Organic electroluminescent materials and devices

Abstract

An organic electroluminescent material and device are disclosed. The organic electroluminescent material is a compound having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and a similar structure, and can be used as a charge transport material, a charge injection material and a charge generation material in an electroluminescent device. These novel compounds can greatly improve the voltage and life of the organic electroluminescent device. An electroluminescent device and a compound formula are also disclosed.

Description

[0001] This patent application is a divisional application of Chinese invention patent application No. 201911046002.3, whose application date is October 30, 2019 and whose invention name is “Organic electroluminescent materials and devices”. Technical Field

[0002] The present invention relates to compounds for organic electronic devices, such as organic light-emitting devices, and more particularly to novel compounds having dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and similar structures, and organic electroluminescent devices and compound formulations containing the compounds. Background Art

[0003] Organic electronic devices include but are not limited to the following categories: organic light emitting diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes and organic plasmonic light emitting devices.

[0004] In 1987, Tang and Van Slyke of Eastman Kodak reported a double-layer organic electroluminescent device, which included an arylamine hole transport layer and a tri-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987, 51 (12): 913-915). Once a bias voltage is applied to the device, green light is emitted from the device. This invention laid the foundation for the development of modern organic light-emitting diodes (OLEDs). The most advanced OLEDs can include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light-emitting layers between the cathode and the anode. Since OLEDs are self-luminous solid-state devices, they offer great potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, can make them very suitable for special applications, such as on flexible substrates.

[0005] OLEDs can be divided into three different types based on their light emission mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It uses only singlet light emission. The triplet generated in the device is wasted through non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation has hindered the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which used triplet light emission from heavy metals containing complexes as emitters. Therefore, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributed to the commercialization of active matrix OLEDs (AMOLEDs). Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return from triplet to singlet. In TADF devices, triplet excitons can generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

[0006] OLEDs can also be classified into small molecule and polymer OLEDs based on the form of the material used. Small molecules are any organic or organometallic material that is not a polymer. Small molecules can have a large molecular weight as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant luminescent groups. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the manufacturing process.

[0007] There are various OLED manufacturing methods. Small molecule OLEDs are usually manufactured by vacuum thermal evaporation. Polymer OLEDs are manufactured by solution methods such as spin coating, inkjet printing, and nozzle printing. Small molecule OLEDs can also be manufactured by solution methods if the material can be dissolved or dispersed in a solvent.

[0008] Organic light-emitting display devices use hole injection layers and electron injection layers to promote charge injection. The hole injection layer is a functional layer formed by a single material or more than one material. The single material method generally uses a deep LUMO material, while the more than one material method is formed by doping a P-type, deep LUMO material with a hole transport material. The common point between the two is that they need to use a deep LUMO material.

[0009] US20050121667 discloses an organic meso compound as an organic dopant to dope an organic semiconductive matrix material to change its electrical properties. The meso compound is a quinone or a quinone derivative, and has a lower volatility than F4-TCNQ under the same evaporation conditions. The general structure disclosed includes the following:

[0010]

[0011] This application mainly focuses on the unique properties of quinone or quinone derivatives as dopants, but it does not disclose or teach the properties and applications of any compounds with a core structure similar to that of the present application.

[0012] However, deep LUMO materials are not easy to synthesize due to their strong electron-pulling substituents, and it is difficult to simultaneously possess the characteristics of deep LUMO, high stability, and high film-forming properties. For example, F4-TCNQ (P-type hole injection material), although it has a deep LUMO, the evaporation temperature is too low, which affects the control of deposition, the reproducibility of production performance, and the thermal stability of the device; for another example, HATCN has film-forming problems in the device due to its strong crystallinity, and the LUMO is not deep enough to be used as a P-type doping. Given that the hole injection layer has a great impact on the voltage, efficiency, and life of OLED devices, it is very important and urgent in the industry to develop materials with deep LUMO, high stability, and high film-forming properties. Summary of the invention

[0013] The present invention aims to provide a series of novel compounds having dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole or similar structures to solve at least part of the above problems. The compounds can be used as charge transport materials and charge injection materials in organic electroluminescent devices. These novel compounds can greatly improve the performance of organic electroluminescent devices such as voltage and life.

[0014] According to one embodiment of the present invention, a compound having a structure of Formula 1 is disclosed:

[0015]

[0016] wherein X and Y are identically or differently selected at each occurrence from CR"R"', NR', O, S or Se;

[0017] wherein Z1 and Z2 are identically or differently selected from O, S or Se at each occurrence;

[0018] R, R', R" and R'" are each identically or differently selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0019] wherein each R may be the same or different, and at least one of R, R', R", and R'" is a group having at least one electron withdrawing group;

[0020] Adjacent substituents may be optionally linked to form a ring.

[0021] According to another embodiment of the present invention, an electroluminescent device is also disclosed, which includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer includes a compound having Formula 1:

[0022]

[0023] wherein X and Y are identically or differently selected at each occurrence from CR"R"', NR', O, S or Se;

[0024] wherein Z1 and Z2 are identically or differently selected from O, S or Se at each occurrence;

[0025] R, R', R" and R'" are each identically or differently selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0026] Adjacent substituents can be optionally linked to form a ring;

[0027] Each R may be the same or different, and at least one of R, R', R", and R'" is a group having at least one electron withdrawing group.

[0028] According to another embodiment of the present invention, a compound formulation is also disclosed, which contains the compound having the structure of Formula 1.

[0029] The novel compounds disclosed in the present invention having a structure similar to dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole can be used as charge transport materials and charge injection materials in electroluminescent devices. These novel compounds can greatly improve the voltage and life of organic electroluminescent devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a schematic diagram of an organic light-emitting device that may contain the compounds and compound formulations disclosed herein.

[0031] Figure 2 is a schematic diagram of a tandem organic light-emitting device that can contain the compounds and compound formulations disclosed herein.

[0032] Figure 3 is a schematic diagram of another tandem organic light-emitting device that may contain the compounds and compound formulations disclosed herein.

[0033] Figure 4 is a diagram showing structural formula 1 of a compound as disclosed herein. DETAILED DESCRIPTION

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] In one embodiment, two or more OLED units may be connected in series to form a series OLED. 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.

[0039] 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 device. 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.

[0040] Devices manufactured according to embodiments of the present invention can be incorporated into various consumer products having one or more electronic component modules (or units) of the device. 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.

[0041] The materials and structures described herein may also be used in other organic electronic devices listed above.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin-statistical limit through delayed fluorescence. Delayed fluorescence can generally be divided into two types, namely P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

[0046] On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but on the conversion between triplet and singlet excited state. Compounds capable of producing E-type delayed fluorescence need to have a very small single-triplet gap for the conversion between energy states. Thermal energy can activate the transition from triplet back to singlet. This type of delayed fluorescence is also called thermally activated delayed fluorescence (TADF). The notable feature of TADF is that the delayed component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize the non-radiative decay by triplet, the fraction of backfilling singlet excited state may reach 75%. The total singlet fraction can be 100%, far exceeding the 25% of the spin statistics of the electrically generated excitons.

[0047] The E-type delayed fluorescence feature can be seen in an exciplex system or a single compound. Without being bound by theory, it is believed that the E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE S-T ). Organic non-metal-containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is usually characterized by donor-acceptor charge transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds usually produces a small ΔE S-TThese states may include CT states. Generally, donor-acceptor light-emitting materials are constructed by linking an electron donor moiety (eg, an amino group or a carbazole derivative) to an electron acceptor moiety (eg, a six-membered aromatic ring containing N).

[0048] Definition of Substituent Terms

[0049] Halogen or halide - as used herein includes fluorine, chlorine, bromine and iodine.

[0050] Alkyl - includes straight chain and branched chain alkyl groups. Examples of alkyl groups 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, the alkyl group may be optionally substituted. The carbon in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.

[0051] Cycloalkyl - as used herein includes cyclic alkyl groups. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. In addition, cycloalkyl groups may be optionally substituted. The carbons in the ring may be substituted with other heteroatoms.

[0052] Alkenyl - As used herein, linear and branched olefin groups are encompassed. Preferred alkenyl groups are alkenyl groups containing 2 to 15 carbon atoms. Examples of alkenyl groups 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 groups may be optionally substituted.

[0053] Alkynyl - as used herein, encompasses both straight and branched chain alkynyl groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, alkynyl groups may be optionally substituted.

[0054] Aryl or aromatic group - As used herein, both non-fused and fused systems are contemplated. 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, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl can be optionally substituted. Examples of non-condensed aryl 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-quadrenyl.

[0055] Heterocyclyl or heterocycle - As used herein, both aromatic and non-aromatic cyclic groups are contemplated. 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.

[0056] Heteroaryl - As used herein, non-fused and fused heteroaromatic groups that may contain from 1 to 5 heteroatoms are contemplated. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups 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 is substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazole and its aza analogs. In some embodiments, the heteroaryl group is substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazole and its aza analogs. In some embodiments, the heteroaryl group is substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazole and its aza analogs. In addition, the heteroaryl group may be optionally substituted.

[0057] Alkoxy - is represented by -O-alkyl. Examples and preferred examples of alkyl are the same as those described above. Examples of alkoxy having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. Alkoxy having 3 or more carbon atoms may be linear, cyclic or branched.

[0058] Aryloxy- is represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as described above. Examples of aryloxy having 6 to 40 carbon atoms include phenoxy and biphenyloxy.

[0059] Aralkyl - As used herein, 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, Preferably, benzyl, 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-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl are used. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferred.

[0060] The term "aza" in azadibenzofuran, aza-dibenzothiophene, etc. means that one or more CH groups in the corresponding aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene includes dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-mentioned aza derivatives can be easily thought of by those of ordinary skill in the art, and all such analogs are determined to be included in the terms described herein.

[0061] 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.

[0062] In the compounds mentioned in this disclosure, hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. The replacement of other stable isotopes in the compounds may be preferred because it enhances the efficiency and stability of the device.

[0063] In the compounds mentioned in the present disclosure, multiple substitution refers to the range including disubstitution up to the maximum number of available substitutions. When a substituent in the compounds mentioned in the present disclosure represents multiple substitutions (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can exist in multiple available substitution positions on its connection structure, and the substituents existing in multiple available substitution positions can be of the same structure or different structures.

[0064] In the present disclosure, unless otherwise defined, when any one of the terms in the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphinooxy is used, it means that any one of alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphinooxy may be selected from one or more deuterium, halogen, unsubstituted 1-20 atoms. The invention also includes an alkyl group having 3 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted alkynyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphinoyl group, and combinations thereof.

[0065] In the compounds mentioned in the present disclosure, unless explicitly defined, for example, adjacent substituents can be optionally connected to form a ring, otherwise adjacent substituents in the compound cannot be connected to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally connected to form a ring, including both the situation where adjacent substituents can be connected to form a ring and the situation where adjacent substituents are not connected to form a ring. When adjacent substituents can be optionally connected to form a ring, the formed ring can be a monocyclic or polycyclic ring, as well as an alicyclic, heteroalicyclic, aromatic or heteroaromatic ring. In this statement, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0066] The expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0067]

[0068] The expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0069]

[0070] Furthermore, the statement that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the two substituents bonded to the carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

[0071]

[0072] According to one embodiment of the present invention, a compound having Formula 1 is disclosed:

[0073]

[0074] wherein X and Y are identically or differently selected at each occurrence from CR"R"', NR', O, S or Se;

[0075] wherein Z1 and Z2 are identically or differently selected from O, S or Se at each occurrence;

[0076] R, R', R" and R'" are each identically or differently selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0077] wherein each R may be the same or different, and at least one of R, R', R", and R'" is a group having at least one electron withdrawing group;

[0078] Adjacent substituents may be optionally linked to form a ring.

[0079] In this embodiment, R, R', R", and R'" are selected from the same or different substituent groups each time they appear. It is obvious to those skilled in the art that two substituents with the same number (e.g., R, R', R", or R'") that appear simultaneously in Formula 1 can be selected from the same substituent or different substituents.

[0080] According to one embodiment of the present invention, X and Y are the same or different each time and are selected from CR'R" or NR'", R', R" and R'" are groups having at least one electron withdrawing group.

[0081] According to one embodiment of the present invention, wherein X and Y are the same or different each time they appear and are selected from CR'R" or NR'", R, R', R" and R'" are groups having at least one electron withdrawing group.

[0082] According to one embodiment of the present invention, X and Y are the same or different when they appear each time and are selected from O, S or Se, and at least one of R is a group having at least one electron withdrawing group.

[0083] According to one embodiment of the present invention, X and Y are the same or different when they appear each time and are selected from O, S or Se, and R is a group having at least one electron withdrawing group.

[0084] According to one embodiment of the present invention, the Hammett constant of the electron-withdrawing basis is ≥0.05, or the Hammett constant of the electron-withdrawing basis is ≥0.3, or the Hammett constant of the electron-withdrawing basis is ≥0.5.

[0085] The Hammett substituent constant value of the electron-withdrawing group of the present invention is ≥0.05, preferably ≥0.3, and more preferably ≥0.5. It has a strong electron-withdrawing ability and can significantly reduce the LUMO energy level of the compound, thereby achieving the effect of improving charge mobility.

[0086] It should be noted that the Hammett substituent constant value includes the Hammett substituent para constant and / or meta constant. As long as one of the para constant and the meta constant satisfies greater than or equal to 0.05, the group can be selected as the group of the present invention.

[0087] According to one embodiment of the present invention, the electron withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, azaaromatic ring group, or any of the following groups substituted by one or more of halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, azaaromatic ring group: having 1 -20 carbon atoms, alkyl groups having 3-20 ring carbon atoms, cycloalkyl groups having 3-20 ring carbon atoms, heteroalkyl groups having 1-20 carbon atoms, aralkyl groups having 7-30 carbon atoms, alkoxy groups having 1-20 carbon atoms, aryloxy groups having 6-30 carbon atoms, alkenyl groups having 2-20 carbon atoms, alkynyl groups having 2-20 carbon atoms, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, alkylsilyl groups having 3-20 carbon atoms, arylsilyl groups having 6-20 carbon atoms, and combinations thereof.

[0088] According to one embodiment of the present invention, the electron-withdrawing group is selected from the group consisting of: F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pyrimidine, triazine, and combinations thereof.

[0089] According to one embodiment of the present invention, each occurrence of X and Y is identically or differently selected from the group consisting of the following structures:

[0090]

[0091]

[0092] wherein R1 is selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0093] Where V and W are selected from CR in the same or different manner at each occurrence. v R w , NR v , O, S, Se;

[0094] wherein Ar is selected, at each occurrence, identically or differently, from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

[0095] Among them, A, R a , R b , R c , R d , R e , R f , R g , R h , R v and R wis selected, at each occurrence, identically or differently, from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0096] wherein A is a group having at least one electron withdrawing group, and for any of the structures, when R a , R b , R c , R d , R e , R f , R g , R h , R v and R w When one or more of are present, at least one of them is a group having at least one electron withdrawing group.

[0097] In this embodiment, “*” indicates the position where the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodiselenazole ring in Formula 1.

[0098] According to one embodiment of the present invention, R1 is selected from the group consisting of: F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazine, and combinations thereof, at each occurrence, the same or different.

[0099] According to one embodiment of the present invention, the group having at least one electron-withdrawing group is selected from the group consisting of: F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazine, and combinations thereof.

[0100] According to one embodiment of the present invention, each occurrence of X and Y is identically or differently selected from the group consisting of the following structures:

[0101]

[0102] In this embodiment, “*” indicates the position where the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodiselenazole ring in Formula 1.

[0103] According to one embodiment of the present invention, each occurrence of R is identically or differently selected from the group consisting of: hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, Unsubstituted heteroaryl groups having 3-30 carbon atoms, and any of the following groups substituted by one or more of halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl and phosphino groups: alkyl groups having 1-20 carbon atoms, cycloalkyl groups having 3-20 ring carbon atoms, alkoxy groups having 1-20 carbon atoms, alkenyl groups having 2-20 carbon atoms, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof;

[0104] According to one embodiment of the present invention, each occurrence of R is identically or differently selected from the group consisting of: hydrogen, deuterium, methyl, isopropyl, NO2, SO2CH3, SCF3, C2F5, OC2F5, OCH3, diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, vinyl substituted with one or more of CN and CF3, vinyl substituted with CN or CF 3, ethynyl substituted by one of the following: dimethylphosphinoyl, diphenylphosphinoyl, F, CF3, OCF3, SF5, SO2CF3, cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis(trifluoromethyl)phenyl, bis(trifluoromethoxy)phenyl, 4-cyanotetrafluorophenyl, phenyl or biphenyl substituted by one or more of F, CN and CF3, tetrafluoropyridyl, pyrimidinyl, triazine, diphenylboryl, oxaboranthenyl, and combinations thereof.

[0105] According to one embodiment of the present invention, wherein X and Y are

[0106] According to one embodiment of the present invention, each occurrence of R is identically or differently selected from the group consisting of the following structures:

[0107]

[0108]

[0109] In this embodiment, It represents the position where the R group is connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodiselenazole ring in Formula 1.

[0110] According to one embodiment of the present invention, in one compound represented by Formula 1, two Rs are the same.

[0111] According to one embodiment of the present invention, the compound is selected from the group consisting of Compound 1 to Compound 1356, and Compound 1 to Compound 1356 have a structure represented by Formula 2:

[0112]

[0113] Wherein, the two Z in Formula 2 have the same structure, the two R structures are the same or different, and the Z, X, Y, and R correspond to atoms or groups selected from the following table:

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] According to one embodiment of the present invention, an electroluminescent device is also disclosed, comprising:

[0131] anode,

[0132] cathode,

[0133] and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having Formula 1:

[0134]

[0135] wherein X and Y are identically or differently selected at each occurrence from CR"R"', NR', O, S or Se;

[0136] wherein Z1 and Z2 are identically or differently selected from O, S or Se at each occurrence;

[0137] R, R', R" and R'" are each identically or differently selected from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF5, borane, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

[0138] wherein each R may be the same or different, and at least one of R, R', R", and R'" is a group having at least one electron withdrawing group;

[0139] Adjacent substituents may be optionally linked to form a ring.

[0140] According to an embodiment of the present invention, in the device, the organic layer is a hole injection layer, and the hole injection layer is formed of the compound alone.

[0141] According to one embodiment of the present invention, in the device, the organic layer is a hole injection layer, and the hole injection layer is formed by the compound containing the doping, the doping contains at least one hole transport material; the hole transport material contains a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000.

[0142] According to an embodiment of the present invention, in the hole injection layer, the molar doping ratio of the compound to the hole transport material is 10:1 to 1:100.

[0143] According to one embodiment of the present invention, the electroluminescent device includes a plurality of stacked layers between an anode and a cathode, the stacked layers include a first light-emitting layer and a second light-emitting layer, wherein the first stacked layer includes a first light-emitting layer, the second stacked layer includes a second light-emitting layer, and a charge generation layer is arranged between the first stacked layer and the second stacked layer, wherein the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer; wherein the organic layer containing the compound having formula 1 is a p-type charge generation layer.

[0144] According to one embodiment of the present invention, the p-type charge generation layer further comprises at least one hole transport material, and the p-type charge generation layer is formed by doping the compound in the at least one hole transport material, and the hole transport material comprises a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000.

[0145] According to one embodiment of the present invention, in the p-type charge generation layer, the molar doping ratio of the compound to the hole transport material is 10:1 to 1:100.

[0146] According to one embodiment of the present invention, the charge generation layer further includes a buffer layer disposed between the p-type charge generation layer and the n-type charge generation layer, and the buffer layer includes the compound.

[0147] According to another embodiment of the present invention, a compound formula is also disclosed, which comprises a compound represented by Formula 1. The specific structure of the compound is shown in any of the above embodiments.

[0148] Combination with other materials

[0149] The materials for specific layers in the organic light-emitting device described in the present invention can be used in combination with various other materials present in the device. 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.

[0150] The materials described herein as specific layers that can be used in organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the light-emitting 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 U.S. 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.

[0151] In the embodiment of material synthesis, unless otherwise stated, all reactions are carried out under nitrogen protection. All reaction solvents are anhydrous and used as they are from commercial sources. The synthetic product uses one or more conventional equipment in the art (including but not limited to Bruker's nuclear magnetic resonance instrument, Shimadzu's liquid chromatograph, liquid chromatography-mass spectrometer, gas chromatography-mass spectrometer, differential scanning calorimeter, Shanghai Lingguang Technology's fluorescence spectrophotometer, Wuhan Cost's electrochemical workstation, Anhui Bei Yi Ke's sublimator, etc.), and the structure is confirmed and the characteristics are tested by methods well known to those skilled in the art. In the embodiment of the device, the characteristics of the device are also tested by methods well known to those skilled in the art using conventional equipment in the art (including but not limited to Angstrom Engineering's evaporation machine, Suzhou Fushida's optical test system, life test system, Beijing Liangtuo's ellipsometer, etc.). Since those skilled in the art are aware of the use of the above-mentioned equipment, test methods and other related contents, it is possible to obtain the inherent data of the sample with certainty and without being affected, so the above-mentioned related contents are no longer expanded in this patent.

[0152] Material synthesis example:

[0153] The preparation method of the compound of the present invention is not limited, and the following compounds are typically but not limitedly exemplified, and their synthetic routes and preparation methods are as follows:

[0154] Synthesis Example 1: Synthesis of Compound 56

[0155] Step 1: Synthesis of [Intermediate 1-a]

[0156]

[0157] DMSO (150 mL) was added to a 500 mL three-necked flask, nitrogen was bubbled for half an hour, HC(OEt)3 (22.2 g, 150 mmol), Y(OTf)3 (2.15 g, 4 mmol) were added in sequence, and bubbling was continued for 5 minutes, 2,5-diamino-3,6-dibromobenzene-1,4-diphenol (8.94 g, 30 mmol) was added, and the temperature was raised to 60°C. After 20 minutes, the solution turned brown or khaki and stirred overnight. After the reaction was completed, DCM / PE (1:1, 500 mL) was added, the solid was collected by filtration, washed with acetone, and filtered to obtain an off-white solid 1-a (7.2 g, 75% yield). 1 HNMR (400MHz, d6-DMSO) δ = 9.03 (s, 2H).

[0158] Step 2: Synthesis of [Intermediate 1-b]

[0159]

[0160] Add dioxane (50 mL) to a 250 mL two-necked bottle, bubble nitrogen for 15 minutes, add Pd(OAc)2 (225 mg, 10 mol%, 1.0 mmol) and XPhos (1.0 g, 2.1 mmol) under stirring, and continue stirring for 10 minutes, then add 1-a (3.18 g, 10 mmol), p-trifluoromethoxyphenylboronic acid (8.24 g, 40 mmol), potassium carbonate (8.34 g, 60 mmol) in sequence. Heat to 110 ° C and reflux, stir overnight under nitrogen protection. After the reaction is completed, cool down, filter with diatomaceous earth, wash thoroughly with dichloromethane, and separate by silica gel column chromatography to obtain a white solid 1-b (4.36 g, 91% yield). 1 HNMR (400MHz, d6-DMSO) δ = 9.00 (s, 2H), 8.33 (d, J = 8.8Hz, 4H), 7.63 (d, J = 8.8Hz, 4H).

[0161] Step 3: Synthesis of [Intermediate 1-c]

[0162]

[0163] Under nitrogen atmosphere, intermediate 1-b (4.36 g, 9.1 mmol) was added to THF (114 mL, 0.08 M), the temperature was lowered to -94 ° C (acetone / liquid nitrogen cold bath), n-butyl lithium (13.8 mL, 20.93 mmol, 1.6 M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 h, and then slowly raised to -78 ° C (acetone / dry ice cold bath) and reacted for 8 h. A THF solution (15 mL) of elemental iodine (6.93 g, 27.3 mmol) was added, and the temperature was slowly raised to room temperature overnight, and a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the white solid product 1-c (4.0 g, 60% yield) was purified by silica gel column chromatography (PE: DCM = 3: 1-1: 1). 1 HNMR (400MHz, d6-DMSO) δ = 8.16 (d, J = 8.8 Hz, 4H), 7.62 (d, J = 8.8 Hz, 4H).

[0164] Step 4: Synthesis of [Intermediate 1-d]

[0165]

[0166] Under nitrogen atmosphere, malononitrile (2.78 g, 42 mmol) was added to anhydrous DMF (70 mL), and NaH (1.67 g, 42 mmol, 60% content) was added several times at 0 ° C, stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes, and then 1-c (5.08 g, 7 mmol) and Pd (PPh4) 3 (1.62 g, 1.4 mmol) were added, and the temperature was raised to 90 ° C for 24-36 hours. After complete conversion, it was poured into ice water, 4N dilute hydrochloric acid was used to adjust the pH <1, and a large amount of yellow solid was precipitated after sufficient stirring. Filter and collect the solid. Wash with dichloromethane to obtain 4.38 g of yellow solid. Then use dichloromethane to wash twice continuously, and filter to obtain yellow solid 1-d (4.2 g, 98% yield). 1 HNMR (400MHz, d6-DMSO) δ = 8.08 (d, J = 8.8 Hz, 4H), 7.56 (d, J = 8.8 Hz, 4H).

[0167] Step 5: Synthesis of compound 56

[0168]

[0169] Under nitrogen atmosphere, 1-d (3.04 g, 5 mmol) was added to DCM (150 mL), cooled to 0 ° C, PIFA (6.45 g, 15 mmol) was added in batches, and stirred at room temperature for 3 days. The solution was purple-black. n-Hexane (450 mL) was added to the reaction solution, stirred for 10 minutes, and then filtered to obtain a dark green solid. It was washed twice with (DCM / PE=2:1-1:1) to obtain a dark green solid compound 56 (2.5 g, 83% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.30 (d, J = 8.4 Hz, 4H), 7.73 (d, J = 8.4 Hz, 4H).

[0170] Synthesis Example 2: Synthesis of Compound 68

[0171] Step 1: Synthesis of [Intermediate 2-a]

[0172]

[0173] Add dioxane (80 mL) to a 250 mL two-necked bottle, bubble nitrogen for 15 minutes, add Pd(OAc)2 (360 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) under stirring, and continue stirring for 10 minutes, then add 1-a (4.1 g, 13 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (14.0 g, 54 mmol), cesium fluoride (9.12 g, 60 mmol) in sequence. Heat to 110 ° C and reflux, stir overnight under nitrogen protection. After the reaction is completed, cool down, filter with diatomaceous earth, wash thoroughly with dichloromethane, and separate by silica gel column chromatography to obtain a white solid 2-a (6.7 g, 88% yield). 1 HNMR (400MHz, CDCl3) δ = 8.87 (s, 4H), 8.41 (s, 2H), 8.00 (s, 2H).

[0174] Step 2: Synthesis of [Intermediate 2-b]

[0175]

[0176] Under nitrogen atmosphere, 2-a (6.2 g, 10.6 mmol) was added to THF (212 mL, 0.05 M), the temperature was lowered to -94 ° C (acetone / liquid nitrogen cold bath), n-butyl lithium (15.2 mL, 24.4 mmol, 1.6 M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 h, and then slowly raised to -78 ° C (acetone / dry ice cold bath) and reacted for 8 h. A THF solution (20 mL) of elemental iodine (8.07 g, 31.8 mmol) was added, and the temperature was slowly raised to room temperature overnight, and a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the white solid product 2-b (4.7 g, 53% yield) was purified by silica gel column chromatography (PE: DCM = 6: 1-2: 1). 1 HNMR (400MHz, CDCl3) δ = 8.69 (s, 4H), 8.01 (s, 2H).

[0177] Step 3: Synthesis of [Intermediate 2-c]

[0178]

[0179] Under nitrogen atmosphere, malononitrile (1.56g, 23.7mmol) was added to anhydrous DMF (55mL, 0.1M), and NaH (948mg, 23.7mmol, 60% content) was added several times at 0°C, stirred at 0°C for 10 minutes and at room temperature for 20 minutes, and then 2-b (3.3g, 3.95mmol) and Pd (PPh4) 3 (456mg, 0.39mmol) were added, and the temperature was raised to 90°C for reaction for 24-36h. After complete conversion, it was poured into ice water, 4N dilute hydrochloric acid was used to adjust pH <1, and a large amount of yellow solid was precipitated after sufficient stirring, and the solid was filtered and collected. Washed with dichloromethane to obtain 2.98g of yellow solid. Then, it was washed twice with solvent (DCM / PE = 2:1, 200mL) and filtered to obtain yellow solid 2-c (2.81g, 99% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.57 (s, 4H), 8.33 (s, 2H).

[0180] Step 4: Synthesis of Compound 68

[0181]

[0182] Under nitrogen atmosphere, 2-c (2.85 g, 4.0 mmol) was divided into 3 portions (0.95 g / portion) and placed in three two-necked bottles, and DCM (200 mL) was added respectively, and the temperature was lowered to 0 ° C. PIFA (1.73 g, 4.0 mmol) was added in batches, and stirred at room temperature for 3 days. The solution was purple-black. The three bottles of solution were then placed in a 1L single-necked bottle, and the solution was spin-dried to about 50 mL. Hexane (450 mL) was added thereto, and filtered after stirring for 10 minutes to obtain a dark green solid. It was washed twice with (DCM / PE=2:1, 200 mL) to obtain a dark green solid compound 68 (2.4 g, 85% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.86 (s, 4H), 8.37 (s, 2H).

[0183] Synthesis Example 3: Synthesis of Compound 70

[0184] Step 1: Synthesis of [Intermediate 4-a]

[0185]

[0186] In a 250mL two-necked bottle, add dioxane (80mL), bubbling nitrogen for 15 minutes, adding Pd(OAc)2 (360mg, 1.6mmol) and XPhos (1.53g, 3.2mmol) under stirring, and continue stirring for 10 minutes, then add 1-a (4.1g, 13mmol), 2,4-bis(trifluoromethyl)phenylboronic acid (14.0g, 54mmol), cesium fluoride (9.12g, 60mmol), heating to 110°C and reflux, stirring overnight under nitrogen protection. After the reaction is completed, cool down, filter with diatomaceous earth, wash thoroughly with dichloromethane, and separate by silica gel column chromatography to obtain white solid 4-a (6.83g, 90% yield). 1 HNMR (400MHz, CDCl3) δ = 8.19 (s, 2H), 8.12 (s, 2H), 8.02 (d, J = 8.0Hz, 2H), 7.77 (d, J = 8.0Hz, 2H).

[0187] Step 2: Synthesis of [Intermediate 4-b]

[0188]

[0189] Under nitrogen atmosphere, 4-a (6.4 g, 11 mmol) was added to THF (150 mL), the temperature was lowered to -94 °C (acetone / liquid nitrogen cold bath), n-butyl lithium (15.8 mL, 25.3 mmol, 1.6 M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 h, then slowly raised to -78 °C (acetone / dry ice cold bath) and reacted for 8 h. A THF solution (20 mL) of elemental iodine (8.4 g, 33 mmol) was added, and the temperature was slowly raised to room temperature overnight, a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the white solid product 4-b (6.89 g, 75% yield) was purified by silica gel column chromatography (PE: DCM = 10: 1-2: 1). 1 HNMR (400MHz, CDCl3) δ = 8.16 (s, 2H), 8.01 (d, J = 7.6Hz, 2H), 7.73 (d, J = 7.6Hz, 2H).

[0190] Step 3: Synthesis of [Intermediate 4-c]

[0191]

[0192] Under nitrogen atmosphere, malononitrile (2.14 g, 32 mmol) was added to anhydrous DMF (60 mL), and NaH (1.40 g, 35 mmol, 60% content) was added several times at 0 ° C, stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes, and then 4-b (4.51 g, 5.4 mmol) and Pd (PPh4) 3 (1.15 g, 1.0 mmol) were added, and the temperature was raised to 90 ° C for 24-36 hours. After complete conversion, it was poured into ice water, 4N dilute hydrochloric acid was used to adjust the pH <1, and a large amount of yellow solid was precipitated after sufficient stirring. Filter and collect the solid. Wash with dichloromethane to obtain 2.98 g of yellow solid. Then use dichloromethane to wash twice continuously, and filter to obtain yellow solid 4-c (2.92 g, 76% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.35 (m, 4H), 8.16 (d, J = 7.6Hz, 2H).

[0193] Step 4: Synthesis of compound 70

[0194]

[0195] Under nitrogen atmosphere, 4-c (2.92 g, 4.1 mmol) was divided into 3 portions (1 g / portion) and placed in three two-necked bottles, and DCM (100 mL) was added respectively, and the temperature was lowered to 0 ° C. Then PIFA (1.8 g, 4.2 mmol) was added in batches respectively, and stirred at room temperature for 3 days. The solution was purple-black. The three bottles of solution were then placed in a 1L single-necked bottle, the solution was concentrated to about 50 mL, and n-hexane (450 mL) was added thereto. After stirring for 10 minutes, a purple solid was obtained. It was washed twice with (DCM / PE=2:1, 200 mL) respectively, and finally a purple solid compound 70 (2.0 g, 70% yield) was obtained. 1 HNMR (400MHz, CD2Cl2) δ = 8.22 (s, 2H), 8.11 (d, J = 8.4Hz, 2H), 7.75 (d, J = 8.0Hz, 2H).

[0196] Synthesis Example 4: Synthesis of Compound 101

[0197] Step 1: Synthesis of [Intermediate 5-a]

[0198]

[0199] Add distilled water (50 mL), 1,4-phenylenediamine (17.0 g, 157 mmol) and hydrochloric acid (30.7 mL, 125 mmol) to a 500 mL two-necked bottle, heat to 50 ° C, add NH4SCN (48.4 g, 636 mmol), continue to heat to 90 ° C, and stir for 24 hours. After the reaction is completed, cool down, filter, wash with ethanol, and filter to obtain a gray solid compound 5-a (31.5 g, 90% yield). 1 HNMR (400MHz, d6-DMSO) δ = 9.69 (s, 2H), 7.32 (s, 4H).

[0200] Step 2: Synthesis of [Intermediate 5-b]

[0201]

[0202] Compound 5-a (15 g, 66.5 mmol) and chloroform (100 mL) were added to a 500 mL three-necked flask in sequence, the temperature was raised to 50 ° C, and a solution of bromine (8 mL, 309 mmol) in chloroform (100 mL) was very slowly dripped in. After the addition was complete, the mixture was refluxed for 24-36 h. After the reaction was completed, the temperature was lowered to 0 ° C, filtered, and the filter cake was washed three times with chloroform. The solid was collected, washed with saturated sodium thiosulfate solution, filtered, and the solid was collected. After that, it was washed with methanol and dichloromethane, respectively, and filtered to obtain a brown solid 5-b (12.5 g, 83% yield). 1HNMR (400MHz, d6-DMSO) δ = 8.56 (bs, 4H), 7.83 (s, 2H).

[0203] Step 3: Synthesis of [Intermediate 5-c]

[0204]

[0205] Acetonitrile (500 mL) was added to a 1L three-necked flask, and nitrogen was bubbled for 20 minutes. Compound 5-b (11 g, 50 mmol), iodine (76 g, 300 mmol) and tBuONO (20.6 g, 200 mmol) were then added in sequence, and the mixture was reacted at 70°C for 24 h. After the reaction was completed, the temperature was lowered, the acetonitrile was evaporated under reduced pressure, 200 mL of dichloromethane was added, the mixture was filtered, and the mixture was washed with petroleum ether to obtain a brick-red solid 5-c (11 g, 50% yield). 1 HNMR (400MHz, d6-DMSO) δ = 8.74 (s, 2H).

[0206] Step 4: Synthesis of [Intermediate 5-d]

[0207]

[0208] Under nitrogen atmosphere, malononitrile (5.35 g, 81 mmol) was added to anhydrous DMF (135 mL), and NaH (3.24 g, 81 mmol, 60% content) was added several times at 0°C, stirred at 0°C for 10 minutes and at room temperature for 20 minutes, and then compound 5-c (6.08 g, 13.5 mmol) and Pd(PPh4)3 (3.12 g, 2.7 mmol) were added, and the temperature was raised to 90°C for reaction for 24-36 hours. After complete conversion, it was poured into ice water, and 4N dilute hydrochloric acid was used to adjust the pH to <1. After sufficient stirring, a large amount of brown solid precipitated, and the solid was filtered and collected. Washed with dichloromethane to obtain 4.2 g of brown solid. Then, it was washed twice with dichloromethane and filtered to obtain brown solid 5-d (4.02 g, 93% yield). LCMS (ESI): m / z 319 [MH] - .

[0209] Step 5: Synthesis of compound 101

[0210]

[0211] Under nitrogen atmosphere, compound (3.20 g, 10 mmol) was added to DCM (1 L), cooled to 0 °C, PIFA (12.9 g, 30 mmol) was added in batches, stirred at room temperature for 3 days, and the solution was purple-black. After the reaction, the solution was dried to about 100 mL, and then n-hexane (450 mL) was added to the reaction solution, stirred for 10 minutes, and filtered to obtain a purple-black solid. Washed twice with dichloromethane to obtain a purple-black solid compound 101 (3.0 g, 94% yield). LCMS (ESI): m / z 317 [MH] - .

[0212] Synthesis Example 5: Synthesis of Compound 69

[0213] Step 1: Synthesis of [Intermediate 6-a]

[0214]

[0215] In a 250mL two-necked bottle, add 2,5-bis(trifluoromethyl)bromobenzene (18.5g, 63mmol) and ultra-dry tetrahydrofuran (100mL) under nitrogen atmosphere, cool to -78℃, slowly drip isopropylmagnesium chloride lithium chloride solution (54mL, 69mmol, 1.3M tetrahydrofuran solution), react at -78℃ for 1h after the addition is complete, then move to room temperature for 4h. Slowly drip ZnCl2 (35mL, 69.3mmol, 2.0M 2-methyltetrahydrofuran solution) solution at room temperature, stir at room temperature for 1h after the addition is complete. Pd(OAc)2 (337mg, 1.5mmol), XPhos (1.43g, 3.0mmol) and 1-a (5.0g, 15.7mmol) were added at once under nitrogen protection, and stirring continued for 10 minutes, then the temperature was raised and refluxed for 24h. After the reaction was completed, the temperature was lowered, a small amount of saturated ammonium chloride solution was added to quench, the reaction mixture was filtered through celite, washed thoroughly with dichloromethane, and separated by silica gel column chromatography to obtain an off-white solid 6-a (4.23 g, 46% yield). 1 HNMR (400MHz, CDCl3) δ = 8.13 (s, 2H), 8.07 (d, J = 8.4Hz, 2H), 7.95 (d, J = 8.4Hz, 2H), 7.87 (s, 2H).

[0216] Step 2: Synthesis of [Intermediate 6-b]

[0217]

[0218] Under nitrogen atmosphere, 6-a (4.23 g, 7.2 mmol) was added to THF (200 mL), the temperature was lowered to -94 °C, n-butyl lithium (10.4 mL, 16.6 mmol, 1.6 M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 h, and then the temperature was slowly raised to -78 °C for reaction for 8 h. A THF solution (30 mL) of elemental iodine (5.49 g, 33 mmol) was added at -78 °C, and after the addition, the temperature was slowly raised to room temperature for reaction overnight, a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly added to mix the sample, and the light yellow solid product 6-b (2.7 g, 45% yield) was purified by silica gel column chromatography (PE: DCM 10:1-1:1). 1 HNMR (400MHz, CDCl3) δ = 8.05 (s, J = 8.4Hz, 2H), 7.94 (d, J = 8.4Hz, 2H), 7.83 (s, 2H).

[0219] Step 3: Synthesis of [Intermediate 6-c]

[0220]

[0221] Under nitrogen atmosphere, malononitrile (792 mg, 12 mmol) was added to anhydrous DMF (20 mL), and NaH (480 mg, 12 mmol, 60% content) was added several times at 0 ° C. After stirring at 0 ° C for 10 minutes, it was stirred at room temperature for 20 minutes, and then 6-b (1.70 g, 2 mmol) and Pd (PPh4) 3 (277 mg, 0.24 mmol) were added, and the temperature was raised to 90 ° C for 24-36 hours. After complete conversion, it was poured into ice water, and the pH was adjusted to <1 with 4N dilute hydrochloric acid. After sufficient stirring, a large amount of yellow solid precipitated, filtered, and the solid was collected. Washed with dichloromethane to obtain 1.50 g of yellow solid. Then, it was washed twice with dichloromethane and filtered to obtain a yellow solid 6-c (1.40 g, 98% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.37-8.26 (m, 5H), 8.13 (s, 1H).

[0222] Step 4: Synthesis of compound 69

[0223]

[0224] Under nitrogen atmosphere, 6-c (1.40 g, 2 mmol) and DCM (200 mL) were added to a 500 mL two-necked bottle, cooled to 0 ° C, and then PIFA (1.72 g, 4.0 mmol) was added in batches. Stir at room temperature for 7 days, and the solution was purple-black. After the reaction, the solution was concentrated to about 20 mL, and n-hexane (450 mL) was added thereto. After stirring for 10 minutes, a gray-black solid was obtained. It was washed twice with (DCM / PE=2:1, 100 mL) to obtain a gray-black solid compound 69 (1.2 g, 85% yield). 1 HNMR (400MHz, d6-acetone) δ = 8.38-8.27 (m, 5H), 8.13 (s, 1H).

[0225] Those skilled in the art should be aware that the above preparation method is only an illustrative example, and those skilled in the art can obtain other compound structures of the present invention by improving it.

[0226] Device Example 1

[0227] Device Example 1.1:

[0228] A glass substrate with an 80 nm thick indium tin oxide (ITO) transparent electrode was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot plate in a glove box before evaporation. The following materials were heated to a vacuum of about 10 -8 In the case of support, the glass surface is sequentially evaporated at a rate of 0.2-2 angstroms / second. First, the compound 56 of the present invention is evaporated on the surface of the glass substrate to form a 10nm thick film as a hole injection layer (HIL). Next, the compound HT1 is evaporated on the above-mentioned obtained film to form a 120nm thick film as a hole transport layer (HTL). Then, the compound EB1 is evaporated on the above-mentioned obtained film to form a 5nm thick film as an electron blocking layer (EBL). Then, the compound BH and the compound BD (weight ratio of 96:4) are co-evaporated on the above-mentioned obtained film to form a 25nm thick film as a light-emitting layer (EML). Then, the compound HB1 is evaporated on the above-mentioned obtained film to form a 5nm thick film as a hole blocking layer (HBL). Then, 8-hydroxyquinoline-lithium (Liq) and the compound ET1 (weight ratio of 60:40) are co-evaporated on the above-mentioned obtained film to form a 30nm thick film as an electron transport layer (ETL). Finally, Liq was evaporated to form a 1 nm thick film as an electron injection layer (EIL) and 120 nm thick aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorber to complete the device.

[0229] Device Example 1.2:

[0230] Device Example 1.2 was fabricated in the same manner as Device Example 1.1, except that Compound 68 was used instead of Compound 56 as the HIL.

[0231] Device Example 1.3:

[0232] Device Example 1.3 was fabricated in the same manner as Device Example 1.1, except that Compound 70 was used instead of Compound 56 as the HIL.

[0233] Device Example 1.4:

[0234] Device Example 1.4 was fabricated in the same manner as Device Example 1.3, except that Compound 70 was used to form a 5 nm thick film as the HIL.

[0235] Device Example 1.5:

[0236] Device Example 1.5 was fabricated in the same manner as Device Example 1.3, except that Compound 70 was used to form a 2 nm thick film as the HIL.

[0237] Device Example 1.6:

[0238] Device Example 1.6 was produced in the same manner as Device Example 1.3, except that Compound HT2 was used instead of Compound HT1 as HTL.

[0239] Device Example 1.7:

[0240] Device Example 1.7 was fabricated in the same manner as Device Example 1.6, except that Compound 70 was used to form a 2 nm thick film as the HIL.

[0241] Device Example 1.8:

[0242] Device Example 1.8 was fabricated in the same manner as Device Example 1.6, except that Compound 70 was used to form a 1 nm thick film as the HIL.

[0243] Device comparison example 1.1:

[0244] Comparative Device Example 1.1 was fabricated in the same manner as in Device Example 1.1, except that Comparative Compound HI1 was used as the HIL instead of Compound 56.

[0245] Device comparison example 1.2:

[0246] Comparative device example 1.2 was prepared in the same manner as device example 1.6, except that compound 70 was not used and there was no hole injection layer.

[0247] The detailed device layer structure and thickness are shown in the table below. For layers using more than one material, different compounds are doped in the weight ratios recorded.

[0248] Table 1 Device structures of device embodiments and comparative examples

[0249]

[0250]

[0251] The material structure used in the device is shown below:

[0252]

[0253] For the above devices, at 10mA / cm 2 The IVL characteristics were measured, and the voltage (V), power efficiency (PE) and lifetime (LT95) were recorded and shown in Table 2.

[0254] Table 2 Device data

[0255]

[0256]

[0257] Discussion 1:

[0258] As can be seen from the above table, when 8 preferred embodiments of the present invention and comparative examples use a single material as a hole injection layer, the preferred embodiments are superior to the comparative examples in terms of voltage, power efficiency and lifespan. The voltage can be reduced by about 0.5V, the power efficiency is improved, and the lifespan is doubled. Even when the thickness of the hole injection layer is reduced to 5nm and 2nm, or even 1nm, the voltage, efficiency and lifespan are also very excellent. Especially in the absence of a hole injection layer, the voltage of the device is as high as 8.34V, and the power efficiency and lifespan are not as good as those of the device with a hole injection layer. It can be seen from this that when used as a hole injection layer alone, the compound of the present invention is a better choice than the comparative compound, and the improvement brought is completely unexpected.

[0259] Device Example 2

[0260] Device Example 2.1:

[0261] A glass substrate with an 80 nm thick indium tin oxide (ITO) transparent electrode was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot plate in a glove box before evaporation. The following materials were heated to a vacuum of about 10 -8The deposition was carried out sequentially on the glass surface at a rate of 0.2-2 angstroms / second under the condition of support. First, the compound 56 (dopant) of the present invention and the compound HT1 (weight ratio of 3:97) were co-deposited on the surface of the glass substrate to form a 10nm thick film as a hole injection layer (HIL). Then, the compound HT1 was evaporated on the above-obtained film to form a 120nm thick film as a hole transport layer (HTL). Then, the compound EB1 was evaporated on the above-obtained film to form a 5nm thick film as an electron blocking layer (EBL). Then, the compound BH and the compound BD (weight ratio of 96:4) were co-evaporated on the above-obtained film to form a 25nm thick film as a light-emitting layer (EML). Then, the compound HB1 was evaporated on the above-obtained film to form a 5nm thick film as a hole blocking layer (HBL). Then, 8-hydroxyquinoline-lithium (Liq) and compound ET1 (weight ratio of 60:40) were co-evaporated onto the above-obtained film to form a 30nm thick film as an electron transport layer (ETL). Finally, Liq was evaporated to form a 1nm thick film as an electron injection layer (EIL) and 120nm thick aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device.

[0262] Device Example 2.2:

[0263] Device Example 2.2 was fabricated in the same manner as Device Example 2.1, except that Compound 68 was used instead of Compound 56 as the dopant in the HIL.

[0264] Device Example 2.3:

[0265] Device Example 2.3 was fabricated in the same manner as Device Example 2.1, except that Compound 70 was used instead of Compound 56 as the dopant in the HIL.

[0266] Device Example 2.4:

[0267] Device Example 2.4 was fabricated in the same manner as Device Example 2.1, except that Compound HT2 was used instead of Compound HT1 and co-evaporated with Compound 56 (weight ratio 97:3) as HIL, and Compound HT2 was used instead of Compound HT1 as HTL.

[0268] Device Example 2.5:

[0269] Device Example 2.5 was fabricated in the same manner as Device Example 2.4, except that Compound 68 was used instead of Compound 56 as the dopant in the HIL.

[0270] Device Comparison Example 2:

[0271] Device Comparative Example 2 was fabricated in the same manner as Device Example 2.1, except that Compound HI1 was used as a dopant in the HIL instead of Compound 56.

[0272] The specific structures of the compounds used in the device are shown in Device Example 1.

[0273] The detailed device layer structure and thickness are shown in the table below. For layers using more than one material, different compounds are doped in the weight ratios recorded.

[0274] Table 3 Device structures of device embodiments and comparative examples

[0275]

[0276] For the above devices, at 10mA / cm 2 The IVL characteristics were measured, and the voltage (V), power efficiency (PE) and lifetime (LT95) were recorded and shown in Table 4.

[0277] Table 4 Device data

[0278]

[0279] Discussion 2:

[0280] As can be seen from the above table, when the five preferred embodiments and comparative examples of the present invention are used as dopants in HT1 or HT2 as hole injection layers, the performance of the two materials on the device is very different. First of all, in terms of voltage, the voltage of the comparative example is as high as 8.57V, while the voltage of the preferred example is only about 4.18V, which is reduced by half. The power efficiency of the embodiment is also twice or more than that of the comparative example. In particular, in terms of life, the preferred example is dozens of times that of the comparative example, which is not at the same order of magnitude at all. Therefore: When used as a dopant, the compound disclosed in the present invention is a hole injection material that is much better than the comparative compound. The improvement brought about by the compound of the present invention on device performance, especially in reducing voltage and increasing life, is completely unexpected and has an overwhelming advantage.

[0281] Device Example 3

[0282] Device Example 3.1:

[0283] A glass substrate with an 80 nm thick indium tin oxide (ITO) transparent electrode was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot plate in a glove box before evaporation. The following materials were heated to a vacuum of about 10 -8The deposition was carried out on the glass surface in sequence at a rate of 0.2-2 angstroms / second under the condition of support. First, compound 56 was evaporated onto the surface of the glass substrate to form a 10nm thick film as a hole injection layer (HIL). Next, compound HT1 was evaporated onto the above-obtained film to form a 35nm thick film as a hole transport layer (HTL). Then, compound EB2 was evaporated onto the above-obtained film to form a 5nm thick film as an electron blocking layer (EBL). Then, compound EB2, compound HB2 and compound GD (weight ratio of 46:46:8) were co-evaporated onto the above-obtained film to form a 40nm thick film as an emitting layer (EML). Then, compound HB2 was evaporated onto the above-obtained film to form a 5nm thick film as a hole blocking layer (HBL). 8-Hydroxyquinoline-lithium (Liq) and compound ET2 (weight ratio of 60:40) were co-evaporated onto the above-obtained film to form a 35nm thick film as an electron transport layer (ETL). Finally, Liq was evaporated to form a 1 nm thick film as an electron injection layer (EIL) and 120 nm thick aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorber to complete the device.

[0284] Device Example 3.2:

[0285] Device Example 3.2 was fabricated in the same manner as Device Example 3.1, except that Compound 56 (dopant) and Compound HT1 (weight ratio of 3:97) were co-evaporated instead of Compound 56 as the hole injection layer (HIL).

[0286] Device Example 3.3:

[0287] Device Example 3.3 was fabricated in the same manner as Device Example 3.1, except that Compound 70 was used instead of Compound 56 as the hole injection layer (HIL), and Compound HT2 was used instead of Compound HT1 as the HTL.

[0288] Device Example 3.4:

[0289] Device Example 3.4 was fabricated in the same manner as Device Example 3.3, except that Compound 70 (dopant) and Compound HT2 (weight ratio of 3:97) were co-evaporated instead of Compound 70 as the hole injection layer (HIL).

[0290] The specific structure of the new compound used in the device is shown below:

[0291]

[0292]

[0293] The detailed device layer structure and thickness are shown in the table below. For layers using more than one material, different compounds are doped in the weight ratios recorded.

[0294] Table 5 Device structure of device example

[0295]

[0296] For the above devices, at 10mA / cm 2 The IVL characteristics were measured, and the voltage (V), power efficiency (PE) and life (LT95) were recorded and shown in Table 6.

[0297] Table 6 Device data

[0298]

[0299] Discussion 3:

[0300] It can be seen from the green light device that when compound 56 and compound 70 are used alone as a hole injection layer, the voltage, efficiency and life performance are very excellent. When compound 56 and compound 70 are used as a hole injection layer as a dopant, compared with Example 3.1 and Example 3.3, the voltage is similar, the efficiency is slightly higher, and the life is longer when compound 56 and compound 70 are used alone as a hole injection layer.

[0301] Device Example 4

[0302] Device Example 4.1:

[0303] A glass substrate with an 80 nm thick indium tin oxide (ITO) transparent electrode was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot plate in a glove box before evaporation. The following materials were heated to a vacuum of about 10 -8The deposition was carried out on the glass surface in sequence at a rate of 0.2-2 angstroms / second under the condition of support. First, compound 56 was evaporated onto the surface of the glass substrate to form a 10nm thick film as a hole injection layer (HIL). Next, compound HT1 was evaporated onto the above-obtained film to form a 40nm thick film as a hole transport layer (HTL). Then, compound EB2 was evaporated onto the above-obtained film to form a 5nm thick film as an electron blocking layer (EBL). Then, compound RH and compound RD (weight ratio of 98:2) were co-evaporated onto the above-obtained film to form a 40nm thick film as a light-emitting layer (EML). Then, compound HB2 was evaporated onto the above-obtained film to form a 5nm thick film as a hole blocking layer (HBL). 8-Hydroxyquinoline-lithium (Liq) and compound ET2 (weight ratio of 60:40) were co-evaporated onto the above-obtained film to form a 35nm thick film as an electron transport layer (ETL). Finally, Liq was evaporated to form a 1 nm thick film as an electron injection layer (EIL) and 120 nm thick aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorber to complete the device.

[0304] Device Example 4.2 was prepared in the same manner as Device Example 4.1, except that Compound 56 (dopant) and Compound HT1 (weight ratio of 3:97) were co-evaporated onto the surface of the glass substrate to form a 10 nm thick film as a hole injection layer (HIL).

[0305] Device Example 4.3:

[0306] Device Example 4.3 was prepared in the same manner as Device Example 4.1, except that Compound 70 was used instead of Compound 56 as the hole injection layer (HIL), and Compound HT2 was used instead of Compound HT1 as the HTL.

[0307] Device Example 4.4:

[0308] Device Example 4.4 was fabricated in the same manner as Device Example 4.3, except that Compound 70 (dopant) and Compound HT2 (weight ratio of 3:97) were co-evaporated instead of Compound 70 as the hole injection layer (HIL).

[0309] The specific structure of the new compound used in the device is shown below:

[0310]

[0311] The detailed device layer structure and thickness are shown in the table below. For layers using more than one material, different compounds are doped in the weight ratios recorded.

[0312] Table 7 Device structure of device example

[0313]

[0314]

[0315] For the above devices, at 10mA / cm 2 The IVL characteristics were measured, and the voltage (V), power efficiency (PE) and lifetime (LT95) were recorded and shown in Table 8.

[0316] Table 8 Device data

[0317]

[0318] Discussion 4:

[0319] From the red light device, we can also see that when compound 56 and compound 70 are used alone as a hole injection layer, the voltage, efficiency and life are very good. When compound 56 and compound 70 are used as a hole injection layer as a dopant, compared with Example 4.1 and Example 4.3, the voltage is similar, the efficiency is slightly higher, and the life is longer when compound 56 is used alone as a hole injection layer.

[0320] Based on the above results, it can be concluded that the dehydrobenzobisoxazole derivative has excellent effect in red, green and blue devices whether used as a hole injection layer alone or as a dopant, and is a rare hole injection material.

[0321] The compounds disclosed in the present invention are dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole derivatives. Due to the different heteroatoms contained in their molecular mother nuclei, their lowest unoccupied molecular orbitals (LUMO) are different. The LUMOs of three types of compounds, dehydrobenzodioxazole (NO compounds), dehydrobenzodithiazole (NS compounds) and dehydrobenzodiselenazole derivatives (NSe compounds), are calculated by DFT (GAUSS-09, under the condition of B3LYP / 6-311G (d)), as shown in the following table:

[0322] Table 9 DFT calculation results

[0323]

[0324] From the previous device results, it can be seen that the device results of dehydrobenzodioxazole derivatives are excellent in all aspects and are highly efficient hole injection materials. From the above DFT calculation results, it can be seen that in the same series of molecular comparisons, the LUMO of dehydrobenzodioxazole derivatives, dehydrobenzodithiazole derivatives and dehydrobenzodiselenazole derivatives are almost the same, at around 0.2ev, indicating that all three types of compounds may have a deeper LUMO and have extremely electron-deficient characteristics. Therefore, dehydrobenzodithiazole derivatives and dehydrobenzodiselenazole derivatives also have the potential to become excellent hole injection materials, which may greatly improve OLED performance, such as longer device life, higher efficiency and lower voltage, and have very broad industrial application prospects.

[0325] It can be concluded from the above device results and DFT calculations that the dehydrobenzobisoxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and novel compounds with similar structures of the present invention are very important charge transfer materials, especially have unparalleled advantages in hole transport, and are suitable for different types of organic semiconductor devices, including but not limited to fluorescent OLED, phosphorescent OLED, white light OLED, stacked OLED, OTFT, OPV, etc.

[0326] It should be understood that the various embodiments described herein are only examples and are not intended to limit the scope of the present invention. Therefore, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the present invention. It should be understood that the various theories about why the present invention works are not intended to be restrictive.

Claims

1. A compound having formula 1: wherein X and Y are selected from CR"R"'; wherein Z1 and Z2 are selected from O or S at each occurrence, the same or different; R is selected, at each occurrence, identically or differently, from substituted or unsubstituted aryl having 6 to 20 carbon atoms; R" and R"' are selected from cyano; in, Each R may be the same or different, and at least one of R, R″ and R″′ is a group having at least one electron withdrawing group; Substituted aryl means that the aryl group is substituted with one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1-20 carbon atoms, unsubstituted cycloalkyl having 3-20 ring carbon atoms, unsubstituted heteroalkyl having 1-20 carbon atoms, unsubstituted alkoxy having 1-20 carbon atoms, unsubstituted aryl having 6-30 carbon atoms, unsubstituted heteroaryl having 3-30 carbon atoms, cyano, and combinations thereof.

2. The compound of claim 1, wherein R, R" and R'" are groups having at least one electron withdrawing group.

3. The compound of claim 1, wherein the Hammett constant of the electron withdrawing group is ≥0.05; the substituted aryl group refers to an aryl group substituted by one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, cyano, and combinations thereof.

4. The compound of claim 1, wherein the Hammett constant of the electron withdrawing group is ≥0.3; the substituted aryl group refers to an aryl group substituted by one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, and combinations thereof.

5. The compound of claim 1, wherein the Hammett constant of the electron withdrawing group is ≥ 0.

5.

6. The compound of claim 1, wherein the electron withdrawing group is selected from the group consisting of: halogen, cyano, azaaromatic ring group, and any of the following groups substituted by one or more of halogen, cyano, and azaaromatic ring group: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and combinations thereof.

7. The compound according to claim 1, wherein The electron withdrawing group is selected from the group consisting of F, CF3, OCF3, cyano, pyrimidinyl, triazine, and combinations thereof.

8. The compound of claim 1, wherein R is selected from the group consisting of unsubstituted aryl groups having 6 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms substituted by one or more groups of halogen, cyano, etc., at each occurrence.

9. The compound of claim 1, wherein R is selected, at each occurrence, identically or differently, from the group consisting of phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, trifluoromethylphenyl, trifluoromethoxyphenyl, bis(trifluoromethyl)phenyl, bis(trifluoromethoxy)phenyl, 4-cyanotetrafluorophenyl, and combinations thereof.

10. The compound of claim 1, wherein R is selected, at each occurrence, identically or differently, from phenyl or biphenyl substituted with one or more of F, CN or CF3.

11. The compound of claim 1, wherein each occurrence of R is identically or differently selected from the group consisting of:

12. The compound according to claim 11, wherein In one compound represented by Formula 1, two Rs are the same.

13. The compound according to claim 11, which has a structure represented by Formula 2: in, The two Z in Formula 2 have the same structure, the two RR structures are the same or different, and the Z, X, Y, and R are respectively selected from atoms or groups shown in the following table: Where A1 is 14. An electroluminescent device comprising: anode, cathode, An organic layer is disposed between the anode and the cathode, wherein the organic layer comprises the compound according to any one of claims 1 to 13. 15 . The electroluminescent device according to claim 14 , wherein the organic layer is a hole injection layer, and the hole injection layer is formed of the compound alone.

16. The electroluminescent device of claim 14, wherein the organic layer is a hole injection layer, and the hole injection layer is formed by the compound comprising a dopant, wherein the dopant comprises at least one hole transport material; the hole transport material comprises a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000.

17. The electroluminescent device of claim 16, wherein the molar doping ratio of the compound to the hole transport material is 10:1 to 1:

100.

18. The electroluminescent device of claim 14, comprising a plurality of stacked layers between an anode and a cathode, the stacked layers comprising a first light emitting layer and a second light emitting layer, wherein: The first stacked layer includes a first light-emitting layer, the second stacked layer includes a second light-emitting layer, and the charge generation layer is disposed between the first stacked layer and the second stacked layer, wherein the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer; The organic layer comprising the compound of Formula 1 is a p-type charge generating layer.

19. The electroluminescent device of claim 18, wherein the p-type charge generating layer may further comprise at least one hole transporting material, the p-type charge generating layer being formed by doping the compound into the at least one hole transporting material, the hole transporting material comprising a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the compound to the hole transporting material is 10000:1 to 1:10000.

20. The electroluminescent device of claim 19, wherein the molar doping ratio of the compound to the hole transport material is 10:1 to 1:

100.

21. The electroluminescent device of claim 18, wherein the charge generation layer further comprises a buffer layer disposed between the p-type charge generation layer and the n-type charge generation layer, the buffer layer comprising the compound.

22. A compound composition comprising the compound according to any one of claims 1-13.

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