CN112745333B

CN112745333B - Organic electroluminescent material and device

Info

Publication number: CN112745333B
Application number: CN201911046002.3A
Authority: CN
Inventors: 崔至皓; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2019-10-30
Filing date: 2019-10-30
Publication date: 2022-12-20
Anticipated expiration: 2039-10-30
Also published as: CN115716838A; CN112745333A; KR20210053130A; JP2021070681A; JP2022089838A; DE102020104604A1; JP7054537B2; KR102408338B1; KR102541819B1; KR20220080058A

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 the like, and can be used as a charge transport material, a charge injection material and a charge generation material in an electroluminescent device. The novel compounds can greatly improve the performances of voltage, service life and the like of the organic electroluminescent device. An electroluminescent device and compound formulation are also disclosed.

Description

Organic electroluminescent material and device

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. More particularly, it relates to a novel compound having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and the like, and an organic electroluminescent device and a compound formulation comprising the same.

Background

Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic Light Emitting Transistors (OLETs), organic Photovoltaics (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 plasma light emitting devices.

In 1987, tang and Van Slyke, by Isman Kodak, reported a two-layer organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters,1987,51 (12): 913-915). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). The most advanced OLEDs may comprise 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 anode. Since OLEDs are a self-emissive solid state device, it offers great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in the fabrication of flexible substrates.

OLEDs can be classified into three different types according to their light emitting mechanism. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes to the commercialization of Active Matrix OLEDs (AMOLEDs). Recently, adachi has 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 the triplet state to the singlet state. In TADF devices, triplet excitons are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.

Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.

The organic light emitting display device uses a hole injection layer and an electron injection layer to facilitate charge injection. Wherein the hole injection layer is a functional layer formed of a single material or more than one material. Single material approaches typically utilize deep LUMO materials, while approaches with more than one material form by doping hole-transporting materials with P-type, deep LUMO materials. The common point for both is the need to utilize deep LUMO materials.

US20050121667 discloses the use of an organic mesogenic compound, which is a quinone or quinone derivative and which has a lower volatility than F4-TCNQ under the same evaporation conditions, as an organic dopant to dope an organic semiconducting matrix material to alter its electrical properties. The general structure disclosed therein comprises the following:

this application focuses primarily on the unique properties of quinones or quinone derivatives as dopants, but it does not disclose or teach the characteristics and applications of any compound having a similar core structure as the present application.

However, deep LUMO materials are not easily synthesized due to their strongly electron-withdrawing substituents, and it is difficult to have the properties of deep LUMO, high stability, and high film-forming properties at the same time. For example, F4-TCNQ (P-type hole injection material), although having a deep LUMO, has a too low evaporation temperature, affecting the control of deposition and reproducibility of production properties and thermal stability of devices; for example, HATCN has a problem of film-forming property in a device because of its high crystallinity, and LUMO is not deep enough to be used as P-type doping. Since the hole injection layer has a great influence on the voltage, efficiency and lifetime of the OLED device, it is very important and urgent to develop a deep LUMO, high-stability and high-film-forming material in the industry.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of novel compounds having a structure similar to dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole. The compound can be used as a charge transport material and a charge injection material in an organic electroluminescent device. The novel compounds can greatly improve the performances of voltage, service life and the like of the organic electroluminescent device.

According to one embodiment of the present invention, a compound having the structure of formula 1 is disclosed:

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

wherein Z ₁ And Z ₂ Identically or differently on each occurrence is selected from O, S or Se;

r, R ', R "and R'" are, identically or differently on each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ A boryl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

wherein 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;

adjacent substituents can optionally be joined to form a ring.

According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having formula 1:

r, R ', R "and R'" are, identically or differently at each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ A boryl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

adjacent substituents can optionally be joined to form a ring;

wherein 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.

According to another embodiment of the present invention, a compound formulation comprising the compound having the structure of formula 1 is also disclosed.

The novel compound with the structure similar to that of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole can be used as a charge transport material and a charge injection material in an electroluminescent device. The novel compounds can greatly improve the performances of voltage, service life and the like of the organic electroluminescent device.

Drawings

FIG. 1 is a schematic representation of an organic light emitting device that can contain the compounds and compound formulations disclosed herein.

Fig. 2 is a schematic diagram of a tandem organic light emitting device that can contain compounds and compound formulations disclosed herein.

Fig. 3 is a schematic diagram of another tandem organic light emitting device that may contain compounds and compound formulations disclosed herein.

Figure 4 is structural formula 1 showing compounds as disclosed herein.

Detailed Description

OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. 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, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the described layers. The properties and functions of the various layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.

There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50 ₄ m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson (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. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose the use of cathodesExamples include composite cathodes having a thin layer of a metal such as Mg: ag with an overlying layer of transparent, conductive, sputter-deposited ITO. 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 implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of a protective layer can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.

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.

In one embodiment, two or more OLED cells can be connected in series to form a series OLED, as shown schematically and without limitation in FIG. 2 for a series OLED device 500. The apparatus 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, an emission 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, an emission 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 may be fabricated by sequentially depositing the described layers.

The OLED may also be provided with an encapsulation layer, as shown schematically and non-limitingly in fig. 3 for an organic light emitting device 600, which differs from fig. 2 in that an encapsulation layer 102 may also be included over the cathode 290 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.

Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.

The materials and structures described herein may also be used in other organic electronic devices as previously listed.

As used herein, "top" means furthest from the substrate, and "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. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.

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.

A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties 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 properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.

It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).

On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch between energy states. Thermal energy can activate a transition from a triplet state back to a singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the retardation component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, the fraction of the backfill singlet excited state may reach 75%. The total singlet fraction may be 100%, far exceeding 25% of the spin statistics of the electrogenerated excitons.

The delayed fluorescence characteristic of type E can be found in excited complex systems or in single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small singlet-triplet energy gap (Δ Ε) _S-T ). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ E _S-T . These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).

Definition of terms with respect to substituents

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

Alkyl-comprises both straight 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 carbons 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 preferable.

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

Alkenyl-as used herein, encompasses straight and branched chain alkene groups. Preferred alkenyl groups are those 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.

Alkynyl-as used herein, straight and branched alkynyl groups are contemplated. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group,biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,

perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-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- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylphenyl and m-quaterphenyl.

Heterocyclyl or heterocyclic-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing from 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups are contemplated which may contain 1 to 5 heteroatoms. 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, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, quinoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, benzothiophene, cinnoline, selenobenzene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 3236 zzborane, 5262-oxazaborane, 5262 z3763, azazft-3, and aza-azole analogs thereof. In addition, the heteroaryl group may be optionally substituted.

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

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

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

The term "aza" in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the aza derivatives described above will be readily apparent to one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as described herein.

It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.

In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitutions of other stable isotopes in the compounds may be preferred because they enhance the efficiency and stability of the device.

In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.

In this 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 phosphinoxy, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphinoxy any of which may be substituted with one or more groups selected from deuterium, halogen, an unsubstituted alkyl group having 1 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, thio, sulfinyl, sulfonyl, phosphinoxy, and combinations thereof.

In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may 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 as well as substituents bonded to carbon atoms directly bonded to each other.

The expression that adjacent substituents can optionally be linked to form a ring is also intended 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:

the expression that adjacent substituents can optionally be linked to form a ring is also intended 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:

further, the expression 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 two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at a position to which a hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following equation:

according to one embodiment of the invention, there is disclosed a compound having formula 1:

r, R 'and R' are selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ A boryl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

adjacent substituents can optionally be linked to form a ring.

In this embodiment, each occurrence of R, R ', R ", and R'" is selected from the group of substituents, which may be the same or different, and it will be readily apparent to one skilled in the art that certain substituents having the same number (e.g., R ', R ", or R'") for two occurrences at the same time in formula 1 may be selected from the same substituent or different substituents.

According to one embodiment of the invention, wherein X and Y are the same or different at each occurrence and are selected from CR 'R "or NR'", R ', R "and R'" are groups having at least one electron-withdrawing group.

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

According to one embodiment of the invention, wherein X and Y are the same or different at each occurrence and are selected from O, S or Se, at least one of R is a group with at least one electron-withdrawing group.

According to one embodiment of the invention, wherein X and Y are the same or different at each occurrence and are selected from O, S or Se, R being a group having at least one electron-withdrawing group.

According to an embodiment of the invention, the Hammett constant of the electron withdrawing group is 0.05 or more, or the Hammett constant of the electron withdrawing group is 0.3 or more, or the Hammett constant of the electron withdrawing group is 0.5 or more.

The Hammett substituent constant value of the electron withdrawing group is more than or equal to 0.05, preferably more than or equal to 0.3, more preferably more than or equal to 0.5, the electron withdrawing capability is strong, the LUMO energy level of the compound can be remarkably reduced, and the effect of improving the charge mobility is achieved.

Note that the hammett substituent constant value includes a para-constant and/or a meta-constant of the hammett substituent, and any one of the para-constant and the meta-constant satisfies 0.05 or more may be used as a group selected in the present invention.

According to one embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boryl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, or substituted halo, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boryl, sulfinyl, sulfonyl, phosphinoxy, an azaaryl group, substituted with one or more of any of the following: 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 aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein the electron-withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl, and combinations thereof.

According to one embodiment of the invention, wherein X and Y, on each occurrence, are selected, identically or differently, from the group consisting of:

wherein R is ₁ Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ A boryl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

wherein V and W are selected, identically or differently on each occurrence, from CR _v R _w ，NR _v ，O，S，Se；

Wherein Ar, identically or differently at each occurrence, is selected 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;

wherein, A, R _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v And R _w The same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ A boryl group, a sulfinyl group, a sulfonyl group, a phosphinoxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

wherein A is a group having at least one electron-withdrawing group, and for either structure when R is _a ，R _b ，R _c ，R _d ，R _e ，R _f ，R _g ，R _h ，R _v And R _w At least one of which is a group having at least one electron withdrawing group.

In this example, "' indicates the position where the X and Y groups are attached to the dehydrobenzodioxazole, dehydrobenzodithiazole, or dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the present invention, wherein R ₁ The same or different at each occurrence is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof.

According to one embodiment of the invention, the group having at least one electron-withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof.

According to one embodiment of the invention, wherein X and Y are, on each occurrence, selected identically or differently from the group consisting of:

O，S，Se，

in this embodiment, "-" indicates the position where the X and Y groups are attached to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the invention, wherein R is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ Boryl, sulfinyl, sulfonyl, phosphinoxy, 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 having 3 to 30 carbon atoms, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any of the following groups substituted with one or more of a boryl group, a sulfinyl group, a sulfonyl group and a phosphinyl group: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 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;

according to one embodiment of the invention, wherein R is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, methyl, isopropyl, NO ₂ ，SO ₂ CH ₃ ，SCF ₃ ，C ₂ F ₅ ，OC ₂ F ₅ ，OCH ₃ Diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, mesityl oxide, and CF ₃ By CN or CF ₃ Substituted ethynyl, dimethylphosphinoxy, diphenylphosphinoxy, F, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, substituted by F, CN and CF ₃ One or more substituted phenyl or biphenyl groups of (a), a tetrafluoropyridyl group, a pyrimidinyl group, a triazinyl group, a diphenylboryl group, a oxaboro-anthracenyl group, and combinations thereof.

According to one embodiment of the invention, wherein X and Y are

According to one embodiment of the invention, wherein R is selected, identically or differently on each occurrence, from the group consisting of:

in the present embodiment, it is preferred that,

represents a position where the R group is linked to a dehydrobenzodioxazole ring, a dehydrobenzodithiazole ring or a dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the present invention, wherein two R are the same in one compound represented by formula 1.

According to one embodiment of the present invention, wherein the compound is selected from the group consisting of compound 1 to compound 1356, the compound 1 to compound 1356 has a structure represented by formula 2:

wherein, two Z structures in formula 2 are the same, two R structures are the same or different, and Z, X, Y, R is respectively corresponding to atoms or groups selected from the following table:

according to an embodiment of the present invention, there is also disclosed an electroluminescent device, including:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having formula 1:

adjacent substituents can optionally be linked to form a ring.

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

According to one embodiment of the present invention, in the device, wherein the organic layer is a hole injection layer, and the hole injection layer is formed of the compound containing a dopant containing at least one hole transport material; the hole transport material comprises a compound with triarylamine units, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylethylene 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.

according to an embodiment of the present invention, wherein in the hole injection layer, a molar doping ratio of the compound to the hole transport material is 10.

According to an embodiment of the present invention, the electroluminescent device includes a plurality of stacked layers between an anode and a cathode, the stacked layers including a first light emitting layer and a second light emitting layer, wherein the first stacked layer includes the first light emitting layer, the second stacked layer includes the second light emitting layer, and a 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; wherein the organic layer comprising the compound having formula 1 is a p-type charge generation layer.

According to an embodiment of the present invention, the p-type charge generation layer further includes at least one hole transport material, 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 includes a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylethylene compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein a molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000.

according to an embodiment of the present invention, wherein in the p-type charge generation layer, a molar doping ratio of the compound to the hole transport material is 10.

According to an embodiment of the present invention, 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.

According to another embodiment of the present invention, a compound formulation comprising a compound represented by formula 1 is also disclosed. The specific structure of the compound is shown in any one of the embodiments.

In combination with other materials

The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application US2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application US2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

In the examples of material synthesis, all reactions were carried out under nitrogen unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product is subjected to structural confirmation and characterization using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai prism-based fluorescence spectrophotometer, wuhan Corset's electrochemical workstation, anhui Bei Yi g sublimator, etc.) in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.

Materials synthesis example:

the preparation method of the compound of the present invention is not limited, and the following compounds are typically but not limited, and the synthetic route and preparation method thereof are as follows:

synthesis example 1: synthesis of Compound 56

Step 1: [ intermediate 1-a ] Synthesis

DMSO (150 mL) was placed in a 500mL three-necked flask, nitrogen was bubbled for half an hour, and HC (OEt) was added sequentially ₃ (22.2g，150mmol)，Y(OTf) ₃ (2.15g, 4mmol) and bubbling was continued for 5 minutes, 2,5-diamino-3,6-dibromobenzene-1,4-diol (8.94g, 30mmol) was added, the temperature was raised to 60 ℃ and the solution became brown or khaki after 20 minutes, and the mixture was stirred overnight. After the reaction was complete, DCM/PE (1:1, 500 mL) was added, the solid collected by filtration, washed with acetone, and filtered to give off-white solid 1-a (7.2g, 75% yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝9.03(s,2H)。

And 2, step: synthesis of [ intermediate 1-b ]

Into a 250mL two-necked flask, dioxane (50 mL) was added, nitrogen was bubbled for 15 minutes, and Pd (OAc) was added with stirring ₂ (225mg, 10mol%,1.0 mmol) and XPhos (1.0g, 2.1mmol) and stirring was continued for 10 minutes, and then 1-a (3.18g, 10mmol), p-trifluoromethoxybenzeneboronic acid (8.24g, 40mmol) and potassium carbonate (8.34g, 60mmol) were added in this order. The mixture was heated to 110 ℃ and refluxed, and stirred overnight under nitrogen. After the reaction, the temperature is reduced, the reaction product is filtered by diatomite, fully washed by dichloromethane and separated by silica gel column chromatography to obtain a white solid 1-b (4.36g, 91 percent yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝9.00(s,2H)，8.33(d,J＝8.8Hz,4H)，7.63(d,J＝8.8Hz,4H)。

And step 3: synthesis of [ intermediate 1-c ]

Intermediate 1-b (4.36g, 9.1mmol) was added to THF (114mL, 0.08M) under nitrogen, cooled to-94 deg.C (acetone/liquid nitrogen cold bath), n-butyllithium (13.8mL, 20.93mmol,1.6M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1h, and then slowly increased to-78 deg.C (acetone/dry ice cold bath) and reacted for 8h. A THF solution (15 mL) of elemental iodine (6.93g, 27.3 mmol) was added and the mixture was slowly warmed to room temperature overnight, quenched with a small amount of saturated aqueous ammonium chloride, and then directly stirred with celite and purified by silica gel column chromatography (PE: DCM = 3:1-1:1) to give the product 1-c as a white solid (4.0g, 60% yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝8.16(d,J＝8.8Hz,4H)，7.62(d,J＝8.8Hz,4H)。

And 4, step 4: synthesis of [ intermediate 1-d ]

Under nitrogen atmosphere, malononitrile (2.78g, 42mmol) was added to anhydrous DMF (70 mL), naH (1.67g, 42mmol,60% content) was added in portions at 0 ℃ and stirred at 0 ℃ for 10 minutes and at room temperature for 20 minutes, after which 1-c (5.08g, 7mmol) and Pd (PPh) were added ₄ ) ₃ (1.62g, 1.4 mmol), heating to 90 ℃ and reacting for 24-36h. Pouring into ice water after complete conversion, and adjusting pH with 4N dilute hydrochloric acid<1, after fully stirring, a large amount of yellow solid is separated out, filtered and collected. Washing with dichloromethane gave 4.38g of a yellow solid. After which it was washed twice in succession with dichloromethane and filtered to give 1-d as a yellow solid (4.2g, 98% yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝8.08(d,J＝8.8Hz,4H)，7.56(d,J＝8.8Hz,4H)。

And 5: synthesis of Compound 56

Under nitrogen atmosphere, 1-d (3.04g, 5 mmol) is added into DCM (150 mL), the temperature is reduced to 0 ℃, PIFA (6.45g, 15mmol) is added in batches, and the mixture is stirred at room temperature for 3 days, so that the solution is purple black. N-hexane (450 mL) was added to the reaction solution, and the mixture was stirred for 10 minutes and then filtered to obtain a greenish black solid. Washed twice with each of (DCM/PE = 2:1-1:1) to give dark green solid compound 56 (2.5g, 83% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.30(d,J＝8.4Hz,4H)，7.73(d,J＝8.4Hz,4H)。

Synthetic example 2: synthesis of Compound 68

Step 1: [ intermediate 2-a ] Synthesis

Into a 250mL two-necked flask, dioxane (80 mL) was added, nitrogen was bubbled for 15 minutes, and Pd (OAc) was added with stirring ₂ (360mg, 1.6mmol) and XPhos (1.53g, 3.2mmol) and stirring was continued for 10 minutes, after which 1-a (4.1g, 13mmol), 3,5-bis (R) (1.533 mmol) were addedTrifluoromethyl) phenylboronic acid (14.0g, 54mmol), cesium fluoride (9.12g, 60mmol). The mixture was heated to 110 ℃ and refluxed, and stirred overnight under nitrogen. After the reaction, the temperature was reduced, and the reaction mixture was filtered through celite, washed with dichloromethane, and separated by silica gel column chromatography to give 2-a (6.7g, 88% yield) as a white solid. ¹ HNMR(400MHz,CDCl ₃ )δ＝8.87(s,4H)，8.41(s,2H)，8.00(s,2H)。

Step 2: [ intermediate 2-b ] Synthesis

Under a nitrogen atmosphere, 2-a (6.2g, 10.6 mmol) was added to THF (212mL, 0.05M), the temperature was lowered to-94 deg.C (acetone/liquid nitrogen cooling bath), n-butyllithium (15.2mL, 24.4mmol,1.6M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 hour, and then slowly raised to-78 deg.C (acetone/dry ice cooling bath) and reacted for 8 hours. A THF solution (20 mL) of elemental iodine (8.07g, 31.8mmol) was added, the mixture was slowly warmed to room temperature overnight, quenched with a small amount of saturated aqueous ammonium chloride, and directly stirred with celite, and purified by silica gel column chromatography (PE: DCM = 6:1-2:1) to give the product 2-b as a white solid (4.7g, 53% yield). ¹ HNMR(400MHz,CDCl ₃ )δ＝8.69(s,4H),8.01(s,2H)。

And step 3: [ intermediate 2-c ] Synthesis

Under nitrogen atmosphere, malononitrile (1.56g, 23.7mmol) was added to anhydrous DMF (55mL, 0.1M), naH (948mg, 23.7mmol, content: 60%) was added in several portions at 0 ℃ and stirred at 0 ℃ for 10 minutes and at room temperature for 20 minutes, and then 2-b (3.3g, 3.95mmol) and Pd (PPh) ₄ ) ₃ (456 mg, 0.39mmol), and the temperature is raised to 90 ℃ for reaction for 24-36h. Pouring into ice water after complete conversion, and adjusting pH with 4N dilute hydrochloric acid<1, after fully stirring, a large amount of yellow solid is separated out, filtered and collected. Washing with dichloromethane gave 2.98g of a yellow solid. Then washed twice in succession with solvent (DCM/PE =2:1, 200 mL) and filteredYellow solid 2-c was obtained (2.81g, 99% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.57(s,4H),8.33(s,2H)。

And 4, step 4: synthesis of Compound 68

Under nitrogen atmosphere, 2-c (2.85g, 4.0 mmol) is placed into three two-mouth bottles in 3 parts (0.95 g/part), DCM (200 mL) is added respectively, after cooling to 0 ℃, PIFA (1.73g, 4.0 mmol) is added in batches, and the solution is stirred at room temperature for 3 days to be purple black. Then, the three bottles of the solution were placed in a 1L single-necked bottle, the solution was spin-dried to about 50mL, n-hexane (450 mL) was added thereto, stirred for 10 minutes, and then filtered to obtain a dark green solid. Washed twice with each (DCM/PE =2:1, 200 mL) to give blackish green solid compound 68 (2.4 g,85% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.86(s,4H),8.37(s,2H)。

Synthetic example 3: synthesis of Compound 70

Step 1: [ intermediate 4-a ] Synthesis

Into a 250mL two-necked flask, dioxane (80 mL) was added, nitrogen was bubbled for 15 minutes, and Pd (OAc) was added with stirring ₂ (360mg, 1.6mmol) and XPhos (1.53g, 3.2mmol) and stirring was continued for 10 minutes, after which 1-a (4.1g, 13mmol), 2,4-bis (trifluoromethyl) phenylboronic acid (14.0g, 54mmol), cesium fluoride (9.12g, 60mmol) were added in that order, the mixture was refluxed at 110 ℃ and stirred overnight under nitrogen protection. After the reaction was completed, the temperature was reduced, and the mixture was filtered through celite, washed with dichloromethane, and separated by silica gel column chromatography to give 4-a (6.83g, 90% yield) as a white solid. ¹ HNMR(400MHz,CDCl ₃ )δ＝8.19(s,2H),8.12(s,2H)，8.02(d,J＝8.0Hz,2H)，7.77(d,J＝8.0Hz,2H)。

Step 2: [ intermediate 4-b ] Synthesis

Under a nitrogen atmosphere, 4-a (6.4g, 111mmol) was added to THF (150 mL), the temperature was lowered to-94 deg.C (acetone/liquid nitrogen cooling bath), n-butyllithium (15.8mL, 25.3mmol,1.6M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 hour, and then the temperature was slowly raised to-78 deg.C (acetone/dry ice cooling bath) and reacted for 8 hours. A THF solution (20 mL) of elemental iodine (8.4g, 33mmol) was added and slowly warmed to room temperature overnight, quenched with a small amount of saturated aqueous ammonium chloride, and directly stirred with celite and purified by silica gel column chromatography (PE: DCM =10, 1-2:1) to give the product 4-b as a white solid (6.89g, 75% yield). ¹ HNMR(400MHz,CDCl ₃ )δ＝8.16(s,2H)，8.01(d,J＝7.6Hz,2H)，7.73(d,J＝7.6Hz,2H)。

And step 3: [ intermediate 4-c ] Synthesis

Malononitrile (2.14g, 32mmol) was added to anhydrous DMF (60 mL) under nitrogen, naH (1.40g, 35mmol,60% content) was added in portions at 0 deg.C, stirred at 0 deg.C for 10 minutes and at room temperature for 20 minutes, after which 4-b (4.51g, 5.4mmol) and Pd (PPh) ₄ ) ₃ (1.15g, 1.0mmol), and the reaction was carried out at 90 ℃ for 24 to 36 hours. Pouring into ice water after complete conversion, and adjusting pH with 4N dilute hydrochloric acid<1, after fully stirring, a large amount of yellow solid is separated out, filtered and collected. Washing with dichloromethane gave 2.98g of a yellow solid. This was followed by two successive washes with dichloromethane and filtered to give 4-c as a yellow solid (2.92g, 76% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.35(m,4H)，8.16(d,J＝7.6Hz,2H)。

And 4, step 4: synthesis of Compound 70

Under nitrogen atmosphere, 4-c (2.92g, 4.1mmol)Placing 3 parts (1 g/part) in three two-mouth bottles, respectively adding DCM (100 mL), cooling to 0 ℃, respectively adding PIFA (1.8g, 4.2mmol) in batches, and stirring at room temperature for 3 days to obtain a purple black solution. Then, the three bottles of the solution were placed in a 1L single-necked bottle, the solution was concentrated to about 50mL, n-hexane (450 mL) was added thereto, and after stirring for 10 minutes, filtration was performed to obtain a purple solid. Washed twice with each (DCM/PE =2:1, 200 mL) to give compound 70 as a violet solid (2.0 g,70% yield). ¹ HNMR(400MHz,CD ₂ Cl ₂ )δ＝8.22(s,2H),8.11(d,J＝8.4Hz,2H)，7.75(d,J＝8.0Hz,2H)。

Synthetic example 4: synthesis of Compound 101

Step 1: [ intermediate 5-a ] Synthesis

A500 mL two-necked flask was charged with distilled water (50 mL), 1,4-phenylenediamine (17.0g, 157mmol) and hydrochloric acid (30.7mL, 125mmol), heated to 50 ℃ and NH was added ₄ SCN (48.4g, 636mmol) was stirred for 24h while the temperature was increased to 90 ℃. After the reaction was completed, the temperature was decreased, and the reaction mixture was filtered, washed with ethanol, and then filtered to obtain a gray solid compound 5-a (31.5 g,90% yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝9.69(s,2H),7.32(s,4H)。

And 2, step: [ intermediate 5-b ] Synthesis

A500 mL three-necked flask was charged with compound 5-a (15g, 66.5mmol) and chloroform (100 mL) in this order, heated to 50 ℃ and then a solution of bromine (8mL, 309mmol) in chloroform (100 mL) was added dropwise very slowly, and the mixture was refluxed for 24 to 36 hours after the addition. After the reaction is finished, the temperature is reduced to 0 ℃, the filtration is carried out, and the filter cake is washed by chloroform for three times. The solid was collected, washed with saturated sodium thiosulfate solution, filtered, collected, washed with methanol and dichloromethane, respectively, and filtered to give 5-b (12.5 g,83% yield) as a brown solid. ¹ HNMR(400MHz,d ₆ -DMSO)δ＝8.56(bs,4H),7.83(s,2H)。

And step 3: [ intermediate 5-c ] Synthesis

Acetonitrile (500 mL) was charged into a 1L three-necked flask, nitrogen was bubbled for 20 minutes, and then compound 5-b (11g, 50mmol), iodine (76g, 300mmol) and tBuONO (20.6 g, 200mmol) were added in this order and reacted at 70 ℃ for 24 hours. After the reaction was completed, the temperature was decreased, acetonitrile was distilled off under reduced pressure, 200mL of dichloromethane was added, filtered, and washed with petroleum ether to obtain brick red solid 5-c (11g, 50% yield). ¹ HNMR(400MHz,d ₆ -DMSO)δ＝8.74(s,2H)。

And 4, step 4: synthesis of [ intermediate 5-d ]

Under nitrogen atmosphere, malononitrile (5.35g, 81mmol) was added to anhydrous DMF (135 mL), naH (3.24g, 81mmol,60% content) was added in portions at 0 ℃, stirred at 0 ℃ for 10 minutes and at room temperature for 20 minutes, after which compounds 5-c (6.08g, 13.5 mmol) and Pd (PPh) were added ₄ ) ₃ (3.12g, 2.7mmol), heating to 90 deg.C and reacting for 24-36h. Pouring into ice water after complete conversion, and adjusting pH with 4N dilute hydrochloric acid<1, after fully stirring, a large amount of brown solid is separated out, filtered and collected. Washing with dichloromethane gave 4.2g of a brown solid. Then washed twice with dichloromethane and filtered to give a brown solid 5-d (4.02g, 93% yield). LCMS (ESI): m/z 319[ m-H ]] ^- 。

And 5: synthesis of Compound 101

Under nitrogen atmosphere, the compound (3.20g, 10mmol) was added into DCM (1L), the temperature was reduced to 0 deg.C, PIFA (12.9g, 30mmol) was added in portions, and the mixture was stirred at room temperature for 3 days to obtain a solutionPurple black. After the reaction, the solution was spin-dried to about 100mL, and then n-hexane (450 mL) was added to the reaction solution, followed by stirring for 10 minutes and filtration to obtain a violet-black solid. The residue was washed twice with dichloromethane to give a violet black solid compound 101 (3.0 g,94% yield). LCMS (ESI): m/z 317[ m-H ]] ^- 。

Synthesis example 5: synthesis of Compound 69

Step 1: [ intermediate 6-a ] Synthesis

In a 250mL two-mouth bottle, 2,5-bis (trifluoromethyl) bromobenzene (18.5g, 63mmol) and super-dry tetrahydrofuran (100 mL) are added under nitrogen atmosphere, the temperature is reduced to-78 ℃, an isopropyl magnesium chloride lithium chloride solution (54mL, 69mmol,1.3M tetrahydrofuran solution) is slowly dropped, after dropping, the reaction is carried out for 1h at-78 ℃, and then the reaction is carried out for 4h at room temperature. ZnCl is slowly dropped into the solution at room temperature ₂ (35mL, 69.3mmol,2.0M 2-methyltetrahydrofuran solution), and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Adding Pd (OAc) in one time under the protection of nitrogen ₂ (337mg, 1.5mmol), XPhos (1.43g, 3.0mmol) and 1-a (5.0g, 15.7mmol) and stirring was continued for 10 minutes, after which the temperature was raised and reflux was carried out for 24 hours. After the reaction is finished, the temperature is reduced, a small amount of saturated ammonium chloride solution is added for quenching, diatomite is filtered, dichloromethane is fully washed, and silica gel column chromatography separation is carried out to obtain off-white solid 6-a (4.23g, 46 percent yield). ¹ HNMR(400MHz,CDCl ₃ )δ＝8.13(s,2H)，8.07(d,J＝8.4Hz,2H)，7.95(d,J＝8.4Hz,2H)，7.87(s,2H)。

Step 2: [ intermediate 6-b ] Synthesis

6-a (4.23g, 7.2mmol) was added to THF (200 mL) under a nitrogen atmosphere, cooled to-94 ℃ and n-butyllithium (10.4 mL,16.6mmol,1.6M n-hexane solution) was slowly added dropwise, the temperature was maintained for 1 hour, and then the reaction was slowly raised to-78 ℃ for 8 hours. Adding elementary iodine at-78 deg.C(5.49g, 33mmol) in THF (30 mL), slowly warmed to room temperature after addition overnight, quenched with a small amount of saturated aqueous ammonium chloride, directly stirred with celite, and purified by silica gel column chromatography (PE: DCM10: 1-1:1) to give 6-b (2.7g, 45% yield) as a pale yellow solid. ¹ HNMR(400MHz,CDCl ₃ )δ＝8.05(s,J＝8.4Hz,2H)，7.94(d,J＝8.4Hz,2H)，7.83(s,2H)。

And step 3: [ intermediate 6-c ] Synthesis

Under nitrogen atmosphere, malononitrile (792mg, 12mmol) was added to anhydrous DMF (20 mL), naH (480mg, 12mmol,60% content) was added in several portions at 0 ℃, stirring was carried out at 0 ℃ for 10 minutes, then at room temperature for 20 minutes, and then 6-b (1.70g, 2mmol) and Pd (PPh) were added ₄ ) ₃ (277mg, 0.24mmol), heating to 90 deg.C and reacting for 24-36h. After complete conversion, the mixture is poured into ice water and the pH is adjusted with 4N dilute hydrochloric acid<1, after fully stirring, a large amount of yellow solid is separated out, filtered and collected. Washing with dichloromethane gave 1.50g of a yellow solid. This was followed by two successive washes with dichloromethane and filtered to give 6-c as a yellow solid (1.40g, 98% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.37-8.26(m,5H)，8.13(s,1H)。

And 4, step 4: synthesis of Compound 69

6-c (1.40g, 2mmol) and DCM (200 mL) were added to a 500mL two-necked flask under nitrogen, the temperature was reduced to 0 deg.C, PIFA (1.72g, 4.0 mmol) was added in portions, and the mixture was stirred at room temperature for 7 days, whereby the solution was purple-black. After the reaction, the solution was concentrated to about 20mL, and n-hexane (450 mL) was added thereto, stirred for 10 minutes, and then filtered to obtain a gray black solid. Washing twice with (DCM/PE =2:1, 100 mL) gave compound 69 as a grey black solid (1.2g, 85% yield). ¹ HNMR(400MHz,d ₆ -acetone)δ＝8.38-8.27(m,5H),8.13(s,1H)。

It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other structures of the compounds of the present invention.

Device embodiment one

Device example 1.1:

a glass substrate with an Indium Tin Oxide (ITO) transparent electrode 80nm thick was treated with oxygen plasma and UV ozone. And drying the cleaned glass substrate on a hot table in a glove box before vapor deposition. The following materials were used at a vacuum of about 10 ^-8 In the case of Torr, vapor deposition is sequentially carried out on the surface of glass at a rate of 0.2 to 2A/sec. First, the compound 56 of the present invention was deposited on the surface of a 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 120nm thick film as a Hole Transport Layer (HTL). Then, compound EB1 was evaporated on the above-obtained film to form a 5 nm-thick film as an Electron Blocking Layer (EBL). Then, a 25nm thick film was formed as an emission layer (EML) on the above-obtained film by co-evaporation of compound BH and compound BD (weight ratio 96. Then, compound HB1 was vapor-deposited on the above-obtained film to form a 5 nm-thick film as a hole-blocking layer (HBL). Then, 8-hydroxyquinoline-lithium (Liq) and a compound ET1 (in a weight ratio of 60. Finally, liq was deposited to form a 1nm thick film as an Electron Injection Layer (EIL) and aluminum was deposited to form a 120nm thick film as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device example 1.2:

device example 1.2 was fabricated in the same manner as device example 1.1, except that compound 68 was used as the HIL instead of compound 56.

Device example 1.3:

device example 1.3 was fabricated in the same manner as device example 1.1, except that compound 70 was used as the HIL instead of compound 56.

Device example 1.4:

device example 1.4 was fabricated in the same manner as device example 1.3, except that compound 70 was used to form a 5nm thick film as the HIL.

Device example 1.5:

device example 1.5 was fabricated in the same manner as device example 1.3, except that compound 70 was used to form a 2nm thick film as the HIL.

Device example 1.6:

device example 1.6 was fabricated in the same manner as device example 1.3, except that compound HT2 was used as the HTL instead of compound HT 1.

Device example 1.7:

device example 1.7 was fabricated in the same manner as device example 1.6, except that compound 70 was used to form a 2nm thick film as the HIL.

Device example 1.8:

device example 1.8 was fabricated in the same manner as device example 1.6, except that compound 70 was used to form a 1nm thick film as the HIL.

Device comparative example 1.1:

device comparative example 1.1 was made in the same manner as device example 1.1 except that comparative compound HI1 was used as the HIL instead of compound 56.

Device comparative example 1.2:

device comparative example 1.2 was fabricated in the same manner as device example 1.6, except that compound 70 was not used, and there was no hole injection layer.

The detailed device layer structure and thickness are shown in the table below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.

TABLE 1 device structures of device examples and comparative examples

The material structure used in the device is as follows:

the above device, at 10mA/cm ² Next, IVL characteristics were measured, and the voltage (V), power Efficiency (PE), and lifetime (LT 95) thereof were recorded and shown in table 2.

TABLE 2 device data

Discussion of the first:

as can be seen from the above table, when 8 preferred embodiments of the present invention and comparative examples use a single material for the hole injection layer, the preferred embodiments are superior to the comparative examples in terms of voltage, power efficiency, and lifetime. The voltage can be reduced by about 0.5V, the power efficiency is improved, and the service life is improved by times. Even when the thickness of the hole injection layer is reduced to 5nm and 2nm, even 1nm, efficiency and lifetime are excellent regardless of voltage. Particularly, in the case of a device without a hole injection layer, the voltage of the device is as high as 8.34V, and the power efficiency and the lifetime are inferior to those of a device with a hole injection layer. It can thus be seen that the compounds of the present invention are a better choice than the comparative compounds when used alone as hole injection layers, and the improvement is completely unexpected.

Device embodiment two

Device example 2.1:

a glass substrate with an Indium Tin Oxide (ITO) transparent electrode 80nm thick was treated with oxygen plasma and UV ozone. Before evaporationAnd drying the cleaned glass substrate on a hot table in a glove box. The following materials were used at a vacuum of about 10 ^-8 In the case of Torr, vapor deposition is sequentially carried out on the surface of glass at a rate of 0.2 to 2A/sec. First, compound 56 (dopant) of the present invention and compound HT1 (weight ratio 3. Then, compound HT1 was evaporated onto the above-obtained film to form a 120nm thick film as a Hole Transport Layer (HTL). Then, compound EB1 was evaporated on the above-obtained film to form a 5 nm-thick film as an Electron Blocking Layer (EBL). Then, a 25nm thick film was formed as an emission layer (EML) on the above-obtained film by co-evaporation of compound BH and compound BD (weight ratio 96. Then, compound HB1 was vapor-deposited on the above-obtained film to form a 5 nm-thick film as a hole-blocking layer (HBL). Then, 8-hydroxyquinoline-lithium (Liq) and a compound ET1 (in a weight ratio of 60. Finally, liq was evaporated to form a 1nm thick film as an Electron Injection Layer (EIL) and aluminum was evaporated to 120nm thick as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device example 2.2:

device example 2.2 was made in the same manner as device example 2.1 except that compound 68 was used as the dopant instead of compound 56 in the HIL.

Device example 2.3:

device example 2.3 was made in the same manner as device example 2.1 except that compound 70 was used as the dopant instead of compound 56 in HIL.

Device example 2.4:

device example 2.4 was fabricated in the same manner as device example 2.1, except that compound HT2 was used as the HIL instead of compound HT1 and compound 56 was co-evaporated (weight ratio 97.

Device example 2.5:

device example 2.5 was made in the same manner as device example 2.4 except that compound 68 was used as the dopant instead of compound 56 in the HIL.

Device comparative example 2:

device comparative example 2 was made in the same manner as device example 2.1 except that compound HI1 was used as the dopant instead of compound 56 in HIL.

The specific structure of the compound used in the device is shown in device example one.

Table 3 device structures of device examples and comparative examples

The above device, at 10mA/cm ² Next, IVL characteristics were measured, and the voltage (V), power Efficiency (PE), and lifetime (LT 95) thereof were recorded and shown in table 4.

TABLE 4 device data

Discussion II:

as can be seen from the above table, the 5 preferred embodiments of the present invention and the comparative example as in the case where the dopant of HT1 or HT2 is used as the hole injection layer, the difference in the device performance of the two materials is very large. First, the voltage of the comparative example was as high as 8.57V, while the voltage of the preferred example was only around 4.18V, which is a half reduction. The power efficiency of the example was also twice or more that of the comparative example. Especially in terms of lifetime, the preferred embodiment is tens of times that of the comparative example, not at all an order of magnitude. Thus: the compounds disclosed herein are a much superior class of hole injection materials to the comparative compounds for use as dopants, and the improvements brought by the compounds of the present invention are entirely unexpected and have overwhelming advantages in device performance, particularly in terms of reduced voltage and increased lifetime.

Device example three

Device example 3.1:

a glass substrate with an Indium Tin Oxide (ITO) transparent electrode 80nm thick was treated with oxygen plasma and UV ozone. And drying the cleaned glass substrate on a hot table in a glove box before vapor deposition. The following materials were used at a vacuum of about 10 ^-8 In the case of Torr, vapor deposition is sequentially carried out on the surface of glass at a rate of 0.2 to 2A/sec. First, compound 56 was evaporated onto the surface of a 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 on the above-obtained film to form a 5 nm-thick film as an Electron Blocking Layer (EBL). Then, a film having a thickness of 40nm was formed as an emission layer (EML) by co-evaporation of a compound EB2, a compound HB2 and a compound GD (46 in weight ratio. Then, a compound HB2 was deposited on the above-obtained film to form a film having a thickness of 5nm as a hole-blocking layer (HBL). 8-hydroxyquinoline-lithium (Liq) and compound ET2 (60 weight ratio. Finally, liq was evaporated to form a 1nm thick film as an Electron Injection Layer (EIL) and aluminum was evaporated to 120nm thick as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device example 3.2:

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 3.

Device example 3.3:

device example 3.3 was fabricated in the same manner as device example 3.1, except that compound 70 was used as the Hole Injection Layer (HIL) instead of compound 56, and compound HT2 was used as the HTL instead of compound HT 1.

Device example 3.4:

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 a Hole Injection Layer (HIL).

The specific structure of the novel compounds used in the devices is shown below:

TABLE 5 device Structure of device embodiments

The above device, at 10mA/cm ² Next, IVL characteristics were measured, and the voltage (V), power Efficiency (PE), and lifetime (LT 95) thereof were recorded and shown in table 6.

TABLE 6 device data

Discussion III:

as can be seen from the green device, when compound 56 and compound 70 were used alone as the hole injection layer, the voltage, efficiency and lifetime performance were very excellent. When compound 56 and compound 70 are used as dopants for the hole injection layer, the difference in voltage is small, the efficiency is slightly high, and the lifetime is long when compound 56 and compound 70 are used alone as the hole injection layer, as compared with example 3.1 and example 3.3.

Device example four

Device example 4.1:

a glass substrate with an Indium Tin Oxide (ITO) transparent electrode 80nm thick was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot table in a glove box before evaporation. The following materials were used at a vacuum of about 10 ^-8 In the case of Torr, vapor deposition is sequentially carried out on the surface of glass at a rate of 0.2 to 2A/sec. First, compound 56 was evaporated onto the surface of a 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 on the above-obtained film to form a 5 nm-thick film as an Electron Blocking Layer (EBL). Then, a compound RH and a compound RD (weight ratio 98. Then, compound HB2 was vapor-deposited on the above-obtained film to form a 5 nm-thick film as a hole-blocking layer (HBL). 8-hydroxyquinoline-lithium (Liq) and compound ET2 (60 weight ratio. Finally, liq was deposited to form a 1nm thick film as an Electron Injection Layer (EIL) and aluminum was deposited to form a 120nm thick film as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device example 4.2 was fabricated in the same manner as device example 4.1, except that compound 56 (dopant) and compound HT1 (weight ratio 3.

Device example 4.3:

device example 4.3 was fabricated in the same manner as device example 4.1, except that compound 70 was used as the Hole Injection Layer (HIL) instead of compound 56, and compound HT2 was used as the HTL instead of compound HT 1.

Device example 4.4:

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.

Table 7 device structure of device embodiments

The above device, at 10mA/cm ² Next, IVL characteristics were measured, and the voltage (V), power Efficiency (PE), and lifetime (LT 95) thereof were recorded and shown in table 8.

TABLE 8 device data

Discussion four:

it can also be seen from the red device that when compound 56 and compound 70 are used alone as hole injection layers, the effect is very good in terms of voltage, efficiency and lifetime. When compound 56 and compound 70 are used as dopants for the hole injection layer, the difference in voltage is small, the efficiency is slightly high, and the lifetime is long when compound 56 alone is used as a hole injection layer, as compared with examples 4.1 and 4.3.

From the above results, it can be seen that the dehydrobenzodioxazole derivative is extremely excellent in the effect in red, green and blue devices and is an indispensable hole injection material, whether used alone as a hole injection layer or as a dopant.

The compound disclosed by the invention is a derivative of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole, and because the parent nucleus of the molecule contains different heteroatoms, the Lowest Unoccupied Molecular Orbital (LUMO) of the compound has difference. LUMO of three types of compounds, namely, dehydrobenzodioxazole (NO-based compound), dehydrobenzodithiazole (NS-based compound) and dehydrobenzodiselenazole-based derivative (NSe-based compound), was calculated by DFT (GAUSS-09, provided that B3LYP/6-311G (d)) as shown in the following table:

TABLE 9DFT calculation results

From the foregoing device results, it can be seen that the device results of the dehydrobenzodiazole derivatives are excellent in various aspects, and are a highly efficient hole injection material. According to the DFT calculation result, compared with the same series of molecules, the LUMO of the dehydrobenzodioxazole derivative, the dehydrobenzodithiazole derivative and the dehydrobenzodiselenazole derivative is almost different, and about 0.2ev shows that the three compounds can have deep LUMO and have the characteristic of extremely lack of electrons, so that the dehydrobenzodithiazole derivative and the dehydrobenzodiselenazole derivative also have the potential of becoming excellent hole injection materials, the OLED performance can be greatly improved, such as longer service life of a device, higher efficiency and lower voltage, and the Organic Light Emitting Diode (OLED) has very wide industrial application prospect.

From the above device results and DFT calculations, it can be concluded that the novel compounds of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and similar structures of the present invention are very important charge transfer materials, having incomparable advantages especially in hole transport, and suitable for different types of organic semiconductor devices, including but not limited to fluorescent OLEDs, phosphorescent OLEDs, white OLEDs, tandem OLEDs, OTFTs, OPVs, etc.

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

Claims

1. A compound having formula 1:

wherein X and Y are selected from CR "R'"; r "and R'" are selected from cyano;

wherein Z ₁ And Z ₂ Is selected from O;

r is selected, identically or differently on each occurrence, from substituted or unsubstituted aryl radicals having from 6 to 30 carbon atoms;

wherein substituted aryl means that the aryl group is substituted with one or more groups selected from deuterium, halogen, unsubstituted alkyl groups having 1 to 20 carbon atoms, unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, unsubstituted alkoxy groups having 1 to 20 carbon atoms, unsubstituted alkenyl groups having 2 to 20 carbon atoms, unsubstituted alkynyl groups having 2 to 20 carbon atoms, unsubstituted aryl groups having 6 to 12 carbon atoms, unsubstituted heteroaryl groups having 3 to 12 carbon atoms, unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, nitro groups, sulfinyl groups, sulfonyl groups, phosphinoxy groups, and combinations thereof;

wherein each R may be the same or different.

2. The compound of claim 1, wherein at least one of R is a group having at least one electron withdrawing group.

3. The compound of claim 2, wherein R are each a group having at least one electron withdrawing group.

4. The compound of claim 2, wherein the electron withdrawing group has a Hammett constant ≧ 0.05.

5. The compound of claim 2, wherein the electron withdrawing group has a Hammett constant ≧ 0.3.

6. The compound of claim 2, wherein the electron withdrawing group has a Hammett constant ≧ 0.5.

7. The compound of claim 2, wherein the electron-withdrawing group is selected from the group consisting of: halogen, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SF ₅ Sulfinyl, sulfonyl, phosphinoxy, azaaryl, and halogen-, nitro-, acyl-, carbonyl-, carboxylic acid-, ester-, cyano-, isocyano-, SF ₅ Sulfinyl, sulfonyl, phosphinoxy, azaaryl substituted with one or more of any of the following: 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 alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, and combinations thereof.

8. The compound of claim 2, wherein the electron-withdrawing group is selected from the group consisting of: f, CF ₃ ，OCF ₃ ，SF ₅ ，SO ₂ CF ₃ Cyano, isocyano, pyrimidinyl, triazinyl, and combinations thereof.

9. The compound of claim 1, whereinR is selected, identically or differently on each occurrence, from the group consisting of: unsubstituted aryl having 6 to 30 carbon atoms, and substituted by halogen, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SF ₅ Aryl having 6 to 30 carbon atoms substituted with one or more of sulfinyl, sulfonyl and phosphinyl.

10. The compound of claim 1, wherein R, on each occurrence, is selected, identically or differently, from the group consisting of: phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, nitrophenyl, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, substituted with F, CN or CF ₃ One or more substituted phenyl or biphenyl groups, and combinations thereof.

11. The compound of claim 1, wherein X and Y are

R is selected, identically or differently on each occurrence, from substituted or unsubstituted aryl radicals having from 6 to 20 carbon atoms.

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

13. the compound of claim 12, wherein two R are the same in one compound represented by formula 1.

14. The compound of claim 12, having a structure represented by formula 2:

wherein, two Z in formula 2 are the same, two R are the same or different, and Z, X, Y, R is respectively corresponding to the atom or group selected from the following:

numbering Z X Y R R Numbering Z X Y R R Compound 16 O A1 A1 B16 B16 Compound 17 O A1 A1 B17 B17 Compound 18 O A1 A1 B18 B18 Compound 19 O A1 A1 B19 B19 Compound 20 O A1 A1 B20 B20 Compound 21 O A1 A1 B21 B21 Compound 22 O A1 A1 B22 B22 Compound 25 O A1 A1 B25 B25 Compound 26 O A1 A1 B26 B26 Compound 27 O A1 A1 B27 B27 Compound 28 O A1 A1 B28 B28 Compound 30 O A1 A1 B30 B30 Compound 31 O A1 A1 B31 B31 Compound 32 O A1 A1 B32 B32 Compound 33 O A1 A1 B33 B33 Compound 34 O A1 A1 B34 B34 Compound 35 O A1 A1 B35 B35 Compound 36 O A1 A1 B36 B36 Compound 37 O A1 A1 B37 B37 Compound 38 O A1 A1 B38 B38 Compound 39 O A1 A1 B39 B39 Compound 41 O A1 A1 B41 B41 Compound 42 O A1 A1 B42 B42 Compound 43 O A1 A1 B43 B43 Compound 44 O A1 A1 B44 B44 Compound 45 O A1 A1 B45 B45 Compound 46 O A1 A1 B46 B46 Compound 47 O A1 A1 B47 B47 Compound 48 O A1 A1 B48 B48 Compound 49 O A1 A1 B49 B49 Compound 50 O A1 A1 B50 B50 Compound 51 O A1 A1 B51 B51 Compound 52 O A1 A1 B52 B52 Compound 54 O A1 A1 B54 B54 Compound 55 O A1 A1 B55 B55 Compound 56 O A1 A1 B56 B56 Compound 57 O A1 A1 B57 B57 Compound 58 O A1 A1 B58 B58 Compound 59 O A1 A1 B59 B59 Compound 60 O A1 A1 B60 B60 Compound 61 O A1 A1 B61 B61 Compound 62 O A1 A1 B62 B62 Compound 63 O A1 A1 B63 B63 Compound 64 O A1 A1 B64 B64 Compound 68 O A1 A1 B68 B68 Compound 69 O A1 A1 B69 B69 Compound 70 O A1 A1 B70 B70 Compound 71 O A1 A1 B71 B71 Compound 72 O A1 A1 B72 B72 Compound 73 O A1 A1 B73 B73 Compound 74 O A1 A1 B74 B74 Compound 75 O A1 A1 B75 B75 Compound 76 O A1 A1 B76 B76 Compound 1023 O A1 A1 B25 B26 Compound 1024 O A1 A1 B27 B28 Compound 1027 O A1 A1 B54 B41 Compound 1028 O A1 A1 B54 B52 Compound 1029 O A1 A1 B52 B56 Compound 1030 O A1 A1 B55 B56 Compound 1031 O A1 A1 B64 B56 Compound 1032 O A1 A1 B68 B69 Compound 1033 O A1 A1 B69 B70 Compound 1034 O A1 A1 B71 B72

Wherein A1 is

15. An electroluminescent device, comprising:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

an organic layer disposed between the anode and cathode, the organic layer comprising a compound of any one of claims 1-14.

16. The electroluminescent device of claim 15, wherein the organic layer is a hole injection layer, and the hole injection layer is formed from the compound alone.

17. The electroluminescent device of claim 15, wherein the organic layer is a hole injection layer and the hole injection layer is formed from the compound comprising a doping comprising at least one hole transport material; the hole transport material comprises a compound with triarylamine units, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylethylene 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.

18. the electroluminescent device of claim 17, wherein the molar doping ratio of the compound to the hole transport material is 10.

19. The electroluminescent device of claim 15, comprising a plurality of stacked layers between the anode and the cathode, the stacked layers comprising a first light emitting layer and a second light emitting layer, wherein the first stacked layer comprises the first light emitting layer and the second stacked layer comprises the second light emitting layer, and a charge generation layer disposed between the first stacked layer and the second stacked layer, wherein the charge generation layer comprises a p-type charge generation layer and an n-type charge generation layer;

wherein the organic layer comprising the compound having formula 1 is a p-type charge generation layer.

20. The electroluminescent device of claim 19, wherein the p-type charge generation layer further comprises at least one hole transport material, the p-type charge generation layer is formed by doping the compound in the at least one hole transport material, the hole transport material comprises a compound having triarylamine units, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylethylene 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.

21. the electroluminescent device of claim 20, wherein the molar doping ratio of the compound to the hole transport material is 10.

22. The electroluminescent device of claim 19, said charge generation layer further comprising a buffer layer disposed between the p-type charge generation layer and the n-type charge generation layer, said buffer layer comprising said compound.

23. A compound composition comprising a compound of any one of claims 1-14.