, then the temperature was lowered to room temperature, 200 mL of water was added, and the mixture was filtered. The filter cake was washed with water and ethanol to obtain compound Int-6 as a yellow solid with a yield of 85-90%.

[0146] Step 2: Preparation of compound Int-7

[0147]

[0148] 30.0 mmol of raw material Int-6 was dissolved in 120 mL of methanol, and then 126.0 mmol of sodium methoxide was added. The temperature was raised to reflux and stirred for reaction for 5 hours, then cooled to room temperature, concentrated under reduced pressure, added with 200 mL of water, extracted with dichloromethane, dried the organic phase, filtered, and concentrated the filtrate to obtain compound Int-7 as a yellow solid. The yield was 82-86%.

[0149] Step 3: Preparation of compound Int-8

[0150]

[0151] Mix 90.0 mmol of tert-butyl nitrite, 120.0 mmol of iodine and 200 mL of acetonitrile, heat to 50°C, add 30.0 mmol of raw material Int-7 in batches, stir and react for 2 hours, cool to room temperature, add 200 mL of saturated aqueous sodium bisulfite solution, filter, wash the filter cake with saturated aqueous sodium bisulfite solution and water to obtain compound Int-8 as a pink solid, yield: 70-75%.

[0152] Step 4: Preparation of compound Int-9

[0153]

[0154] 10.0 mmol of Int-8, 0.2 mmol of palladium acetate, 20.0 mmol of anhydrous sodium carbonate and 50 mL of DMF were mixed, and 6 mL of isopropanol was added. The temperature was raised to 140°C, and 60.0 mmol of potassium ferrocyanide was added in batches. The mixture was stirred for 6 hours, cooled to room temperature, 300 mL of water was added, and the mixture was filtered. The filter cake was washed with water to obtain compound Int-9 as a yellow solid. The yield was 55-65%.

[0155] Step 5: Preparation of compound Int-10

[0156]

[0157] 30.0 mmol of Int-9 was dissolved in 60 mL of THF, and 120.0 mmol of hydrated lithium hydroxide and 10 mL of water were added. The temperature was raised to 75 °C and stirred for 12 hours. The temperature was lowered to room temperature, 100 mL of water was added, and the THF was removed by concentration under reduced pressure. Concentrated hydrochloric acid was added dropwise to adjust the acidity. The mixture was filtered, and the filter cake was washed with ethanol and dried to obtain compound Int-10 as a yellow solid. The yield was 90-95%.

[0158] Step 6: Preparation of compound Int-11

[0159]

[0160] 50.0 mmol of Int-10 and 10.0 mmol of copper powder were dispersed in 80 mL of quinoline, heated to 260 °C and stirred for reaction for 3 hours under oxygen, cooled to room temperature, added with 250 mL of 3N dilute hydrochloric acid aqueous solution, filtered, and the filtrate was extracted with dichloromethane. The organic phase was washed with dilute hydrochloric acid, washed with water, dried, concentrated under reduced pressure, and separated and purified by silica gel column to obtain compound Int-11 as a white solid with a yield of 58-60%.

[0161] Step 7: Preparation of Compound Int-12

[0162]

[0163] Referring to the synthesis method of the third step of Example 1, only Int-2 in the third step of Example 1 was replaced by Int-11 to prepare compound Int-12, and a white solid was obtained after separation and purification using a silica gel column. The yield was 84%.

[0164] Step 8: Preparation of Compound Int-13

[0165]

[0166] 30.0 mmol of Int-12 was dissolved in 120 mL of dry THF. Under nitrogen protection, the temperature was lowered to -100°C. 66.0 mL of 1.0 M lithium diisopropylamide in THF solution was added dropwise. The reaction was stirred for 30 minutes. Then 66.0 mmol of iodine dissolved in THF was added dropwise. The temperature was raised to room temperature and stirred for 2 hours. 100 mL of saturated aqueous sodium bisulfite solution was added. The mixture was extracted with dichloromethane, dried, filtered, and the filtrate was concentrated under reduced pressure. The mixture was separated and purified on a silica gel column to obtain compound Int-13 as a white solid with a yield of 65-70%.

[0167] Step 9: Preparation of compound Int-14

[0168]

[0169] Referring to the synthesis method of the fifth step of Example 1, only Int-4 in the fifth step of Example 1 was replaced by Int-13 to prepare compound Int-14 with a yield of 86-90%.

[0170] Step 10: In compound CJHM413, G is O or S, and Z is CR 4 Preparation

[0171]

[0172] Referring to the synthesis method of step 6 of Example 1, only Int-5 in step 6 of Example 1 was replaced by Int-14 to prepare compound CJHM413 (G=O or S, R 4 =CN), after sublimation and purification, a white solid was obtained, yield: 70-75%, MS (TOF-SIMS) m / z: 778.0182 (G=O), 809.9727 (G=S), 1 HNMR (300MHz, CDCl3), G=O, δ=7.20~7.18 (d, 4H). G=S, δ=7.30~7.28 (d, 4H).

[0173] Example 3

[0174] The preparation method of the compound CJHM507 wherein G is O or S and Z is N comprises the following steps:

[0175] Step 1: Preparation of compound Int-15

[0176]

[0177] Referring to the synthesis method of the second step of Example 1, only Int-1 in the second step of Example 1 was replaced by SM2 to prepare compound Int-15 with a yield of 76-80%.

[0178] Step 2: Preparation of compound Int-16

[0179]

[0180] Referring to the synthesis method of the third step of Example 1, Int-2 in the third step of Example 1 was replaced by Int-15, and 3,5-difluoro-4-trifluoromethoxyphenylboronic acid was replaced by 2,3,4,5,6-pentafluorophenylboronic acid to prepare compound Int-16, which was separated and purified by silica gel column to obtain a white solid with a yield of 70-75%.

[0181] Step 3: Preparation of compound Int-17

[0182]

[0183] Referring to the synthesis method of the fourth step of Example 1, only Int-3 in the fourth step of Example 1 was replaced by Int-16 to prepare compound Int-17, which was separated and purified by silica gel column to obtain a white solid with a yield of 65-70%.

[0184] Step 4: Preparation of compound Int-18

[0185]

[0186] Referring to the synthesis method of the fifth step of Example 1, only Int-4 in the fifth step of Example 1 was replaced by Int-17 to prepare compound Int-18 as a yellow solid with a yield of 90-93%.

[0187] Step 5: Preparation of compound CJHM507 in which G is O or S and Z is N

[0188]

[0189] Referring to the synthesis method of the sixth step of Example 1, only Int-5 in the sixth step of Example 1 was replaced by Int-18 to prepare compound CJHM507. After sublimation and purification, a white solid was obtained with a yield of 72-76%. MS (TOF-SIMS) m / z: 669.9899 (G=O), 701.9466 (G=S).

[0190] Example 4

[0191] In compound CJHM507, G is O or S, and Z is CR 4 Preparation

[0192] Referring to the synthesis method of Example 2, that is, the method steps are the same as those of Example 2, except that 2,6-dichloro-3,7-dihydroxy-4,8-dinitrile-1,5-naphthyridine or 2,6-dichloro-3,7-dimercapto-4,8-dinitrile-1,5-naphthyridine is used to replace SM1 in the first step of Example 2, and the mass amount of the compound is changed according to the molar amount to prepare CJHM507 in which G is O or S, and R 4 The compound is CN, MS (TOF-SIMS) m / z: 717.9973 (G=O), 749.9516 (G=S).

[0193] Example 5

[0194] Preparation of compound CJHM452 wherein G is O or S and Z is N

[0195] Referring to the synthesis method of Example 1, that is, the method steps are the same as those of Example 1, except that 2,6-diamino-4,8-dibromo-3,7-dihydroxy-1,5-naphthyridine or 2,6-diamino-4,8-dibromo-3,7-dimercapto-1,5-naphthyridine is used to replace Int-1 in the second step of Example 1, and 3,5-difluoro-4-trifluoromethoxyphenylboronic acid in the third step of Example 1 is replaced by 2,3,5,6-tetrafluoro-4-cyanophenylboronic acid, and the mass amount of the compound is changed according to the molar amount to prepare the compound in which G is O or S and Z is N in CJHM452, MS (TOF-SIMS) m / z: 684.0064 (G=O), 715.9613 (G=S).

[0196] Example 6

[0197] In compound CJHM452, G is O or S, and Z is CR 4 Preparation

[0198] Referring to the synthesis method of Example 2, that is, the method steps are the same as those of Example 2, except that 4,8-dibromo-3,7-dichloro-2,6-dinitrile-1,5-naphthyridine is used to replace SM1 in the first step of Example 2, and 3,5-difluoro-4-trifluoromethoxyphenylboronic acid in the seventh step of Example 2 is replaced by 2,3,5,6-tetrafluoro-4-cyanophenylboronic acid, and the mass amount of the compound is changed according to the molar amount to prepare CJHM452 in which G is O or S, and R 4 The compound is CN, MS (TOF-SIMS) m / z: 732.0062 (G=O), 763.9609 (G=S).

[0199] Example 7

[0200] Preparation of compound CJHM576 wherein G is O or S and Z is N

[0201] Referring to the synthesis method of Example 1, that is, the method steps are the same as those of Example 1, except that 3,7-diamino-2,6-dichloro-4,8-dihydroxy-1,5-naphthyridine or 3,7-diamino-2,6-dichloro-4,8-dimercapto-1,5-naphthyridine is used to replace Int-1 in the second step of Example 1, and 3,5-difluoro-4-trifluoromethoxyphenylboronic acid in the third step of Example 1 is replaced by 3,4,5-trifluorophenylboronic acid, and the mass amount of the compound is changed according to the molar amount to prepare the compound in which G is O or S and Z is N in CJHM576, MS (TOF-SIMS) m / z: 598.0355 (G=O), 629.9893 (G=S). 1 HNMR (300MHz, CDCl3), G=O, δ=7.66~7.63 (d, 4H). G=S, δ=7.89~7.86(d,4H).

[0202] Example 8

[0203] In compound CJHM576, G is O or S, and Z is CR 4 Preparation

[0204] Referring to the synthesis method of Example 2, that is, the method steps are the same as those of Example 2, except that 2,6-dibromo-4,8-dichloro-3,7-dinitrile-1,5-naphthyridine is used to replace SM1 in the first step of Example 2, 3,5-difluoro-4-trifluoromethoxyphenylboronic acid in the seventh step of Example 2 is replaced by 3,4,5-trifluorophenylboronic acid, and the mass amount of the compound is changed according to the molar amount to prepare CJHM576 in which G is O or S, and R 4 Compound with CN, MS (TOF-SIMS) m / z: 646.0353 (G=O), 677.9897 (G=S), 1HNMR (300MHz, CDCl3), G=O, δ=7.51~7.48 (d, 4H). G=S, δ=7.74~7.71(d,4H).

[0205] Those skilled in the art should be aware that the above preparation methods are only some illustrative examples, and those skilled in the art can obtain other compound structures of the present invention by improving them.

[0206] Light emitting element embodiment

[0207] First, the glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with an ultraviolet light cleaner for 10 minutes, and bombarded with a low-energy cation beam. Then, the treated ITO glass substrate was placed on a bracket and loaded into a vacuum chamber, and evacuated to 1×10 -5 ~9×10 -3 Pa, The following organic layers were sequentially vacuum-deposited at a rate of / s.

[0208] 1) The compound (Formula I) of the present invention is deposited on the above-mentioned ITO anode layer as a doping material and DNTPD as a main material, wherein the compound (Formula I) of the present invention is 3% of the mass of DNTPD, as a hole injection layer (HIL) of the element, and the thickness of the deposited film is

[0209] 2) HT09 is continuously evaporated on the hole injection layer to form a hole transport layer (HTL) with a film thickness of

[0210] 3) Continue to evaporate H02 as the main material and GD as the doping material on the hole transport layer, GD is 5% of the mass of H02, as the organic light-emitting layer of the element, and the film thickness of the organic light-emitting layer obtained by evaporation is

[0211] 4) A layer of ET and LiQ mixture is continuously evaporated on the organic light-emitting layer, with a mass ratio of ET:LiQ of 35:65, as the electron transport layer of the component, and the evaporated film thickness is

[0212] 5) Continue to evaporate a layer of LiF on the electron transport layer as an electron injection layer, and the evaporated film thickness is

[0213] 6) Metal aluminum is evaporated on the electron injection layer as the cathode layer of the element, and the thickness of the evaporated film is The element is then transferred to a glove box and encapsulated with a glass cover plate and a desiccant to complete the OLED element provided by the present invention.

[0214] Comparative Example 1

[0215] According to the same steps as above, the compound of the present invention (Formula I) in step 1) is replaced by F4-TCNQ to obtain comparative element 1;

[0216] The material structure used in the components is as follows:

[0217]

[0218] The IVL and life characteristics of the device were measured at different current densities and voltages. 2 Under the conditions of 50 mA / cm2, the driving voltage, current efficiency, half maximum width (FWHM) and the strongest emission peak λmax of the light-emitting element were measured. The LT90% life of the element was measured at a current density of 50 mA / cm2. 2 Measured under the conditions of .

[0219] Table 1 Component data

[0220]

[0221]

[0222] As can be seen from the data in Table 1 above, the compounds of the present invention are superior to the comparative compounds in various aspects. For example, the embodiments of the present invention have a lower driving voltage than the comparative examples, indicating that the hole injection using the compounds of the present invention is much more efficient and energy-saving than the comparative compounds. The embodiments of the present invention also have higher current efficiency and longer device life than the comparative examples.

[0223] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An organic electroluminescent element, comprising: an anode, a cathode, and a hole injection layer disposed between the anode and the cathode, The hole injection layer is a group consisting of formula CJHM413, CJHM452, CJHM507, CJHM576: Among them, in the compounds represented by formula CJHM413, CJHM452, CJHM507, and CJHM576: G is O or S; Z is N or CR 4 , the R 4 is selected from hydrogen or a group represented by C1 to C70, and the structure of C1 to C70 is as follows:

2. The organic electroluminescent element according to claim 1, characterized in that: The hole injection layer is in contact with the anode.

3. The organic electroluminescent element according to claim 1, characterized in that: The hole injection layer is composed of a compound represented by the formula CJHM413, CJHM452, CJHM507, or CJHM576 as a sole component.

4. The organic electroluminescent element according to claim 1, characterized in that: The hole injection layer further includes an aromatic amine compound.

5. An organic electroluminescent material, characterized in that: The compound comprises the compound represented by the formula CJHM413, CJHM452, CJHM507 or CJHM576 as claimed in claim 1.

6. A tandem organic electroluminescent element, characterized in that: include: An anode, a cathode, and a plurality of stacked layers arranged between the anode and the cathode, each stacked layer comprising at least one light-emitting layer, a charge generation layer arranged between every two adjacent stacked layers, the charge generation layer comprising a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer comprises a compound represented by the formula CJHM413, CJHM452, CJHM507, or CJHM576 as described in claim 1.

7. A consumer product, characterized in that: The organic electroluminescent element comprises the organic electroluminescent element according to any one of claims 1 to 4 or the tandem organic electroluminescent element according to claim 6.

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