KR102541819B1 - Organic electroluminescent materials and devices - Google Patents

Abstract

The present invention discloses organic electroluminescent materials and devices. The organic electroluminescent material is dehydrobenzodioxazole, dehydrobenzodithiazole, dehydrobenzodiselenazole, or a compound having a similar structure, and is a charge transport material, charge injection material, and charge generating material in an electroluminescent device. can be used as These new compounds can significantly improve the performance of organic electroluminescent devices, such as voltage and lifetime. The present invention further discloses an electroluminescent device and compound formulation.

Description

Organic electroluminescent materials and devices {ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES}

The present invention relates to compounds used in organic electronic devices such as organic light emitting devices. In particular, dehydrobenzodioxazole, dehydrobenzodithiazole, or dehydrobenzodiselenazole and new compounds having similar structures, and organic electroluminescent devices and compound preparations containing the compounds It is about.

Organic electronic devices include organic light emitting diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLETs), organic photoelectric devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes and organic plasma light emitting devices, but are not limited thereto.

Tang and Van Slyke of Eastman Kodak in 1987, 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 reported (Applied Physics Letters, 1987,51(12): 913-915). When a bias is applied to the device, green light is emitted from the device. This invention laid the foundation for the development of modern organic light emitting diodes (OLEDs). The most advanced OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or multiple light emitting layers between the cathode and anode. Because OLEDs are self-luminous solid-state devices, they offer tremendous potential for display and lighting applications. In addition, the inherent properties of organic materials (eg their flexibility) make them suitable for special applications (eg manufacturing on flexible substrates).

OLEDs can be classified into three different types according to their light emitting mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It uses only singlet state light emission. The triplet state created in the device is wasted through the non-radiative decay channel. Therefore, the internal quantum efficiency (IQE) of the fluorescent OLED is only 25%. These limitations hinder the commercialization of OLEDs. In 1997, Forrest and Thompson reported a phosphorescent OLED using triplet state emission from a heavy metal containing complex as a light emitting body. Therefore, the singlet state and the triplet state can be obtained, and an IQE of 100% can be achieved. Because of their high efficiency, the discovery and development of phosphorescent OLEDs has directly contributed to the commercialization of active matrix OLEDs (AMOLEDs). Recently, Adachi has achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. Such a light emitting body has a small singlet-triplet state gap so that exciton can return from a triplet state to a singlet state. In a TADF device, triplet excitons can generate singlet state excitons through inverse intersystem crossing, so that a high IQE can be achieved.

OLEDs can also be divided into low-molecular and high-molecular OLEDs depending on the type of material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of a small molecule can be very large if it has the correct structure. Dendritic polymers with well-defined structures are considered small molecules. Polymeric OLEDs include conjugated polymers and non-conjugated polymers with pendant emitting groups. When post-polymerization occurs during the manufacturing process, low-molecular OLEDs can be transformed into high-molecular OLEDs.

There are already various OLED manufacturing methods. Small molecule OLEDs are typically manufactured through vacuum thermal evaporation. Polymer OLEDs are prepared by solution processes such as spin coating, inkjet printing and nozzle printing. If the material can be dissolved or dispersed in a solvent, even low-molecular OLEDs can be prepared by a solution process.

An organic light emitting display device promotes charge injection by using a hole injection layer and an electron injection layer. Here, the hole injection layer is a functional layer formed of a single material or two or more materials. The single material method is generally to use a deep LUMO material, and the two or more material method is to form a hole transport material by doping a P-type material or a deep LUMO material. What both have in common is the need to use deep LUMO materials.

US20050121667 discloses the use of an organic mesomeric compound as an organic dopant to be doped into an organic semiconductor substrate material to change the electrical properties of the organic semiconductor substrate material, the mesomeric compound being a quinone or a quinone derivative. , which has lower volatility than F4TCNQ under the same evaporation conditions. The general chemical structure disclosed by them contains the following formula:

This application mainly focuses on the special performance of quinones or quinone derivatives as dopants, but does not disclose or suggest the properties and applications of any compound having a parent nucleus structure similar to that of this application.

However, deep LUMO materials are not easy to synthesize due to having strong electron withdrawing substituents, and it is difficult to simultaneously have properties such as deep LUMO, high stability, and high film formation. For example, F4-TCNQ (P-type hole injection material) has a very deep LUMO, but the deposition temperature is too low, which affects the control of deposition and the reproducibility of production performance and the thermal stability of the device; Also, for example, HATCN has a strong crystallinity, so there is a problem of film formation in the device, and LUMO is not deep enough to be used as a P-type doping. Since the hole injection layer greatly affects the voltage, efficiency, and lifespan of an OLED device, research and development of deep LUMO, high stability, and high film-forming materials are very important and urgent in the industry.

It is an object of the present invention to solve at least part of the above problems by providing dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and novel compounds having structures similar thereto. The compound can be used as a charge transport material and a charge injection material in an organic electroluminescent device. These new compounds can significantly improve the performance of organic electroluminescent devices, such as voltage and lifetime.

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

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

wherein Z ₁ and Z ₂ are identically or differently selected from O, S or Se each time they occur;

Each time R, R', R" and R"' appear identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and 1 to 20 carbon atoms. A substituted or unsubstituted alkoxy group having 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 alkenyl group having 2 to 20 carbon atoms Or an unsubstituted akinyl group, 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 group having 3 to 20 carbon atoms It is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

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

Adjacent substituents may be optionally linked to form a ring.

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

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

wherein Z ₁ and Z ₂ are identically or differently selected from O, S or Se each time they occur;

Each time R, R', R" and R"' appear identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and 1 to 20 carbon atoms. A substituted or unsubstituted alkoxy group having 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 alkenyl group having 2 to 20 carbon atoms Or an unsubstituted akinyl group, 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 group having 3 to 20 carbon atoms It is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

Adjacent substituents may be optionally linked to form a ring;

Here, each R may be the same or different, and at least one of R, R', R" and R"' is a group having at least one electron withdrawing group.

According to another embodiment of the present invention, a compound preparation containing the compound having the structure of Formula (1) is further disclosed.

The dehydrobenzodioxazole, dehydrobenzodithiazole, dehydrobenzodiselenazole, and novel compounds having structures similar thereto disclosed in the present invention can be used as charge transport materials and charge injection materials in electroluminescent devices. The new compound can significantly improve the performance of organic electroluminescent devices, such as voltage and lifetime.

1 is a schematic diagram of an organic light emitting device that may contain the compounds and compound preparations disclosed herein.
2 is a schematic diagram of a series connected organic light emitting device that may contain compounds and formulations of compounds disclosed herein.
3 is a schematic diagram of another serially connected organic light emitting device that may contain compounds and formulations of compounds disclosed herein.
Figure 4 shows the structural formula (1) of the compound as disclosed in the text.

OLEDs can be fabricated on several types of substrates (eg glass, plastic and metal). 1 schematically and non-limitingly shows an organic light emitting device 100 . The drawings are not necessarily drawn to scale, and some layer structures in the drawings may be omitted if necessary. The device 100 includes a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, an electron transport layer ( 170), an electron injection layer 180, and a cathode 190. Device 100 may be fabricated by sequentially depositing the described layers. The nature and function of each layer and exemplary materials are described in more detail in US Patent US7279704B2, columns 6-10, the entire contents of which are hereby incorporated herein by reference.

Each layer in this layer has more examples. An example is the flexible and transparent substrate-anode combination disclosed in US Pat. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a molar ratio of 50:1 as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. US Pat. No. 6,303,238 (to Thompson et al.), incorporated by reference in its entirety, discloses an example of a host material. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in US Patent Application Publication No. 2003/0230980 combined in an inclusive manner. U.S. Patent Nos. 5703436 and 5707745, incorporated by reference in their entirety, disclose examples of cathodes, which are transparent, conductive, and sputter-deposited over a thin metal layer such as Mg:Ag. It includes a composite anode having an ITO layer deposited thereon. U.S. Patent No. 6097147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety, describe the principle and use of the barrier layer in more detail. US Patent Application Publication No. 2004/0174116, incorporated by reference in its entirety, provides an example of an injection layer. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, incorporated herein by reference in its entirety.

The hierarchical structure is provided through a non-limiting embodiment. The function of the OLED can be realized by combining several types of layers described above, or some layers can be completely omitted. It may further include other layers not explicitly described. Optimum performance can be achieved by using a single material or a mixture of different materials within each layer. Any functional layer may include several sub-layers. For example, the light emitting layer may include two layers of different light emitting materials to realize a desired light emitting spectrum.

In one embodiment, an OLED can be described as having an “organic layer” disposed between a cathode and an anode. The organic layer may include one or a plurality of layers.

In one embodiment, a series-connected OLED may be formed by connecting two or more OLED units in series, and FIG. 2 schematically, but not exclusively, illustrates a series-connected organic light emitting device 500 . The device 500 may include a substrate 101 , an anode 110 , a first unit 100 , a charge generation layer 300 , a second unit 200 and a cathode 290 . Here, the first unit 100 includes a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, and an electron transport layer 170, The second unit 200 includes a hole injection layer 220, a hole transport layer 230, an electron blocking layer 240, a light emitting layer 250, a hole blocking layer 260, an electron transport layer 270, and an electron injection layer 280. ), and the charge generating layer 300 includes an N-type charge generating layer 310 and a P-type charge generating layer 320 . Device 500 may be fabricated by sequentially depositing the described layers.

An OLED may also have an encapsulation layer, and FIG. 3 schematically and non-limitingly illustrates an organic light emitting device 600 . The difference between this and FIG. 2 is that an encapsulation layer 102 is further included on the negative electrode 290 to prevent harmful substances (eg, moisture and oxygen) from the environment. Any material capable of providing an encapsulation function can be used as the encapsulation layer (eg glass or organic-inorganic mixed layer). The encapsulation layer should be placed directly or indirectly on the outside of the OLED device. Multilayer encapsulation is described in US patent US7968146B2, the entire contents of which are incorporated herein by reference.

A device fabricated according to an embodiment of the present invention may be integrated into various types of consumer goods having one or a plurality of electronic member modules (or units) of the device. Some examples of such consumer products are flat panel displays, monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or traffic lights, head-up displays, fully transparent or partially transparent displays, flexible displays, and smartphones. , tablets, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro displays, 3D displays, vehicle displays and taillights.

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

The “top” used in the text means the farthest from the board, and the “bottom” means the closest to the board. When a first layer is described as being “disposed” “on” a second layer, the first layer is disposed relatively far from the substrate. Other layers may be present between the first layer and the second layer, unless it is specified that the first layer "and" the second layer "contact." For example, even though there are some kind of organic layers between the cathode and anode, it can still be described as being “placed” on top of the anode.

As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and/or capable of being precipitated from a liquid medium.

When it is considered that the ligand directly affects the photosensitivity of the light emitting material, the ligand may be referred to as a "photosensitive ligand". If it is considered that the ligand does not affect the light-sensitive performance of the light emitting material, the ligand may be referred to as an "auxiliary ligand", and the auxiliary ligand may change the properties of the photosensitive ligand.

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

In another aspect, E-type delayed fluorescence does not depend on collisions between two triplet states, but rather on a transition between a triplet state and a singlet-excited state. A compound capable of generating E-type delayed fluorescence must have a very small singlet-triplet gap to be able to transition between energy states. Thermal energy can activate a transition from the triplet state to the singlet state. This type of delayed fluorescence is also referred to as thermally activated delayed fluorescence (TADF). A remarkable feature of TADF is that the delay factor increases with increasing temperature. If the rate of reverse intersystem crossing (RISC) is fast enough to minimize the non-radiative attenuation by triplet states, the proportion of back-filled singlet excited states can reach 75%. . The total fraction of singlet states can be 100%, which far exceeds 25% of the field-generated excitons' spin statistics.

Characteristics of type E delayed fluorescence can be found in exciplex systems or 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 (ΔES-T). Organic shell-acceptor luminescent materials containing non-metals have the potential to realize these characteristics. The release of these substances is generally characterized by anticorrelator-receptor charge transfer (CT) type release. Spatial separation of HOMO and LUMO in these antireceptor-receptor compounds usually results in small ΔES-T. Such conditions may include CT conditions. In general, a craft-acceptor luminescent material is constituted by connecting an electron crafting body moiety (eg, an amino group or a carbazole derivative) and an electron acceptor moiety (eg, a 6-membered aromatic ring containing N).

Regarding the definition of substituent terms,

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

Alkyl groups include straight-chain alkyl groups and branched alkyl groups. Examples of the alkyl group are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, secondary butyl group (Sec-butyl), isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Decyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, 3 -Contains a methylpentyl group. Also, the alkyl group may be optionally substituted. Carbons in the chain of alkyl groups may be substituted by other heteroatoms. In the above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, secondary butyl group, isobutyl group, t-butyl group, n-pentyl group and neopentyl group are preferred.

Cycloalkyl groups as used herein include cyclic alkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 4 to 10 ring carbon atoms, which include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamane tyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group, and the like. Also, the cycloalkyl group may be optionally substituted. Carbons in the ring may be substituted by other heteroatoms.

Alkenyl groups as used herein include straight chain olefin groups and branched olefin groups. Preferred alkenyl groups are alkenyl groups containing 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butadienyl group, a 1-methylvinyl group, a styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group and 3-phenyl-1-butenyl group. Also, the alkenyl group may be optionally substituted.

Alkynyl groups as used herein include straight-chain alkynyl groups and branched alkynyl groups. A preferred alkynyl group is an alkynyl group containing 2 to 15 carbon atoms. Also, an alkynyl group may be optionally substituted.

Aryl groups or aromatic groups, as used herein, consider condensed and unfused systems. Preferred aryl groups are aryl groups containing 6 to 60 carbon atoms, more preferably aryl groups containing 6 to 20 carbon atoms, and still more preferably aryl groups containing 6 to 12 carbon atoms. Examples of aryl groups include phenyl group, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, and perylene. (perylene) and azulene, and preferably includes a phenyl group, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Also, an aryl group may be optionally substituted. Examples of non-fused aryl groups are phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-ter Phenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tol Ryl group, p-tolyl group, p-(2-phenylpropyl)phenyl group, 4'-methylbiphenylyl group, 4''-tertbutyl group-p-terphenyl-4-yl group, o-cumenyl group (o-cumenyl ), m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group and m-quaterphenyl group (m -quaterphenyl).

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

Heteroaryl groups, as used herein, are contemplated to include unfused and fused heteroaromatic groups that may contain from 1 to 5 heteroatoms. Preferred heteroaryl groups are heteroaryl groups containing 3 to 30 carbon atoms, more preferably heteroaryl groups containing 3 to 20 carbon atoms, and even more preferably heteroaryl groups containing 3 to 12 carbon atoms. am. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole ), indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, Oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine (oxadiazine), indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cin Noline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, It includes furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, preferably dibenzothiophene, Dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and their aza analogues. Also, a heteroaryl group may be optionally substituted.

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

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

An aralkyl group, as used herein, is an alkyl group having an aryl substituent. Also, an aralkyl group may be optionally substituted. Examples of the aralkyl group are benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl t-butyl group, α-naphthylmethyl group, 1-α-naphthyl group -Ethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthyl-ethyl group, 2-β- Naphthyl-ethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group (p -chlorobenzyl), m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group (p-bromobenzyl), m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group (p- iodobenzyl), m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group (p-hydroxybenzyl), m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-amino Benzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1- It includes a hydroxy-2-phenylisopropyl group and a 1-chloro-2-phenylisopropyl group. In the above, the benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group and 2-phenylisopropyl group desirable.

The term "aza" in azadibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic fragment are replaced by nitrogen atoms. For example, azatriphenylene includes dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline, and other analogs having two or more nitrogens in the ring system. Other nitrogenous analogs of the aza derivatives described above can readily be envisioned by those skilled in the art, and all such analogs are intended to be included within the term set forth herein.

It should be understood that when a fragment of a molecule is described by a substituent or linked to other moieties in some other way, whether it is a fragment (e.g., a phenyl group, a phenylene group, a naphthyl group, a dibenzofuran group) or it is an entire molecule (e.g. , benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating substituents or fragment linkages are considered equivalent.

In the compounds mentioned in this application, hydrogen atoms may be partially or entirely replaced by deuterium. Other elements such as carbon and nitrogen may also be replaced by other stable isotopes of these. As this improves the efficiency and stability of the device, it may be desirable to substitute other stable isotopes in the compound.

In the compounds mentioned in this application, polysubstitution refers to a range up to the maximum usable substitution, including disubstitutions. In the compounds mentioned in this application, when any substituent represents polysubstitution (including di-, tri-, tetra-substitution, etc.), it indicates that the substituent may be present at a plurality of available substitution positions in the linkage structure, Substituents present at a plurality of available substitution positions may have the same structure or may have different structures.

In the present invention, unless otherwise defined, a substituted alkyl group, a substituted cycloalkyl group, a substituted heteroalkyl group, a substituted aralkyl group, a substituted alkoxy group, a substituted aryloxy group, a substituted alkenyl group, a substituted akinyl group, Substituted aryl group, substituted heteroaryl group, substituted alkylsilyl group, substituted arylsilyl group, substituted amino group, substituted acyl group, substituted carbonyl group, substituted carboxylic acid group, substituted ester group, substituted sulfy When any one term from the group consisting of an yl group, a substituted sulfonyl group, and a substituted phosphoroso group is used, it is an alkyl group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an akinyl group , An aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, an amino group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a sulfinyl group, a sulfonyl group, and a group of any one of a phosphoroso group, 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, Unsubstituted aralkyl group having 7 to 30 carbon atoms, unsubstituted alkoxy group having 1 to 20 carbon atoms, unsubstituted aryloxy group having 6 to 30 carbon atoms, unsubstituted having 2 to 20 carbon atoms Alkenyl group, unsubstituted akinyl group having 2 to 20 carbon atoms, unsubstituted aryl group having 6 to 30 carbon atoms, unsubstituted heteroaryl group having 3 to 30 carbon atoms, having 3 to 20 carbon atoms An unsubstituted alkylsilyl group, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, It means that it may be substituted by one or a plurality of groups selected from an ester group, a cyano group, an isocyano group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphoroso group, and combinations thereof.

In the compounds mentioned in the present invention, for example, adjacent substituents in the compound cannot be optionally linked to form a ring, unless it is specifically defined that the adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present invention, adjacent substituents may be optionally linked to form a ring, including cases where adjacent substituents may be linked to form a ring, and also when adjacent substituents are not linked to form a ring. Including case When adjacent substituents can be optionally linked to link rings, the ring formed may be a monocyclic ring, a polycyclic ring, an alicyclic ring, a heteroalicyclic ring, an aromatic ring, or a heteroaromatic ring. 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 apart. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms bonded directly to each other.

The intention of the expression that adjacent substituents may be optionally linked to form a ring is also to consider that two substituents bonded to the same carbon atom are linked to each other by chemical bonds to form a ring, which is exemplified through the following formula :

The intention of the expression that adjacent substituents may be optionally linked to form a ring is also to consider that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by chemical bonds to form a ring, which represents the following formula exemplified via:

In addition, the intention of the expression that adjacent substituents may be arbitrarily linked to form a ring is also that when one of the two substituents bonded to the carbon atom directly bonded to each other represents hydrogen, the second substituent is on the side where the hydrogen atom is bonded. It is intended to be considered to have been combined to form a ring. This is illustrated through the formula:

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

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

wherein Z ₁ and Z ₂ are identically or differently selected from O, S or Se each time they occur;

Each time R, R', R" and R"' appear identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and 1 to 20 carbon atoms. A substituted or unsubstituted alkoxy group having 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 alkenyl group having 2 to 20 carbon atoms Or an unsubstituted akinyl group, 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 group having 3 to 20 carbon atoms It is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

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

Adjacent substituents may be optionally linked to form a ring.

In this embodiment, each time R, R', R" and R"' are selected identically or differently from the substituent group, it can be clearly determined by those skilled in the art, and at the same time in Formula (1) Any two substituents with the same number shown (eg R, R', R" or R"') may be selected from the same substituent or different substituents.

According to one embodiment of the present invention, wherein X and Y are identically or differently selected from CR'R" or NR"' each time they occur, and R', R" and R"' have at least one electron withdrawing group. It is a group.

According to one embodiment of the present invention, wherein X and Y are identically or differently selected from CR'R" or NR"' each time they occur, and R, R', R" and R"' are at least one electron withdrawing group is a group with

According to an embodiment of the present invention, each occurrence of X and Y is identically or differently selected from O, S or Se, and at least one of R is a group having at least one electron withdrawing group.

According to one embodiment of the present invention, where X and Y are identically or differently selected from O, S or Se each time they occur, and R are all groups having at least one electron withdrawing group.

According to an embodiment of the present invention, the Hammett constant of the electron withdrawing group is 0.05 or more, 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 of the present invention is 0.05 or more, preferably 0.3 or more, and more preferably 0.5 or more, the electron withdrawing ability is relatively strong, and the LUMO energy level of the compound is significantly reduced to increase the charge mobility. improvement effect can be achieved.

It should be explained that, as long as the Hammett substituent constant value includes the Hammett substituent para constant and/or meta constant, and one of the para constant and the meta constant satisfies the condition of 0.05 or more, in the present invention Can be used as a selected group.

According to one embodiment of the present invention, wherein the electron withdrawing group is a halogen, a nitroso group, a nitro group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, SCN, OCN, SF ₅ , and a boranyl group. (Boranyl), a sulfinyl group, a sulfonyl group, a phosphoroso group, or selected from the group consisting of an aza aromatic ring, or a halogen, a nitroso group, a nitro group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, and a cyano group. Any one of the following groups substituted with one or a plurality of no groups, isocyano groups, SCN, OCN, SF5, boranyl groups, sulfinyl groups, sulfonyl groups, phosphoroso groups, and aza aromatic rings: 1 to An alkyl group having 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, and a cycloalkyl group having 1 to 20 carbon atoms. Alkoxy group having 20 carbon atoms, aryloxy group having 6 to 30 carbon atoms, alkenyl group having 2 to 20 carbon atoms, akinyl group having 2 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, 3 It is selected from the group consisting of a heteroaryl group having ~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 present invention, the electron withdrawing group is F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pyrimidyl group, triazinyl group, and selected from the group consisting of combinations.

According to one embodiment of the present invention, where X and Y are identically or differently selected from the group consisting of the following structures each time they occur:

Here, each time R ₁ appears, identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF5, violet Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted having 3 to 20 ring carbon atoms cycloalkyl group, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted 1 to 20 carbon atoms Alkoxy group, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted akinyl group having 2 to 20 carbon atoms, 6 A substituted or unsubstituted aryl group having ~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, It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms and combinations thereof;

where V and W are selected identically or differently from CR _v R _w , NR _v , O, S, and Se each time they are indicated;

Here, Ar is selected identically or differently each time it appears 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 are identical or different each time they appear, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, 1~ A substituted or unsubstituted alkyl group having 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms Heteroalkyl group, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, 2 A substituted or unsubstituted alkenyl group having ~20 carbon atoms, a substituted or unsubstituted akinyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 3 to 30 carbon atoms. a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and It is selected from the group consisting of combinations thereof;

Here, A is a group having at least one electron withdrawing group, and in any structure above, R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , R _v and R _w When one or a plurality of them appear, at least one of them is a group having at least one electron withdrawing group.

In this embodiment, "*" represents the position where the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in formula (1).

According to one embodiment of the present invention, each time R ₁ appears, identically or differently, F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pentafluoro It is selected from the group consisting of a phenyl group, a 4-cyanotetrafluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof.

According to one embodiment of the present invention, the group having at least one electron withdrawing group is F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , a cyano group, an isocyano group, SCN, OCN, a pentafluorophenyl group, It is selected from the group consisting of a 4-cyanotetrafluorophenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, and combinations thereof.

According to one embodiment of the present invention, where X and Y are identically or differently selected from the group consisting of the following structures each time they occur:

In this embodiment, "*" represents the position where the X and Y groups are connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in formula (1).

According to one embodiment of the present invention, wherein each time R appears, identically or differently, hydrogen; deuterium; halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group; sulfinyl group; sulfonyl group; a phosphoroso group; an unsubstituted alkyl group having 1 to 20 carbon atoms; an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; an unsubstituted alkoxy group having 1 to 20 carbon atoms; An unsubstituted alkenyl 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; And halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group and phosphoroso group (phosphoroso) any one of the following groups substituted with one or a plurality of groups: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, and 1 to 20 an alkoxy group having 2 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; is selected from the group consisting of

According to an embodiment of the present invention, whenever R appears, identically or differently, hydrogen, deuterium, methyl group, isopropyl group, NO ₂ , SO ₂ CH ₃ , SCF ₃ , C ₂ F ₅ , OC ₂ F ₅ , OCH ₃ , diphenylmethylsilyl group, phenyl group, methoxyphenyl group, p-methylphenyl group, 2,6-diisopropylphenyl group, biphenyl group, polyfluorophenyl group, difluoropyridyl group, nitrophenyl group, dimethylthiazole group, A vinyl group substituted with one or more of CN and CF ₃ , an ethynyl group substituted with one of CN or CF ₃ , a dimethylphosphoroso group, a diphenylphosphoroso group, F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, trifluoromethylphenyl group, trifluoromethoxyphenyl group, bis(trifluoromethyl)phenyl group, bis(trifluoromethoxy)phenyl group, 4-cyanotetrafluoro A phenyl group, a phenyl group substituted with one or a plurality of F, CN, and CF ₃ or a biphenyl group, a tetrafluoropyridyl group, a pyrimidyl group, a triazinyl group, a diphenylboranyl group, an oxaboraanthryl group, and combinations thereof is selected from the group consisting of

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

am.

According to one embodiment of the present invention, where R is identically or differently selected from the group consisting of the following structures each time it appears:

"는 상기 R 그룹이 식 (1)에서의 데하이드로벤조디옥사졸 고리, 데하이드로벤조디티아졸 고리 또는 데하이드로벤조디티아졸 고리와 연결된 위치를 나타낸다.In this embodiment, "

" represents the position where the R group is connected to the dehydrobenzodioxazole ring, dehydrobenzodithiazole ring or dehydrobenzodithiazole ring in formula (1).

According to one embodiment of the present invention, whenever R appears, it is identically or differently selected from the group consisting of B1 to B88. For specific structures of B1 to B88, refer to the foregoing embodiments.

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

According to one embodiment of the present invention, wherein the compound is selected from the group consisting of Compound 1 to Compound 1428, and the specific structure of Compound 1 to Compound 1428 has a structure represented by Formula 2,

Here, the two Z structures in formula (2) are the same, the two R structures are the same or different, and the Z, X, Y and R are each correspondingly selected from atoms or groups shown in the table below.

compound number Z X Y R R compound number Z X Y R R One O A1 A1 B1 B1 2 O A1 A1 B2 B2 3 O A1 A1 B3 B3 4 O A1 A1 B4 B4 5 O A1 A1 B5 B5 6 O A1 A1 B6 B6 7 O A1 A1 B7 B7 8 O A1 A1 B8 B8 9 O A1 A1 B9 B9 10 O A1 A1 B10 B10 11 O A1 A1 B11 B11 12 O A1 A1 B12 B12 13 O A1 A1 B13 B13 14 O A1 A1 B14 B14 15 O A1 A1 B15 B15 16 O A1 A1 B16 B16 17 O A1 A1 B17 B17 18 O A1 A1 B18 B18 19 O A1 A1 B19 B19 20 O A1 A1 B20 B20 21 O A1 A1 B21 B21 22 O A1 A1 B22 B22 23 O A1 A1 B23 B23 24 O A1 A1 B24 B24 25 O A1 A1 B25 B25 26 O A1 A1 B26 B26 27 O A1 A1 B27 B27 28 O A1 A1 B28 B28 29 O A1 A1 B29 B29 30 O A1 A1 B30 B30 31 O A1 A1 B31 B31 32 O A1 A1 B32 B32 33 O A1 A1 B33 B33 34 O A1 A1 B34 B34 35 O A1 A1 B35 B35 36 O A1 A1 B36 B36 37 O A1 A1 B37 B37 38 O A1 A1 B38 B38 39 O A1 A1 B39 B39 40 O A1 A1 B40 B40 41 O A1 A1 B41 B41 42 O A1 A1 B42 B42 43 O A1 A1 B43 B43 44 O A1 A1 B44 B44 45 O A1 A1 B45 B45 46 O A1 A1 B46 B46 47 O A1 A1 B47 B47 48 O A1 A1 B48 B48 49 O A1 A1 B49 B49 50 O A1 A1 B50 B50 51 O A1 A1 B51 B51 52 O A1 A1 B52 B52 53 O A1 A1 B53 B53 54 O A1 A1 B54 B54 55 O A1 A1 B55 B55 56 O A1 A1 B56 B56 57 O A1 A1 B57 B57 58 O A1 A1 B58 B58 59 O A1 A1 B59 B59 60 O A1 A1 B60 B60 61 O A1 A1 B61 B61 62 O A1 A1 B62 B62 63 O A1 A1 B63 B63 64 O A1 A1 B64 B64 65 O A1 A1 B65 B65 66 O A1 A1 B66 B66 67 O A1 A1 B67 B67 68 O A1 A1 B68 B68 69 O A1 A1 B69 B69 70 O A1 A1 B70 B70 71 O A1 A1 B71 B71 72 O A1 A1 B72 B72 73 O A1 A1 B73 B73 74 O A1 A1 B74 B74 75 O A1 A1 B75 B75 76 O A1 A1 B76 B76 77 O A1 A1 B77 B77 78 O A1 A1 B78 B78 79 O A1 A1 B79 B79 80 O A1 A1 B80 B80 81 O A1 A1 B81 B81 82 O A1 A1 B82 B82 83 O A1 A1 B83 B83 84 O A1 A1 B84 B84 85 O A1 A1 B85 B85 86 O A1 A1 B86 B86 87 O A1 A1 B87 B87 88 O A1 A1 B88 B88 89 S A1 A1 B1 B1 90 S A1 A1 B2 B2 91 S A1 A1 B3 B3 92 S A1 A1 B4 B4 93 S A1 A1 B5 B5 94 S A1 A1 B6 B6 95 S A1 A1 B7 B7 96 S A1 A1 B8 B8 97 S A1 A1 B9 B9 98 S A1 A1 B10 B10 99 S A1 A1 B11 B11 100 S A1 A1 B12 B12 101 S A1 A1 B13 B13 102 S A1 A1 B14 B14 103 S A1 A1 B15 B15 104 S A1 A1 B16 B16 105 S A1 A1 B17 B17 106 S A1 A1 B18 B18 107 S A1 A1 B19 B19 108 S A1 A1 B20 B20 109 S A1 A1 B21 B21 110 S A1 A1 B22 B22 111 S A1 A1 B23 B23 112 S A1 A1 B24 B24 113 S A1 A1 B25 B25 114 S A1 A1 B26 B26 115 S A1 A1 B27 B27 116 S A1 A1 B28 B28 117 S A1 A1 B29 B29 118 S A1 A1 B30 B30 119 S A1 A1 B31 B31 120 S A1 A1 B32 B32 121 S A1 A1 B33 B33 122 S A1 A1 B34 B34 123 S A1 A1 B35 B35 124 S A1 A1 B36 B36 125 S A1 A1 B37 B37 126 S A1 A1 B38 B38 127 S A1 A1 B39 B39 128 S A1 A1 B40 B40 129 S A1 A1 B41 B41 130 S A1 A1 B42 B42 131 S A1 A1 B43 B43 132 S A1 A1 B44 B44 133 S A1 A1 B45 B45 134 S A1 A1 B46 B46 135 S A1 A1 B47 B47 136 S A1 A1 B48 B48 137 S A1 A1 B49 B49 138 S A1 A1 B50 B50 139 S A1 A1 B51 B51 140 S A1 A1 B52 B52 141 S A1 A1 B53 B53 142 S A1 A1 B54 B54 143 S A1 A1 B55 B55 144 S A1 A1 B56 B56 145 S A1 A1 B57 B57 146 S A1 A1 B58 B58 147 S A1 A1 B59 B59 148 S A1 A1 B60 B60 149 S A1 A1 B61 B61 150 S A1 A1 B62 B62 151 S A1 A1 B63 B63 152 S A1 A1 B64 B64 153 S A1 A1 B65 B65 154 S A1 A1 B66 B66 155 S A1 A1 B67 B67 156 S A1 A1 B68 B68 157 S A1 A1 B69 B69 158 S A1 A1 B70 B70 159 S A1 A1 B71 B71 160 S A1 A1 B72 B72 161 S A1 A1 B73 B73 162 S A1 A1 B74 B74 163 S A1 A1 B75 B75 164 S A1 A1 B76 B76 165 S A1 A1 B77 B77 166 S A1 A1 B78 B78 167 S A1 A1 B79 B79 168 S A1 A1 B80 B80 169 S A1 A1 B81 B81 170 S A1 A1 B82 B82 171 S A1 A1 B83 B83 172 S A1 A1 B84 B84 173 S A1 A1 B85 B85 174 S A1 A1 B86 B86 175 S A1 A1 B87 B87 176 S A1 A1 B88 B88 177 Se A1 A1 B1 B1 178 Se A1 A1 B2 B2 179 Se A1 A1 B3 B3 180 Se A1 A1 B4 B4 181 Se A1 A1 B5 B5 182 Se A1 A1 B6 B6 183 Se A1 A1 B7 B7 184 Se A1 A1 B8 B8 185 Se A1 A1 B9 B9 186 Se A1 A1 B10 B10 187 Se A1 A1 B11 B11 188 Se A1 A1 B12 B12 189 Se A1 A1 B13 B13 190 Se A1 A1 B14 B14 191 Se A1 A1 B15 B15 192 Se A1 A1 B16 B16 193 Se A1 A1 B17 B17 194 Se A1 A1 B18 B18 195 Se A1 A1 B19 B19 196 Se A1 A1 B20 B20 197 Se A1 A1 B21 B21 198 Se A1 A1 B22 B22 199 Se A1 A1 B23 B23 200 Se A1 A1 B24 B24 201 Se A1 A1 B25 B25 202 Se A1 A1 B26 B26 203 Se A1 A1 B27 B27 204 Se A1 A1 B28 B28 205 Se A1 A1 B29 B29 206 Se A1 A1 B30 B30 207 Se A1 A1 B31 B31 208 Se A1 A1 B32 B32 209 Se A1 A1 B33 B33 210 Se A1 A1 B34 B34 211 Se A1 A1 B35 B35 212 Se A1 A1 B36 B36 213 Se A1 A1 B37 B37 214 Se A1 A1 B38 B38 215 Se A1 A1 B39 B39 216 Se A1 A1 B40 B40 217 Se A1 A1 B41 B41 218 Se A1 A1 B42 B42 219 Se A1 A1 B43 B43 220 Se A1 A1 B44 B44 221 Se A1 A1 B45 B45 222 Se A1 A1 B46 B46 223 Se A1 A1 B47 B47 224 Se A1 A1 B48 B48 225 Se A1 A1 B49 B49 226 Se A1 A1 B50 B50 227 Se A1 A1 B51 B51 228 Se A1 A1 B52 B52 229 Se A1 A1 B53 B53 230 Se A1 A1 B54 B54 231 Se A1 A1 B55 B55 232 Se A1 A1 B56 B56 233 Se A1 A1 B57 B57 234 Se A1 A1 B58 B58 235 Se A1 A1 B59 B59 236 Se A1 A1 B60 B60 237 Se A1 A1 B61 B61 238 Se A1 A1 B62 B62 239 Se A1 A1 B63 B63 240 Se A1 A1 B64 B64 241 Se A1 A1 B65 B65 242 Se A1 A1 B66 B66 243 Se A1 A1 B67 B67 244 Se A1 A1 B68 B68 245 Se A1 A1 B69 B69 246 Se A1 A1 B70 B70 247 Se A1 A1 B71 B71 248 Se A1 A1 B72 B72 249 Se A1 A1 B73 B73 250 Se A1 A1 B74 B74 251 Se A1 A1 B75 B75 252 Se A1 A1 B76 B76 253 Se A1 A1 B77 B77 254 Se A1 A1 B78 B78 255 Se A1 A1 B79 B79 256 Se A1 A1 B80 B80 257 Se A1 A1 B81 B81 258 Se A1 A1 B82 B82 259 Se A1 A1 B83 B83 260 Se A1 A1 B84 B84 261 Se A1 A1 B85 B85 262 Se A1 A1 B86 B86 263 Se A1 A1 B87 B87 264 Se A1 A1 B88 B88 265 O A2 A2 B1 B1 266 O A2 A2 B6 B6 267 O A2 A2 B10 B10 268 O A2 A2 B16 B16 269 O A2 A2 B25 B25 270 O A2 A2 B28 B28 271 O A2 A2 B29 B29 272 O A2 A2 B30 B30 273 O A2 A2 B38 B38 274 O A2 A2 B39 B39 275 O A2 A2 B40 B40 276 O A2 A2 B41 B41 277 O A2 A2 B43 B43 278 O A2 A2 B52 B52 279 O A2 A2 B56 B56 280 O A2 A2 B67 B67 281 O A2 A2 B68 B68 282 O A2 A2 B69 B69 283 O A2 A2 B70 B70 284 O A2 A2 B71 B71 285 O A2 A2 B72 B72 286 O A2 A2 B74 B74 287 O A2 A2 B79 B79 288 O A2 A2 B80 B80 289 O A2 A2 B82 B82 290 O A2 A2 B83 B83 291 O A2 A2 B86 B86 292 O A2 A2 B88 B88 293 S A2 A2 B1 B1 294 S A2 A2 B6 B6 295 S A2 A2 B10 B10 296 S A2 A2 B16 B16 297 S A2 A2 B25 B25 298 S A2 A2 B28 B28 299 S A2 A2 B29 B29 300 S A2 A2 B30 B30 301 S A2 A2 B38 B38 302 S A2 A2 B39 B39 303 S A2 A2 B40 B40 304 S A2 A2 B41 B41 305 S A2 A2 B43 B43 306 S A2 A2 B52 B52 307 S A2 A2 B56 B56 308 S A2 A2 B67 B67 309 S A2 A2 B68 B68 310 S A2 A2 B69 B69 311 S A2 A2 B70 B70 312 S A2 A2 B71 B71 313 S A2 A2 B72 B72 314 S A2 A2 B74 B74 315 S A2 A2 B79 B79 316 S A2 A2 B80 B80 317 S A2 A2 B82 B82 318 S A2 A2 B83 B83 319 S A2 A2 B86 B86 320 S A2 A2 B88 B88 321 Se A2 A2 B1 B1 322 Se A2 A2 B6 B6 323 Se A2 A2 B10 B10 324 Se A2 A2 B16 B16 325 Se A2 A2 B25 B25 326 Se A2 A2 B28 B28 327 Se A2 A2 B29 B29 328 Se A2 A2 B30 B30 329 Se A2 A2 B38 B38 330 Se A2 A2 B39 B39 331 Se A2 A2 B40 B40 332 Se A2 A2 B41 B41 333 Se A2 A2 B43 B43 334 Se A2 A2 B52 B52 335 Se A2 A2 B56 B56 336 Se A2 A2 B67 B67 337 Se A2 A2 B68 B68 338 Se A2 A2 B69 B69 339 Se A2 A2 B70 B70 340 Se A2 A2 B71 B71 341 Se A2 A2 B72 B72 342 Se A2 A2 B74 B74 343 Se A2 A2 B79 B79 344 Se A2 A2 B80 B80 345 Se A2 A2 B82 B82 346 Se A2 A2 B83 B83 347 Se A2 A2 B86 B86 348 Se A2 A2 B88 B88 349 O A3 A3 B1 B1 350 O A3 A3 B6 B6 351 O A3 A3 B10 B10 352 O A3 A3 B16 B16 353 O A3 A3 B25 B25 354 O A3 A3 B28 B28 355 O A3 A3 B29 B29 356 O A3 A3 B30 B30 357 O A3 A3 B38 B38 358 O A3 A3 B39 B39 359 O A3 A3 B40 B40 360 O A3 A3 B41 B41 361 O A3 A3 B43 B43 362 O A3 A3 B52 B52 363 O A3 A3 B56 B56 364 O A3 A3 B67 B67 365 O A3 A3 B68 B68 366 O A3 A3 B69 B69 367 O A3 A3 B70 B70 368 O A3 A3 B71 B71 369 O A3 A3 B72 B72 370 O A3 A3 B74 B74 371 O A3 A3 B79 B79 372 O A3 A3 B80 B80 373 O A3 A3 B82 B82 374 O A3 A3 B83 B83 375 O A3 A3 B86 B86 376 O A3 A3 B88 B88 377 S A3 A3 B1 B1 378 S A3 A3 B6 B6 379 S A3 A3 B10 B10 380 S A3 A3 B16 B16 381 S A3 A3 B25 B25 382 S A3 A3 B28 B28 383 S A3 A3 B29 B29 384 S A3 A3 B30 B30 385 S A3 A3 B38 B38 386 S A3 A3 B39 B39 387 S A3 A3 B40 B40 388 S A3 A3 B41 B41 389 S A3 A3 B43 B43 390 S A3 A3 B52 B52 391 S A3 A3 B56 B56 392 S A3 A3 B67 B67 393 S A3 A3 B68 B68 394 S A3 A3 B69 B69 395 S A3 A3 B70 B70 396 S A3 A3 B71 B71 397 S A3 A3 B72 B72 398 S A3 A3 B74 B74 399 S A3 A3 B79 B79 400 S A3 A3 B80 B80 401 S A3 A3 B82 B82 402 S A3 A3 B83 B83 403 S A3 A3 B86 B86 404 S A3 A3 B88 B88 405 Se A3 A3 B1 B1 406 Se A3 A3 B6 B6 407 Se A3 A3 B10 B10 408 Se A3 A3 B16 B16 409 Se A3 A3 B25 B25 410 Se A3 A3 B28 B28 411 Se A3 A3 B29 B29 412 Se A3 A3 B30 B30 413 Se A3 A3 B38 B38 414 Se A3 A3 B39 B39 415 Se A3 A3 B40 B40 416 Se A3 A3 B41 B41 417 Se A3 A3 B43 B43 418 Se A3 A3 B52 B52 419 Se A3 A3 B56 B56 420 Se A3 A3 B67 B67 421 Se A3 A3 B68 B68 422 Se A3 A3 B69 B69 423 Se A3 A3 B70 B70 424 Se A3 A3 B71 B71 425 Se A3 A3 B72 B72 426 Se A3 A3 B74 B74 427 Se A3 A3 B79 B79 428 Se A3 A3 B80 B80 429 Se A3 A3 B82 B82 430 Se A3 A3 B83 B83 431 Se A3 A3 B86 B86 432 Se A3 A3 B88 B88 433 O A4 A4 B1 B1 434 O A4 A4 B6 B6 435 O A4 A4 B10 B10 436 O A4 A4 B16 B16 437 O A4 A4 B25 B25 438 O A4 A4 B28 B28 439 O A4 A4 B29 B29 440 O A4 A4 B30 B30 441 O A4 A4 B38 B38 442 O A4 A4 B39 B39 443 O A4 A4 B40 B40 444 O A4 A4 B41 B41 445 O A4 A4 B43 B43 446 O A4 A4 B52 B52 447 O A4 A4 B56 B56 448 O A4 A4 B67 B67 449 O A4 A4 B68 B68 450 O A4 A4 B69 B69 451 O A4 A4 B70 B70 452 O A4 A4 B71 B71 453 O A4 A4 B72 B72 454 O A4 A4 B74 B74 455 O A4 A4 B79 B79 456 O A4 A4 B80 B80 457 O A4 A4 B82 B82 458 O A4 A4 B83 B83 459 O A4 A4 B86 B86 460 O A4 A4 B88 B88 461 S A4 A4 B1 B1 462 S A4 A4 B6 B6 463 S A4 A4 B10 B10 464 S A4 A4 B16 B16 465 S A4 A4 B25 B25 466 S A4 A4 B28 B28 467 S A4 A4 B29 B29 468 S A4 A4 B30 B30 469 S A4 A4 B38 B38 470 S A4 A4 B39 B39 471 S A4 A4 B40 B40 472 S A4 A4 B41 B41 473 S A4 A4 B43 B43 474 S A4 A4 B52 B52 475 S A4 A4 B56 B56 476 S A4 A4 B67 B67 477 S A4 A4 B68 B68 478 S A4 A4 B69 B69 479 S A4 A4 B70 B70 480 S A4 A4 B71 B71 481 S A4 A4 B72 B72 482 S A4 A4 B74 B74 483 S A4 A4 B79 B79 484 S A4 A4 B80 B80 485 S A4 A4 B82 B82 486 S A4 A4 B83 B83 487 S A4 A4 B86 B86 488 S A4 A4 B88 B88 489 Se A4 A4 B1 B1 490 Se A4 A4 B6 B6 491 Se A4 A4 B10 B10 492 Se A4 A4 B16 B16 493 Se A4 A4 B25 B25 494 Se A4 A4 B28 B28 495 Se A4 A4 B29 B29 496 Se A4 A4 B30 B30 497 Se A4 A4 B38 B38 498 Se A4 A4 B39 B39 499 Se A4 A4 B40 B40 500 Se A4 A4 B41 B41 501 Se A4 A4 B43 B43 502 Se A4 A4 B52 B52 503 Se A4 A4 B56 B56 504 Se A4 A4 B67 B67 505 Se A4 A4 B68 B68 506 Se A4 A4 B69 B69 507 Se A4 A4 B70 B70 508 Se A4 A4 B71 B71 509 Se A4 A4 B72 B72 510 Se A4 A4 B74 B74 511 Se A4 A4 B79 B79 512 Se A4 A4 B80 B80 513 Se A4 A4 B82 B82 514 Se A4 A4 B83 B83 515 Se A4 A4 B86 B86 516 Se A4 A4 B88 B88 517 O A5 A5 B1 B1 518 O A5 A5 B6 B6 519 O A5 A5 B10 B10 520 O A5 A5 B16 B16 521 O A5 A5 B25 B25 522 O A5 A5 B28 B28 523 O A5 A5 B29 B29 524 O A5 A5 B30 B30 525 O A5 A5 B38 B38 526 O A5 A5 B39 B39 527 O A5 A5 B40 B40 528 O A5 A5 B41 B41 529 O A5 A5 B43 B43 530 O A5 A5 B52 B52 531 O A5 A5 B56 B56 532 O A5 A5 B67 B67 533 O A5 A5 B68 B68 534 O A5 A5 B69 B69 535 O A5 A5 B70 B70 536 O A5 A5 B71 B71 537 O A5 A5 B72 B72 538 O A5 A5 B74 B74 539 O A5 A5 B79 B79 540 O A5 A5 B80 B80 541 O A5 A5 B82 B82 542 O A5 A5 B83 B83 543 O A5 A5 B86 B86 544 O A5 A5 B88 B88 545 S A5 A5 B1 B1 546 S A5 A5 B6 B6 547 S A5 A5 B10 B10 548 S A5 A5 B16 B16 549 S A5 A5 B25 B25 550 S A5 A5 B28 B28 551 S A5 A5 B29 B29 552 S A5 A5 B30 B30 553 S A5 A5 B38 B38 554 S A5 A5 B39 B39 555 S A5 A5 B40 B40 556 S A5 A5 B41 B41 557 S A5 A5 B43 B43 558 S A5 A5 B52 B52 559 S A5 A5 B56 B56 560 S A5 A5 B67 B67 561 S A5 A5 B68 B68 562 S A5 A5 B69 B69 563 S A5 A5 B70 B70 564 S A5 A5 B71 B71 565 S A5 A5 B72 B72 566 S A5 A5 B74 B74 567 S A5 A5 B79 B79 568 S A5 A5 B80 B80 569 S A5 A5 B82 B82 570 S A5 A5 B83 B83 571 S A5 A5 B86 B86 572 S A5 A5 B88 B88 573 Se A5 A5 B1 B1 574 Se A5 A5 B6 B6 575 Se A5 A5 B10 B10 576 Se A5 A5 B16 B16 577 Se A5 A5 B25 B25 578 Se A5 A5 B28 B28 579 Se A5 A5 B29 B29 580 Se A5 A5 B30 B30 581 Se A5 A5 B38 B38 582 Se A5 A5 B39 B39 583 Se A5 A5 B40 B40 584 Se A5 A5 B41 B41 585 Se A5 A5 B43 B43 586 Se A5 A5 B52 B52 587 Se A5 A5 B56 B56 588 Se A5 A5 B67 B67 589 Se A5 A5 B68 B68 590 Se A5 A5 B69 B69 591 Se A5 A5 B70 B70 592 Se A5 A5 B71 B71 593 Se A5 A5 B72 B72 594 Se A5 A5 B74 B74 595 Se A5 A5 B79 B79 596 Se A5 A5 B80 B80 597 Se A5 A5 B82 B82 598 Se A5 A5 B83 B83 599 Se A5 A5 B86 B86 600 Se A5 A5 B88 B88 601 O A6 A6 B1 B1 602 O A6 A6 B6 B6 603 O A6 A6 B10 B10 604 O A6 A6 B16 B16 605 O A6 A6 B25 B25 606 O A6 A6 B28 B28 607 O A6 A6 B29 B29 608 O A6 A6 B30 B30 609 O A6 A6 B38 B38 610 O A6 A6 B39 B39 611 O A6 A6 B40 B40 612 O A6 A6 B41 B41 613 O A6 A6 B43 B43 614 O A6 A6 B52 B52 615 O A6 A6 B56 B56 616 O A6 A6 B67 B67 617 O A6 A6 B68 B68 618 O A6 A6 B69 B69 619 O A6 A6 B70 B70 620 O A6 A6 B71 B71 621 O A6 A6 B72 B72 622 O A6 A6 B74 B74 623 O A6 A6 B79 B79 624 O A6 A6 B80 B80 625 O A6 A6 B82 B82 626 O A6 A6 B83 B83 627 O A6 A6 B86 B86 628 O A6 A6 B88 B88 629 S A6 A6 B1 B1 630 S A6 A6 B6 B6 631 S A6 A6 B10 B10 632 S A6 A6 B16 B16 633 S A6 A6 B25 B25 634 S A6 A6 B28 B28 635 S A6 A6 B29 B29 636 S A6 A6 B30 B30 637 S A6 A6 B38 B38 638 S A6 A6 B39 B39 639 S A6 A6 B40 B40 640 S A6 A6 B41 B41 641 S A6 A6 B43 B43 642 S A6 A6 B52 B52 643 S A6 A6 B56 B56 644 S A6 A6 B67 B67 645 S A6 A6 B68 B68 646 S A6 A6 B69 B69 647 S A6 A6 B70 B70 648 S A6 A6 B71 B71 649 S A6 A6 B72 B72 650 S A6 A6 B74 B74 651 S A6 A6 B79 B79 652 S A6 A6 B80 B80 653 S A6 A6 B82 B82 654 S A6 A6 B83 B83 655 S A6 A6 B86 B86 656 S A6 A6 B88 B88 657 Se A6 A6 B1 B1 658 Se A6 A6 B6 B6 659 Se A6 A6 B10 B10 660 Se A6 A6 B16 B16 661 Se A6 A6 B25 B25 662 Se A6 A6 B28 B28 663 Se A6 A6 B29 B29 664 Se A6 A6 B30 B30 665 Se A6 A6 B38 B38 666 Se A6 A6 B39 B39 667 Se A6 A6 B40 B40 668 Se A6 A6 B41 B41 669 Se A6 A6 B43 B43 670 Se A6 A6 B52 B52 671 Se A6 A6 B56 B56 672 Se A6 A6 B67 B67 673 Se A6 A6 B68 B68 674 Se A6 A6 B69 B69 675 Se A6 A6 B70 B70 676 Se A6 A6 B71 B71 677 Se A6 A6 B72 B72 678 Se A6 A6 B74 B74 679 Se A6 A6 B79 B79 680 Se A6 A6 B80 B80 681 Se A6 A6 B82 B82 682 Se A6 A6 B83 B83 683 Se A6 A6 B86 B86 684 Se A6 A6 B88 B88 685 O A7 A7 B1 B1 686 O A7 A7 B6 B6 687 O A7 A7 B10 B10 688 O A7 A7 B16 B16 689 O A7 A7 B25 B25 690 O A7 A7 B28 B28 691 O A7 A7 B29 B29 692 O A7 A7 B30 B30 693 O A7 A7 B38 B38 694 O A7 A7 B39 B39 695 O A7 A7 B40 B40 696 O A7 A7 B41 B41 697 O A7 A7 B43 B43 698 O A7 A7 B52 B52 699 O A7 A7 B56 B56 700 O A7 A7 B67 B67 701 O A7 A7 B68 B68 702 O A7 A7 B69 B69 703 O A7 A7 B70 B70 704 O A7 A7 B71 B71 705 O A7 A7 B72 B72 706 O A7 A7 B74 B74 707 O A7 A7 B79 B79 708 O A7 A7 B80 B80 709 O A7 A7 B82 B82 710 O A7 A7 B83 B83 711 O A7 A7 B86 B86 712 O A7 A7 B88 B88 713 S A7 A7 B1 B1 714 S A7 A7 B6 B6 715 S A7 A7 B10 B10 716 S A7 A7 B16 B16 717 S A7 A7 B25 B25 718 S A7 A7 B28 B28 719 S A7 A7 B29 B29 720 S A7 A7 B30 B30 721 S A7 A7 B38 B38 722 S A7 A7 B39 B39 723 S A7 A7 B40 B40 724 S A7 A7 B41 B41 725 S A7 A7 B43 B43 726 S A7 A7 B52 B52 727 S A7 A7 B56 B56 728 S A7 A7 B67 B67 729 S A7 A7 B68 B68 730 S A7 A7 B69 B69 731 S A7 A7 B70 B70 732 S A7 A7 B71 B71 733 S A7 A7 B72 B72 734 S A7 A7 B74 B74 735 S A7 A7 B79 B79 736 S A7 A7 B80 B80 737 S A7 A7 B82 B82 738 S A7 A7 B83 B83 739 S A7 A7 B86 B86 740 S A7 A7 B88 B88 741 Se A7 A7 B1 B1 742 Se A7 A7 B6 B6 743 Se A7 A7 B10 B10 744 Se A7 A7 B16 B16 745 Se A7 A7 B25 B25 746 Se A7 A7 B28 B28 747 Se A7 A7 B29 B29 748 Se A7 A7 B30 B30 749 Se A7 A7 B38 B38 750 Se A7 A7 B39 B39 751 Se A7 A7 B40 B40 752 Se A7 A7 B41 B41 753 Se A7 A7 B43 B43 754 Se A7 A7 B52 B52 755 Se A7 A7 B56 B56 756 Se A7 A7 B67 B67 757 Se A7 A7 B68 B68 758 Se A7 A7 B69 B69 759 Se A7 A7 B70 B70 760 Se A7 A7 B71 B71 761 Se A7 A7 B72 B72 762 Se A7 A7 B74 B74 763 Se A7 A7 B79 B79 764 Se A7 A7 B80 B80 765 Se A7 A7 B82 B82 766 Se A7 A7 B83 B83 767 Se A7 A7 B86 B86 768 Se A7 A7 B88 B88 769 O O O B1 B1 770 O O O B6 B6 771 O O O B10 B10 772 O O O B22 B22 773 O O O B25 B25 774 O O O B28 B28 775 O O O B29 B29 776 O O O B30 B30 777 O O O B38 B38 778 O O O B39 B39 779 O O O B40 B40 780 O O O B41 B41 781 O O O B43 B43 782 O O O B52 B52 783 O O O B56 B56 784 O O O B67 B67 785 O O O B68 B68 786 O O O B69 B69 787 O O O B70 B70 788 O O O B71 B71 789 O O O B72 B72 790 O O O B74 B74 791 O O O B79 B79 792 O O O B80 B80 793 O O O B82 B82 794 O O O B83 B83 795 O O O B86 B86 796 O O O B88 B88 797 S O O B1 B1 798 S O O B6 B6 799 S O O B10 B10 800 S O O B22 B22 801 S O O B25 B25 802 S O O B28 B28 803 S O O B29 B29 804 S O O B30 B30 805 S O O B38 B38 806 S O O B39 B39 807 S O O B40 B40 808 S O O B41 B41 809 S O O B43 B43 810 S O O B52 B52 811 S O O B56 B56 812 S O O B67 B67 813 S O O B68 B68 814 S O O B69 B69 815 S O O B70 B70 816 S O O B71 B71 817 S O O B72 B72 818 S O O B74 B74 819 S O O B79 B79 820 S O O B80 B80 821 S O O B82 B82 822 S O O B83 B83 823 S O O B86 B86 824 S O O B88 B88 825 Se O O B1 B1 826 Se O O B6 B6 827 Se O O B10 B10 828 Se O O B22 B22 829 Se O O B25 B25 830 Se O O B28 B28 831 Se O O B29 B29 832 Se O O B30 B30 833 Se O O B38 B38 834 Se O O B39 B39 835 Se O O B40 B40 836 Se O O B41 B41 837 Se O O B43 B43 838 Se O O B52 B52 839 Se O O B56 B56 840 Se O O B67 B67 841 Se O O B68 B68 842 Se O O B69 B69 843 Se O O B70 B70 844 Se O O B71 B71 845 Se O O B72 B72 846 Se O O B74 B74 847 Se O O B79 B79 848 Se O O B80 B80 849 Se O O B82 B82 850 Se O O B83 B83 851 Se O O B86 B86 852 Se O O B88 B88 853 O S S B1 B1 854 O O O B6 B6 855 O S S B10 B10 856 O S S B22 B22 857 O S S B25 B25 858 O S S B28 B28 859 O S S B29 B29 860 O S S B30 B30 861 O S S B38 B38 862 O S S B39 B39 863 O S S B40 B40 864 O S S B41 B41 865 O S S B43 B43 866 O S S B52 B52 867 O S S B56 B56 868 O S S B67 B67 869 O S S B68 B68 870 O S S B69 B69 871 O S S B70 B70 872 O S S B71 B71 873 O S S B72 B72 874 O S S B74 B74 875 O S S B79 B79 876 O S S B80 B80 877 O S S B82 B82 878 O S S B83 B83 879 O S S B86 B86 880 O S S B88 B88 881 S S S B1 B1 882 S S S B6 B6 883 S S S B10 B10 884 S S S B22 B22 885 S S S B25 B25 886 S S S B28 B28 887 S S S B29 B29 888 S S S B30 B30 889 S S S B38 B38 890 S S S B39 B39 891 S S S B40 B40 892 S S S B41 B41 893 S S S B43 B43 894 S S S B52 B52 895 S S S B56 B56 896 S S S B67 B67 897 S S S B68 B68 898 S S S B69 B69 899 S S S B70 B70 900 S S S B71 B71 901 S S S B72 B72 902 S S S B74 B74 903 S S S B79 B79 904 S S S B80 B80 905 S S S B82 B82 906 S S S B83 B83 907 S S S B86 B86 908 S S S B88 B88 909 Se S S B1 B1 910 Se S S B6 B6 911 Se S S B10 B10 912 Se S S B22 B22 913 Se S S B25 B25 914 Se S S B28 B28 915 Se S S B29 B29 916 Se S S B30 B30 917 Se S S B38 B38 918 Se S S B39 B39 919 Se S S B40 B40 920 Se S S B41 B41 921 Se S S B43 B43 922 Se S S B52 B52 923 Se S S B56 B56 924 Se S S B67 B67 925 Se S S B68 B68 926 Se S S B69 B69 927 Se S S B70 B70 928 Se S S B71 B71 929 Se S S B72 B72 930 Se S S B74 B74 931 Se S S B79 B79 932 Se S S B80 B80 933 Se S S B82 B82 934 Se S S B83 B83 935 Se S S B86 B86 936 Se S S B88 B88 937 O Se Se B1 B1 938 O Se Se B6 B6 939 O Se Se B10 B10 940 O Se Se B22 B22 941 O Se Se B25 B25 942 O Se Se B28 B28 943 O Se Se B29 B29 944 O Se Se B30 B30 945 O Se Se B38 B38 946 O Se Se B39 B39 947 O Se Se B40 B40 948 O Se Se B41 B41 949 O Se Se B43 B43 950 O Se Se B52 B52 951 O Se Se B56 B56 952 O Se Se B67 B67 953 O Se Se B68 B68 954 O Se Se B69 B69 955 O Se Se B70 B70 956 O Se Se B71 B71 957 O Se Se B72 B72 958 O Se Se B74 B74 959 O Se Se B79 B79 960 O Se Se B80 B80 961 O Se Se B82 B82 962 O Se Se B83 B83 963 O Se Se B86 B86 964 O Se Se B88 B88 965 S Se Se B1 B1 966 S Se Se B6 B6 967 S Se Se B10 B10 968 S Se Se B22 B22 969 S Se Se B25 B25 970 S Se Se B28 B28 971 S Se Se B29 B29 972 S Se Se B30 B30 973 S Se Se B38 B38 974 S Se Se B39 B39 975 S Se Se B40 B40 976 S Se Se B41 B41 977 S Se Se B43 B43 978 S Se Se B52 B52 979 S Se Se B56 B56 980 S Se Se B67 B67 981 S Se Se B68 B68 982 S Se Se B69 B69 983 S Se Se B70 B70 984 S Se Se B71 B71 985 S Se Se B72 B72 986 S Se Se B74 B74 987 S Se Se B79 B79 988 S Se Se B80 B80 989 S Se Se B82 B82 990 S Se Se B83 B83 991 S Se Se B86 B86 992 S Se Se B88 B88 993 Se Se Se B1 B1 994 Se Se Se B6 B6 995 Se Se Se B10 B10 996 Se Se Se B22 B22 997 Se Se Se B25 B25 998 Se Se Se B28 B28 999 Se Se Se B29 B29 1000 Se Se Se B30 B30 1001 Se Se Se B38 B38 1002 Se Se Se B39 B39 1003 Se Se Se B40 B40 1004 Se Se Se B41 B41 1005 Se Se Se B43 B43 1006 Se Se Se B52 B52 1007 Se Se Se B56 B56 1008 Se Se Se B67 B67 1009 Se Se Se B68 B68 1010 Se Se Se B69 B69 1011 Se Se Se B70 B70 1012 Se Se Se B71 B71 1013 Se Se Se B72 B72 1014 Se Se Se B74 B74 1015 Se Se Se B79 B79 1016 Se Se Se B80 B80 1017 Se Se Se B82 B82 1018 Se Se Se B83 B83 1019 Se Se Se B86 B86 1020 Se Se Se B88 B88 1021 O A1 A1 B1 B6 1022 O A1 A1 B2 B6 1023 O A1 A1 B25 B26 1024 O A1 A1 B27 B28 1025 O A1 A1 B29 B30 1026 O A1 A1 B39 B40 1027 O A1 A1 B54 B41 1028 O A1 A1 B54 B52 1029 O A1 A1 B52 B56 1030 O A1 A1 B55 B56 1031 O A1 A1 B64 B56 1032 O A1 A1 B68 B69 1033 O A1 A1 B69 B70 1034 O A1 A1 B71 B72 1035 O A1 A1 B68 B80 1036 O A1 A1 B68 B83 1037 S A1 A1 B1 B6 1038 S A1 A1 B2 B6 1039 S A1 A1 B25 B26 1040 S A1 A1 B27 B28 1041 S A1 A1 B29 B30 1042 S A1 A1 B39 B40 1043 S A1 A1 B54 B41 1044 S A1 A1 B54 B52 1045 S A1 A1 B52 B56 1046 S A1 A1 B55 B56 1047 S A1 A1 B64 B56 1048 S A1 A1 B68 B69 1049 S A1 A1 B69 B70 1050 S A1 A1 B71 B72 1051 S A1 A1 B68 B80 1052 S A1 A1 B68 B83 1053 Se A1 A1 B1 B6 1054 Se A1 A1 B2 B6 1055 Se A1 A1 B25 B26 1056 Se A1 A1 B27 B28 1057 Se A1 A1 B29 B30 1058 Se A1 A1 B39 B40 1059 Se A1 A1 B54 B41 1060 Se A1 A1 B54 B52 1061 Se A1 A1 B52 B56 1062 Se A1 A1 B55 B56 1063 Se A1 A1 B64 B56 1064 Se A1 A1 B68 B69 1065 Se A1 A1 B69 B70 1066 Se A1 A1 B71 B72 1067 Se A1 A1 B68 B80 1068 Se A1 A1 B68 B83 1069 O A2 A2 B1 B6 1070 O A2 A2 B2 B6 1071 O A2 A2 B25 B26 1072 O A2 A2 B27 B28 1073 O A2 A2 B29 B30 1074 O A2 A2 B39 B40 1075 O A2 A2 B54 B41 1076 O A2 A2 B54 B52 1077 O A2 A2 B52 B56 1078 O A2 A2 B55 B56 1079 O A2 A2 B64 B56 1080 O A2 A2 B68 B69 1081 O A2 A2 B69 B70 1082 O A2 A2 B71 B72 1083 O A2 A2 B68 B80 1084 O A2 A2 B68 B83 1085 S A2 A2 B1 B6 1086 S A2 A2 B2 B6 1087 S A2 A2 B25 B26 1088 S A2 A2 B27 B28 1089 S A2 A2 B29 B30 1090 S A2 A2 B39 B40 1091 S A2 A2 B54 B41 1092 S A2 A2 B54 B52 1093 S A2 A2 B52 B56 1094 S A2 A2 B55 B56 1095 S A2 A2 B64 B56 1096 S A2 A2 B68 B69 1097 S A2 A2 B69 B70 1098 S A2 A2 B71 B72 1099 S A2 A2 B68 B80 1100 S A2 A2 B68 B83 1101 Se A2 A2 B1 B6 1102 Se A2 A2 B2 B6 1103 Se A2 A2 B25 B26 1104 Se A2 A2 B27 B28 1105 Se A2 A2 B29 B30 1106 Se A2 A2 B39 B40 1107 Se A2 A2 B54 B41 1108 Se A2 A2 B54 B52 1109 Se A2 A2 B52 B56 1110 Se A2 A2 B55 B56 1111 Se A2 A2 B64 B56 1112 Se A2 A2 B68 B69 1113 Se A2 A2 B69 B70 1114 Se A2 A2 B71 B72 1115 Se A2 A2 B68 B80 1116 Se A2 A2 B68 B83 1117 O A3 A3 B1 B1 1118 O A3 A3 B6 B6 1119 O A3 A3 B25 B25 1120 O A3 A3 B28 B28 1121 O A3 A3 B29 B29 1122 O A3 A3 B30 B30 1123 O A3 A3 B56 B56 1124 O A3 A3 B67 B67 1125 O A3 A3 B68 B68 1126 O A3 A3 B69 B69 1127 O A3 A3 B70 B70 1128 O A3 A3 B71 B71 1129 O A3 A3 B72 B72 1130 O A3 A3 B74 B74 1131 O A3 A3 B80 B80 1132 O A3 A3 B83 B83 1133 S A3 A3 B1 B1 1134 S A3 A3 B6 B6 1135 S A3 A3 B25 B25 1136 S A3 A3 B28 B28 1137 S A3 A3 B29 B29 1138 S A3 A3 B30 B30 1139 S A3 A3 B56 B56 1140 S A3 A3 B67 B67 1141 S A3 A3 B68 B68 1142 S A3 A3 B69 B69 1143 S A3 A3 B70 B70 1144 S A3 A3 B71 B71 1145 S A3 A3 B72 B72 1146 S A3 A3 B74 B74 1147 S A3 A3 B80 B80 1148 S A3 A3 B83 B83 1149 Se A3 A3 B1 B1 1150 Se A3 A3 B6 B6 1151 Se A3 A3 B25 B25 1152 Se A3 A3 B28 B28 1153 Se A3 A3 B29 B29 1154 Se A3 A3 B30 B30 1155 Se A3 A3 B56 B56 1156 Se A3 A3 B67 B67 1157 Se A3 A3 B68 B68 1158 Se A3 A3 B69 B69 1159 Se A3 A3 B70 B70 1160 Se A3 A3 B71 B71 1161 Se A3 A3 B72 B72 1162 Se A3 A3 B74 B74 1163 Se A3 A3 B80 B80 1164 Se A3 A3 B83 B83 1165 O O A1 B1 B1 1166 O O A1 B6 B6 1167 O O A1 B25 B25 1168 O O A1 B28 B28 1169 O O A1 B29 B29 1170 O O A1 B30 B30 1171 O O A1 B56 B56 1172 O O A1 B67 B67 1173 O O A1 B68 B68 1174 O O A1 B69 B69 1175 O O A1 B70 B70 1176 O O A1 B71 B71 1177 O O A1 B72 B72 1178 O O A1 B74 B74 1179 O O A1 B80 B80 1180 O O A1 B83 B83 1181 S O A1 B1 B1 1182 S O A1 B6 B6 1183 S O A1 B25 B25 1184 S O A1 B28 B28 1185 S O A1 B29 B29 1186 S O A1 B30 B30 1187 S O A1 B56 B56 1188 S O A1 B67 B67 1189 S O A1 B68 B68 1190 S O A1 B69 B69 1191 S O A1 B70 B70 1192 S O A1 B71 B71 1193 S O A1 B72 B72 1194 S O A1 B74 B74 1195 S O A1 B80 B80 1196 S O A1 B83 B83 1197 Se O A1 B1 B1 1198 Se O A1 B6 B6 1199 Se O A1 B25 B25 1200 Se O A1 B28 B28 1201 Se O A1 B29 B29 1202 Se O A1 B30 B30 1203 Se O A1 B56 B56 1204 Se O A1 B67 B67 1205 Se O A1 B68 B68 1206 Se O A1 B69 B69 1207 Se O A1 B70 B70 1208 Se O A1 B71 B71 1209 Se O A1 B72 B72 1210 Se O A1 B74 B74 1211 Se O A1 B80 B80 1212 Se O A1 B83 B83 1213 O A1 A2 B1 B1 1214 O A1 A2 B6 B6 1215 O A1 A2 B25 B25 1216 O A1 A2 B28 B28 1217 O A1 A2 B29 B29 1218 O A1 A2 B30 B30 1219 O A1 A2 B56 B56 1220 O A1 A2 B67 B67 1221 O A1 A2 B68 B68 1222 O A1 A2 B69 B69 1223 O A1 A2 B70 B70 1224 O A1 A2 B71 B71 1225 O A1 A2 B72 B72 1226 O A1 A2 B74 B74 1227 O A1 A2 B80 B80 1228 O A1 A2 B83 B83 1229 S A1 A2 B1 B1 1230 S A1 A2 B6 B6 1231 S A1 A2 B25 B25 1232 S A1 A2 B28 B28 1233 S A1 A2 B29 B29 1234 S A1 A2 B30 B30 1235 S A1 A2 B56 B56 1236 S A1 A2 B67 B67 1237 S A1 A2 B68 B68 1238 S A1 A2 B69 B69 1239 S A1 A2 B70 B70 1240 S A1 A2 B71 B71 1241 S A1 A2 B72 B72 1242 S A1 A2 B74 B74 1243 S A1 A2 B80 B80 1244 S A1 A2 B83 B83 1245 Se A1 A2 B1 B1 1246 Se A1 A2 B6 B6 1247 Se A1 A2 B25 B25 1248 Se A1 A2 B28 B28 1249 Se A1 A2 B29 B29 1250 Se A1 A2 B30 B30 1251 Se A1 A2 B56 B56 1252 Se A1 A2 B67 B67 1253 Se A1 A2 B68 B68 1254 Se A1 A2 B69 B69 1255 Se A1 A2 B70 B70 1256 Se A1 A2 B71 B71 1257 Se A1 A2 B72 B72 1258 Se A1 A2 B74 B74 1259 Se A1 A2 B80 B80 1260 Se A1 A2 B83 B83 1261 O A1 A3 B1 B1 1262 O A1 A3 B6 B6 1263 O A1 A3 B25 B25 1264 O A1 A3 B28 B28 1265 O A1 A3 B29 B29 1266 O A1 A3 B30 B30 1267 O A1 A3 B56 B56 1268 O A1 A3 B67 B67 1269 O A1 A3 B68 B68 1270 O A1 A3 B69 B69 1271 O A1 A3 B70 B70 1272 O A1 A3 B71 B71 1273 O A1 A3 B72 B72 1274 O A1 A3 B74 B74 1275 O A1 A3 B80 B80 1276 O A1 A3 B83 B83 1277 S A1 A3 B1 B1 1278 S A1 A3 B6 B6 1279 S A1 A3 B25 B25 1280 S A1 A3 B28 B28 1281 S A1 A3 B29 B29 1282 S A1 A3 B30 B30 1283 S A1 A3 B56 B56 1284 S A1 A3 B67 B67 1285 S A1 A3 B68 B68 1286 S A1 A3 B69 B69 1287 S A1 A3 B70 B70 1288 S A1 A3 B71 B71 1289 S A1 A3 B72 B72 1290 S A1 A3 B74 B74 1291 S A1 A3 B80 B80 1292 S A1 A3 B83 B83 1293 Se A1 A3 B1 B1 1294 Se A1 A3 B6 B6 1295 Se A1 A3 B25 B25 1296 Se A1 A3 B28 B28 1297 Se A1 A3 B29 B29 1298 Se A1 A3 B30 B30 1299 Se A1 A3 B56 B56 1300 Se A1 A3 B67 B67 1301 Se A1 A3 B68 B68 1302 Se A1 A3 B69 B69 1303 Se A1 A3 B70 B70 1304 Se A1 A3 B71 B71 1305 Se A1 A3 B72 B72 1306 Se A1 A3 B74 B74 1307 Se A1 A3 B80 B80 1308 Se A1 A3 B83 B83 1309 O A2 A6 B1 B1 1310 O A2 A6 B6 B6 1311 O A2 A6 B25 B25 1312 O A2 A6 B28 B28 1313 O A2 A6 B29 B29 1314 O A2 A6 B30 B30 1315 O A2 A6 B56 B56 1316 O A2 A6 B67 B67 1317 O A2 A6 B68 B68 1318 O A2 A6 B69 B69 1319 O A2 A6 B70 B70 1320 O A2 A6 B71 B71 1321 O A2 A6 B72 B72 1322 O A2 A6 B74 B74 1323 O A2 A6 B80 B80 1324 O A2 A6 B83 B83 1325 S A2 A6 B1 B1 1326 S A2 A6 B6 B6 1327 S A2 A6 B25 B25 1328 S A2 A6 B28 B28 1329 S A2 A6 B29 B29 1330 S A2 A6 B30 B30 1331 S A2 A6 B56 B56 1332 S A2 A6 B67 B67 1333 S A2 A6 B68 B68 1334 S A2 A6 B69 B69 1335 S A2 A6 B70 B70 1336 S A2 A6 B71 B71 1337 S A2 A6 B72 B72 1338 S A2 A6 B74 B74 1339 S A2 A6 B80 B80 1340 S A2 A6 B83 B83 1341 Se A2 A6 B1 B1 1342 Se A2 A6 B6 B6 1343 Se A2 A6 B25 B25 1344 Se A2 A6 B28 B28 1345 Se A2 A6 B29 B29 1346 Se A2 A6 B30 B30 1347 Se A2 A6 B56 B56 1348 Se A2 A6 B67 B67 1349 Se A2 A6 B68 B68 1350 Se A2 A6 B69 B69 1351 Se A2 A6 B70 B70 1352 Se A2 A6 B71 B71 1353 Se A2 A6 B72 B72 1354 Se A2 A6 B74 B74 1355 Se A2 A6 B80 B80 1356 Se A2 A6 B83 B83 1357 O A1 A1 B89 B89 1358 O A1 A1 B90 B90 1359 O A1 A1 B91 B91 1360 O A1 A1 B92 B92 1361 O A1 A1 B93 B93 1362 O A1 A1 B94 B94 1363 O A1 A1 B95 B95 1364 O A1 A1 B96 B96 1365 O A1 A1 B97 B97 1366 O A1 A1 B98 B98 1367 O A1 A1 B99 B99 1368 O A1 A1 B100 B100 1369 O A1 A1 B101 B101 1370 O A1 A1 B102 B102 1371 O A1 A1 B103 B103 1372 O A1 A1 B104 B104 1373 O A1 A1 B105 B105 1374 O A1 A1 B106 B106 1375 O A1 A1 B107 B107 1376 O A1 A1 B108 B108 1377 O A1 A1 B109 B109 1378 O A1 A1 B110 B110 1379 O A1 A1 B111 B111 1380 O A1 A1 B112 B112 1381 S A1 A1 B89 B89 1382 S A1 A1 B90 B90 1383 S A1 A1 B91 B91 1384 S A1 A1 B92 B92 1385 S A1 A1 B93 B93 1386 S A1 A1 B94 B94 1387 S A1 A1 B95 B95 1388 S A1 A1 B96 B96 1389 S A1 A1 B97 B97 1390 S A1 A1 B98 B98 1391 S A1 A1 B99 B99 1392 S A1 A1 B100 B100 1393 S A1 A1 B101 B101 1394 S A1 A1 B102 B102 1395 S A1 A1 B103 B103 1396 S A1 A1 B104 B104 1397 S A1 A1 B105 B105 1398 S A1 A1 B106 B106 1399 S A1 A1 B107 B107 1400 S A1 A1 B108 B108 1401 S A1 A1 B109 B109 1402 S A1 A1 B110 B110 1403 S A1 A1 B111 B111 1404 S A1 A1 B112 B112 1405 Se A1 A1 B89 B89 1406 Se A1 A1 B90 B90 1407 Se A1 A1 B91 B91 1408 Se A1 A1 B92 B92 1409 Se A1 A1 B93 B93 1410 Se A1 A1 B94 B94 1411 Se A1 A1 B95 B95 1412 Se A1 A1 B96 B96 1413 Se A1 A1 B97 B97 1414 Se A1 A1 B98 B98 1415 Se A1 A1 B99 B99 1416 Se A1 A1 B100 B100 1417 Se A1 A1 B101 B101 1418 Se A1 A1 B102 B102 1419 Se A1 A1 B103 B103 1420 Se A1 A1 B104 B104 1421 Se A1 A1 B105 B105 1422 Se A1 A1 B106 B106 1423 Se A1 A1 B107 B107 1424 Se A1 A1 B108 B108 1425 Se A1 A1 B109 B109 1426 Se A1 A1 B110 B110 1427 Se A1 A1 B111 B111 1428 Se A1 A1 B112 B112

According to one embodiment of the present invention, an electroluminescent device is further disclosed, wherein the electroluminescent device,

anode,

cathode, and

an organic layer disposed between the anode and the cathode, wherein the organic layer contains a compound having formula (1):

wherein X and Y are identically or differently selected from CR''R'', NR', O, S or Se each time they occur;

wherein Z ₁ and Z ₂ are identically or differently selected from O, S or Se each time they occur;

Each time R, R', R" and R"' appear identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 3 to 20 ring carbon atoms atoms), substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, and 1 to 20 carbon atoms. A substituted or unsubstituted alkoxy group having 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 alkenyl group having 2 to 20 carbon atoms Or an unsubstituted akinyl group, 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 group having 3 to 20 carbon atoms It is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;

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

Adjacent substituents may be optionally linked to form a ring.

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

According to an embodiment of the present invention, in the above device, wherein the organic layer is a hole injection layer, the hole injection layer is formed of the compound containing a dopant and the dopant contains at least one hole transport material; The hole transport material is a compound containing a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylenevinyl compound, and an oligofluorene compound. It contains an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the morph doping ratio between the compound and the hole transport material is 10000:1 to 1:10000.

According to one embodiment of the present invention, in the hole injection layer, a morph doping ratio between the compound and the hole transport material is 10:1 to 1:100.

According to one embodiment of the present invention, the electroluminescent device includes a plurality of stack layers between an anode and a cathode, and the stack layer includes a first light emitting layer and a second light emitting layer, wherein the first stack layer includes a first light emitting layer. The second stack layer includes a light emitting layer and the second stack layer includes a second light emitting layer, and a charge generation layer is disposed between the first stack layer and the second stack layer, wherein the charge generation layer is a p-type charge generation layer and an n-type charge generation layer. includes; Here, the organic layer containing the compound having formula (1) is a p-type charge generating layer.

According to one embodiment of the present invention, the p-type charge generation layer further contains at least one hole transport material, and the p-type charge generation layer is formed by doping the compound into the at least one hole transport material, , The hole transport material is a compound containing a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligo It contains an oligofluorene compound, a porphyrin complex, or a metal phthalocyanine complex, wherein a morph doping ratio between the compound and the hole transport material is 10000:1 to 1:10000.

According to an embodiment of the present invention, in the p-type charge generating layer, a morph doping ratio between the compound and the hole transport material is 10:1 to 1:100.

According to one embodiment of the present invention, wherein the charge generating layer further includes a buffer layer disposed between the p-type charge generating layer and the n-type charge generating layer, and the buffer layer contains the compound.

According to another embodiment of the present invention, a compound preparation containing the compound represented by formula (1) is further disclosed. The specific structure of the compound is shown in any one of the foregoing examples.

Combination with other materials

Materials used for a specific layer in the organic light emitting device described in the present invention may be used in combination with various other materials present in the device. The combination of these materials is described in detail in paragraphs 0132 to 0161 of US patent application US2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily refer to the literature to identify combinations and other materials that can be used.

In this text, it is explained that materials usable for a specific layer in an organic light emitting device can be used in combination with various types of other materials present in the device. For example, the compounds disclosed herein may be used in combination with various types of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of patent application US2015/0349273A1, the entire contents of which are incorporated herein by reference. The materials described or referenced herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily refer to the literature to identify combinations and other materials that can be used.

In the examples of material synthesis, all reactions are conducted under nitrogen protection unless otherwise noted. All reaction solvents were anhydrous and used as received from commercial sources. The synthesized product is synthesized using one or several types of equipment routine in this field (BRUKER's nuclear magnetic resonance spectrometer, SHIMADZU's liquid chromatography, liquid chromatograph-mass spectrometry, gas chromatograph mass spectrometer ( gas chromatograph-mass spectrometry), differential scanning calorimeter, fluorescence spectrophotometer of Shanghai LENGGUANG TECH., electrochemical workstation of Wuhan CORRTEST, and sublimation apparatus of Anhui BEQ, etc. ), the structure is confirmed and the properties are tested by methods well known to those skilled in the art. In the embodiment of the device, the characteristics of the device also include regular equipment in the field (evaporator produced by ANGSTROM ENGINEERING, optical test system and life test system produced by Suzhou FATAR, ellipsometer produced by Beijing ELLITOP, etc. (but not limited thereto) is tested by methods well known to those skilled in the art. A person skilled in the art is well aware of the use of the equipment, the test method, and the like, so that the unique data of the sample can be obtained reliably and unaffected, so the above related details are not further described herein.

Material Synthesis Example:

The present invention does not limit the preparation method of the compound, typical examples include the following compounds, but are not limited thereto, and the synthesis route and preparation method are as follows:

Synthesis Example 1: Synthesis of Compound 56

Step (1): Synthesis of [Intermediate 1-a ]

DMSO (150 mL) was added to a 500 mL three-neck flask, nitrogen was bubbled for half an hour, and HC(OEt) ₃ (22.2 g, 150 mmol) and Y(OTf) ₃ (2.15 g, 4 mmol) were sequentially added. and continued bubbling for 5 min, 2,5-diamino-3,6-dibromobenzene-1,4-diphenol (8.94 g, 30 mmol) was added and the temperature was raised to 60 ° C. After 20 min, the solution It turns a brown or khaki color and is stirred overnight. Upon completion of the reaction, DCM/PE (1:1, 500 mL) was added to the solution, the solid was collected by filtration, washed with acetone and filtered to obtain an off-white solid 1-a (7.2 g, 75 % yield) is obtained. ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 9.03 (s, 2H).

Step (2): Synthesis of [Intermediate 1-b ]

Dioxane (50 mL) was added to a 250 mL two-necked flask, nitrogen was bubbled for 15 min, and Pd(OAc) ₂ (225 mg, 10 mol%, 1.0 mmol) and XPhos (1.0 g, 2.1 mmol) were added while stirring. , continued stirring for 10 min, and then sequentially added 1-a (3.18 g, 10 mmol), p-trifluoromethoxyphenylboronic acid (8.24 g, 40 mmol) and potassium carbonate (8.34 g, 60 mmol). The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is decreased, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain white solid 1-b (4.36 g, 91% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 9.00 (s, 2H), 8.33 (d, J = 8.8 Hz, 4H), 7.63 (d, J = 8.8 Hz, 4H).

Step (3): Synthesis of [Intermediate 1-c ]

Under a nitrogen atmosphere, intermediate 1-b (4.36 g, 9.1 mmol) was added to THF (114 mL, 0.08 M), cooled to -94 °C (acetone/liquid nitrogen cooling bath) and n-butyllithium (13.8 mL) slowly. , 20.93 mmol, 1.6M n-hexane solution) was dripped, the temperature was maintained for 1 h, and then the temperature was slowly raised to -78 ° C (acetone / dry ice cooling bath) and reacted for 8 h. A THF solution (15 mL) of elemental iodine (6.93 g, 27.3 mmol) was added, and when the addition was completed, the temperature was slowly raised to room temperature, left overnight, and quenched by adding a small amount of saturated ammonium chloride aqueous solution. , directly added diatomaceous earth, stirred the sample, and purified by silica gel column chromatography (PE:DCM=3:1-1:1) to obtain a white solid product 1-c (4.0 g, 60% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 8.16 (d, J = 8.8 Hz, 4H), 7.62 (d, J = 8.8 Hz, 4H).

Step (4): Synthesis of [Intermediate 1-d ]

Under a nitrogen atmosphere, malononitrile (2.78 g, 42 mmol) was added to anhydrous DMF (70 mL), NaH (1.67 g, 42 mmol, content of 60%) was added in several portions at 0 ° C, and at 0 ° C After stirring for 10 min and stirring at room temperature for 20 min, 1-c (5.08 g, 7 mmol) and Pd(PPh ₄ ) ₃ (1.62 g, 1.4 mmol) were added, and the temperature was raised to 90 °C and reacted for 24-36 h. . After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 4.38 g of a yellow solid. Then washed twice successively with dichloromethane and filtered to obtain yellow solid 1-d (4.2 g, 98% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 8.08 (d, J = 8.8 Hz, 4H), 7.56 (d, J = 8.8 Hz, 4H).

Step (5): Synthesis of Compound 56

In a nitrogen atmosphere, 1-d (3.04 g, 5 mmol) was added to DCM (150 mL), cooled to 0 ° C, PIFA (6.45 g, 15 mmol) was added in portions and stirred at room temperature for 3 days, The solution becomes purple-black. After adding n-hexane (450 mL) to the reaction solution, stirring for 10 min and filtering, a black-green solid was obtained. Washed twice using each (DCM/PE=2:1-1:1) to finally obtain Compound 56 (2.5 g, 83% yield) as a black-green solid. ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.30 (d, J = 8.4 Hz, 4H), 7.73 (d, J = 8.4 Hz, 4H).

Synthesis Example 2: Synthesis of Compound 68

Step (1): Synthesis of [Intermediate 2-a ]

Dioxane (80 mL) was added to a 250 mL two-neck flask, nitrogen was bubbled for 15 min, Pd(OAc) ₂ (360 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added while stirring, and so on. After stirring for 10 min, 1-a (4.1 g, 13 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (14.0 g, 54 mmol) and cesium fluoride (9.12 g, 60 mmol) is added. The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is decreased, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain a white solid 2-a (6.7 g, 88% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.87 (s, 4H), 8.41 (s, 2H), 8.00 (s, 2H).

Step (2): Synthesis of [Intermediate 2-b ]

In a nitrogen atmosphere, 2-a (6.2 g, 10.6 mmol) was added to THF (212 mL, 0.05 M), cooled to -94→ (acetone/liquid nitrogen cooling bath) and slowly n-butyllithium (15.2 mL, 24.4 mL). mmol, 1.6M n-hexane solution), maintain the temperature for 1h, then slowly raise the temperature to -78°C (acetone/dry ice cooling bath) and react for 8h. A THF solution (20 mL) of pure iodine (8.07 g, 31.8 mmol) was added, and when the addition was complete, the temperature was slowly raised to room temperature, left overnight, a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly After addition, the sample is stirred, and purified by silica gel column chromatography (PE:DCM=6:1-2:1) to give a white solid product 2-b (4.7g, 53% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.69 (s, 4H), 8.01 (s, 2H).

Step (3): Synthesis of [Intermediate 2-c ]

Under a nitrogen atmosphere, malononitrile (1.56 g, 23.7 mmol) was added to anhydrous DMF (55 mL, 0.1 M), and NaH (948 mg, 23.7 mmol, content of 60%) was added in several portions at 0 ° C. , stirred at 0 °C for 10 min and stirred at room temperature for 20 min, then added 2-b (3.3 g, 3.95 mmol) and Pd(PPh ₄ ) ₃ (456 mg, 0.39 mmol), warmed to 90 °C, and React for 36 h. After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 2.98 g of a yellow solid. Then, it was washed twice successively with solvent (DCM/PE=2:1, 200 mL) and filtered to obtain yellow solid 2-c (2.81 g, 99% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.57 (s, 4H), 8.33 (s, 2H).

Step (4): Synthesis of Compound 68

In a nitrogen atmosphere, 2-c (2.85 g, 4.0 mmol) was divided into 3 parts (0.95 g/part) into three two-necked flasks, DCM (200 mL) was added to each, and the temperature was cooled to 0 ° C. PIFA (1.73 g, 4.0 mmol) was added in portions and stirred at room temperature for 3 days, the solution becoming purple-black. Next, the solution in 3 bottles is put into a 1L one-necked flask, and the solution is spun dried until the solution is 50mL left and right, n-hexane (450mL) is added thereto, stirred for 10min, and filtered to obtain a black-green solid. Washed twice with each (DCM/PE=2:1, 200 mL) to finally obtain compound 68 (2.4 g, 85% yield) as a black-green solid. ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.86 (s, 4H), 8.37 (s, 2H).

Synthesis Example 3: Synthesis of Compound 70

Step (1): Synthesis of [Intermediate 4-a ]

Dioxane (80 mL) was added to a 250 mL two-neck flask, nitrogen was bubbled for 15 min, Pd(OAc) ₂ (360 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added while stirring, and so on. After stirring for 10 min, 1-a (4.1 g, 13 mmol), 2,4-bis(trifluoromethyl)phenylboronic acid (14.0 g, 54 mmol) and cesium fluoride (9.12 g, 60 mmol) was added, the temperature was raised to 110° C. to reflux, and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, thoroughly washed with dichloromethane, and separated by silica gel column chromatography to obtain a white solid 4-a (6.83 g, 90% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.19 (s, 2H), 8.12 (s, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.0 Hz, 2H).

Step (2): Synthesis of [Intermediate 4-b ]

Under a nitrogen atmosphere, 4-a (6.4 g, 11 mmol) was added to THF (150 mL), cooled to -94 °C (acetone/liquid nitrogen cooling bath) and slowly n-butyllithium (15.8 mL, 25.3 mmol, 1.6 M n-hexane solution) is dripped, the temperature is maintained for 1 h, then the temperature is slowly raised to -78 ° C (acetone/dry ice cooling bath) and reacted for 8 h. A THF solution (20 mL) of pure iodine (8.4 g, 33 mmol) was added, and when the addition was complete, the temperature was slowly raised to room temperature, left overnight, a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was added directly. The sample was stirred and purified by silica gel column chromatography (PE:DCM=10:1-2:1) to obtain a white solid product 4-b (6.89g, 75% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.16 (s, 2H), 8.01 (d, J = 7.6 Hz, 2H), 7.73 (d, J = 7.6 Hz, 2H).

Step (3): Synthesis of [Intermediate 4-c ]

Under a nitrogen atmosphere, malononitrile (2.14 g, 32 mmol) was added to anhydrous DMF (60 mL), NaH (1.40 g, 35 mmol, content of 60%) was added in portions at 0 ° C, and at 0 ° C After stirring for 10 min and stirring at room temperature for 20 min, 4-b (4.51 g, 5.4 mmol) and Pd(PPh ₄ ) ₃ (1.15 g, 1.0 mmol) were added, the temperature was raised to 90 °C, and the reaction was continued for 24-36 h. let it After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 2.98 g of a yellow solid. Then washed twice successively with dichloromethane and filtered to obtain yellow solid 4-c (2.92 g, 76% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.35 (m, 4H), 8.16 (d, J = 7.6 Hz, 2H).

Step (4): Synthesis of Compound 70

Under a nitrogen atmosphere, divide 4-c (2.92g, 4.1mmol) into 3 parts (1g/part) into 3 two-necked flasks, add DCM (100mL) to each, cool to 0°C, and PIFA to each. (1.8g, 4.2mmol) was added in several portions and stirred at room temperature for 3 days, and the solution became purple-black. Next, the solution in 3 bottles was put into a 1 L one-necked flask and concentrated until the solution was 50 mL left and right, n-hexane (450 mL) was added thereto, stirred for 10 min, and filtered to obtain a purple solid. After washing twice with each (DCM/PE=2:1, 200 mL), a purple solid Compound 70 (2.0 g, 70% yield) was finally obtained. ¹ HNMR (400 MHz, CD ₂ Cl ₂ ) δ = 8.22 (s, 2H), 8.11 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H).

Synthesis Example 4: Synthesis of Compound 101

Step (1): Synthesis of [Intermediate 5-a ]

Distilled water (50mL), 1,4-phenylenediamine (17.0g, 157mmol) and hydrochloric acid (30.7mL, 125mmol) were added to a 500mL two-necked flask, and the temperature was raised to 50°C, and NH ₄ Add SCN (48.4g, 636mmol) and continue to warm to 90° C. and stir for 24h. After the reaction was completed, the mixture was cooled, filtered, washed with ethanol, and filtered to obtain a gray solid compound 5-a (31.5 g, 90% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 9.69 (s, 2H), 7.32 (s, 4H).

Step (2): Synthesis of [Intermediate 5-b ]

Compound 5-a (15g, 66.5mmol) and chloroform (100mL) were sequentially added to a 500mL three-necked flask, the temperature was raised to 50 ° C, and a chloroform (100mL) solution of bromine (8mL, 309mmol) was dripped very slowly. After the drip is completed, it is refluxed for 24-36 h. After the reaction is complete, the temperature is lowered to 0° C., filtered, and the filter cake is washed with chloroform three times. The solid was collected, washed with saturated sodium thiosulfate solution and filtered to collect the solid, followed by washing with methanol and dichloromethane respectively and filtering to obtain a brown solid 5-b (12.5 g, 83% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 8.56 (bs, 4H), 7.83 (s, 2H).

Step (3): Synthesis of [Intermediate 5-c ]

Acetonitrile (500mL) was added to a 1L three-necked flask and nitrogen was bubbled for 20min, followed by compound 5-b (11g, 50mmol), iodine (76g, 300mmol) and tBuONO (20.6g, 200mmol) sequentially. was added and reacted at 70° C. for 24 h. After the reaction was completed, the temperature was decreased, and acetonitrile was removed by distillation under reduced pressure, and 200 mL of dichloromethane was added, filtered, and washed with petroleum ether to obtain brick red solid 5-c (11 g, 50% yield) ) to get ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 8.74 (s, 2H).

Step (4): Synthesis of [Intermediate 5-d ]

In a nitrogen atmosphere, malononitrile (5.35 g, 81 mmol) was added to anhydrous DMF (135 mL), NaH (3.24 g, 81 mmol, content of 60%) was added in several portions at 0 ° C, and at 0 → After stirring for 10 min and stirring at room temperature for 20 min, compound 5-c (6.08 g, 13.5 mmol) and Pd(PPh ₄ ) ₃ (3.12 g, 2.7 mmol) were added, and the temperature was raised to 90 °C for 24-36 h. react After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of brown solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 4.2 g of a brown solid. Then, it was washed twice successively with dichloromethane and filtered to obtain 5-d (4.02 g, 93% yield) as a brown solid. LCMS (ESI): m/z 319 [MH] ^- .

Step (5): Synthesis of Compound 101

Under a nitrogen atmosphere, compound 5-d (3.20 g, 10 mmol) was added to DCM (1 L), cooled to 0 ° C, and PIFA (12.9 g, 30 mmol) was added in several portions and stirred at room temperature for 3 days. , the solution becomes purple-black. After the reaction is complete, the solution is spun dry until the volume is 100 mL, then n-hexane (450 mL) is added to the reaction solution, stirred for 10 min and filtered to obtain a purple-black solid. Washing twice with dichloromethane gave compound 101 (3.0 g, 94% yield) as a purple-black solid. LCMS (ESI): m/z 317 [MH] ^- .

Synthesis Example 5: Synthesis of Compound 69

Step (1): Synthesis of [Intermediate 6-a ]

2,5-bis(trifluoromethyl)bromobenzene (18.5g, 63mmol) and ultra-dry tetrahydrofuran (100mL) were added in a nitrogen atmosphere to a 250mL two-necked flask, and the temperature was cooled to -78°C and slowly isopropyl. Drip magnesium chloride and lithium chloride solution (54 mL, 69 mmol, 1.3 M tetrahydrofuran solution), and after completion of the drip, react at -78 ° C for 1 h, then transfer to room temperature and react for 4 h. A solution of ZnCl ₂ (35mL, 69.3mmol, 2.0M 2-methyltetrahydrofuran solution) was slowly dripped at room temperature, and after dripping was completed, the mixture was stirred at room temperature for 1h. Under nitrogen protection, Pd(OAc) ₂ (337mg, 1.5mmol), XPhos (1.43g, 3.0mmol) and 1-a (5.0g, 15.7mmol) were added at once, stirred continuously for 10min, and then the temperature was raised. and refluxed for 24 h. After completion of the reaction, the temperature is cooled and quenched by adding a small amount of saturated ammonium chloride solution, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain an off-white solid 6-a ( 4.23 g, 46% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.13 (s, 2H), 8.07 (d, J = 8.4 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H), 7.87 (s, 2H).

Step (2): Synthesis of [Intermediate 6-b ]

Under a nitrogen atmosphere, 6-a (4.23g, 7.2mmol) was added to THF (200mL), cooled to -94°C and slowly dripped with n-butyllithium (10.4mL, 16.6mmol, 1.6M n-hexane solution). The temperature is maintained for 1 h, then the temperature is slowly raised to -78 ° C and reacted for 8 h. At -78 ° C, a THF solution (30 mL) of pure iodine (5.49 g, 21.6 mmol) was added, and when the addition was completed, the temperature was slowly raised to room temperature, reacted overnight, and quenched by adding a small amount of saturated ammonium chloride aqueous solution. , directly added diatomaceous earth, stirred the sample, and purified by silica gel column chromatography (PE:DCM=10:1-1:1) to obtain a pale yellow solid product 6-b (2.7 g, 45% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.05 (d, J = 8.4 Hz, 2H), 7.94 (d, J = 8.4 Hz, 2H), 7.83 (s, 2H).

Step (3): Synthesis of [Intermediate 6-c ]

Under a nitrogen atmosphere, malononitrile (792mg, 12mmol) was added to anhydrous DMF (20mL), and NaH (480mg, 12mmol, a content of 60%) was added in portions at 0°C for 10min at 0°C. After stirring and stirring at room temperature for 20 min, 6-b (1.70 g, 2 mmol) and Pd(PPh ₄ ) ₃ (277 mg, 0.24 mmol) were added, the temperature was raised to 90° C., and reacted for 24-36 h. After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 1.50 g of a yellow solid. Then, it was washed twice successively with dichloromethane and filtered to obtain yellow solid 6-c (1.40 g, 98% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.37-8.26 (m, 5H), 8.13 (s, 1H).

Step (4): Synthesis of Compound 69

In a nitrogen atmosphere, 6-c (1.40g, 2mmol) and DCM (200mL) were added to a 500mL two-necked flask, and after the temperature was lowered to 0 ° C, PIFA (1.72g, 4.0mmol) was added in several portions, After stirring at room temperature for 7 days, the solution becomes purple-black. After the reaction is complete, the solution is concentrated until it becomes 20 mL left and right, n-hexane (450 mL) is added thereto, stirred for 10 min, and filtered to obtain a grayish-black solid. (DCM/PE=2:1, 100 mL) to give compound 69 (1.2 g, 85% yield) as an off-black solid. ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.38-8.27 (m, 5H), 8.13 (s, 1H).

Synthesis Example 6: Synthesis of Compound 42

Step (1): Synthesis of [Intermediate 3-b ]

Dioxane (210 mL) was added to a 250 mL two-neck flask, nitrogen was bubbled for 15 min, Pd(OAc) ₂ (293 mg, 1.3 mmol) and SPhos (1.12 g, 2.73 mmol) were added while stirring, and so on. After stirring for 10 min, 3-a (15.8g, 65mmol), B ₂ pin ₂ (23g, 91mmol) and KOAc (12.7g, 130mmol) were sequentially added, and the temperature was raised to 110° C. to reflux, under the protection of nitrogen. Stir overnight. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain white solid 3-b (16 g, 85% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 7.64 (d, J =8.4 Hz, 1H), 7.59 (m, 2H), 1.35 (s, 12H).

Step (2): Synthesis of [Intermediate 3-c ]

Dioxane (150 mL) was added to a 250 mL two-neck flask, nitrogen was bubbled for 15 min, Pd(OAc) ₂ (293 mg, 1.3 mmol) and XPhos (1.34 g, 2.8 mmol) were added while stirring, and so on. After stirring for 10 min, 1-a (4.1 g, 13 mmol), 3-b (15.0 g, 52 mmol) and cesium fluoride (9.5 g, 62.4 mmol) were sequentially added, and the temperature was raised to 110°C. was brought to reflux and stirred overnight under nitrogen protection. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain 3-c (4.4 g, 70% yield) as a white solid. ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.35 (s, 2H), 8.23 (d, J =8.8 Hz, 4H), 7.83 (t, J =8.8 Hz, 2H).

Step (3): Synthesis of [Intermediate 3-d ]

Under a nitrogen atmosphere, 3-c (8.1 g, 16.7 mmol) was added to THF (250 mL), cooled to -94 °C (acetone/liquid nitrogen cooling bath) and slowly n-butyllithium (24 mL, 38.4 mmol, 1.6 M n-hexane solution) is dripped, the temperature is maintained for 1 h, then the temperature is slowly raised to -78 ° C (acetone/dry ice cooling bath) and reacted for 8 h. A THF solution (20 mL) of pure iodine (12.73 g, 50.1 mmol) was added, and when the addition was complete, the temperature was slowly raised to room temperature, left overnight, a small amount of saturated ammonium chloride aqueous solution was added to quench, and then diatomaceous earth was directly After addition, the sample is stirred and purified by silica gel column chromatography to give a white solid product 3-d (6.5 g, 53% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.31-8.27 (m, 4H), 8.02 (t, J =8.0 Hz, 2H).

Step (4): Synthesis of [Intermediate 3-e ]

In a nitrogen atmosphere, malononitrile (1.58 g, 24 mmol) was added to anhydrous DMF (40 mL), NaH (960 mg, 24 mmol, content of 60%) was added in several portions at 0 ° C, and stirred at 0 ° C for 10 min. After stirring for 20 min at room temperature, 3-d (3.0 g, 4 mmol) and Pd(PPh ₄ ) ₃ (462 mg, 0.4 mmol) were added, the temperature was raised to 90 °C, and reacted for 24-36 h. After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. Washing with dichloromethane gave 2.8 g of a yellow solid. Then, it was washed twice successively with solvent (DCM, 200 mL) and filtered to obtain yellow solid 3-e (2.4 g, 99% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.08 (t, J =8.0 Hz, 2H), 8.03-7.96 (m, 4H).

Step (5): Synthesis of Compound 42

Under a nitrogen atmosphere, 3-e (2.4g, 4mmol) was placed in a 500mL one-necked flask, DCM (200mL) was added and cooled to 0 °C, PIFA (3.44g, 8mmol) was added in several portions and room temperature After stirring for 3 days, the solution becomes purple-black. Next, the obtained solution was put into a 1 L one-necked flask, and rotary evaporation was performed until the solution became 50 mL left and right, n-hexane (450 mL) was added thereto, stirred for 10 min, and filtered to obtain a black solid. Washing twice with each (DCM/PE=2:1, 200 mL) gave compound 42 as a black solid (2.0 g, 82% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ =8.23-8.16 (m, 6H).

Synthesis Example 7: Synthesis of Compound 72

Step (1): Synthesis of [Intermediate 7-b ]

Tetrahydrofuran (130 mL) and deionized water (130 mL) were added to a 500 mL two-necked flask, nitrogen was bubbled for 15 min, and then Pd(PPh ₃ ) ₄ (1.73 g, 1.5 mmol), 7-a were sequentially added. (13.0 g, 50 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (14.2 g, 55 mmol) and cesium fluoride (11.1 g, 72 mmol) are added and stirred under nitrogen protection overnight. After the reaction was completed, it was quenched with dichloromethane, dried, and separated by silica gel column chromatography to obtain 7-b as a white solid (7.8 g, 40% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 7.99(s, 2H), 7.96(s, 1H), 7.77(s, 1H), 7.72(s, 2H).

Step (2): Synthesis of [Intermediate 7-c ]

Dioxane (70 mL) was added to a 250 mL two-necked flask and nitrogen was bubbled for 15 min, while stirring, Pd(OAc) ₂ (113 mg, 0.5 mmol) and SPhos (431 mg, 1.05 mmol) were added, followed by 10 min. After stirring for a while, 7-b (7.8 g, 20 mmol), B ₂ pin ₂ (7.1 g, 28 mmol) and KOAc (3.92 g, 40 mmol) were sequentially added. The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and separated by silica gel column chromatography to obtain white solid 7-c (8.2 g, 85% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.16 (d, J = 8 Hz, 2H), 8.04 (s, 2H), 7.90 (d, J = 6.8 Hz, 2H).

Step (3): Synthesis of [Intermediate 7-d ]

Tetrahydrofuran (1 L) was added to a 2 L two-necked flask, nitrogen was bubbled for 15 min, Pd(OAc) ₂ (141 mg, 0.625 mmol) and XPhos (646 mg, 1.38 mmol) were added while stirring, and so on. After stirring for 10 min, 1-a (4.0 g, 12.5 mmol), 7-c (22.2 g, 46 mmol) and cesium fluoride (10.5 g, 68.8 mmol) are sequentially added. The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, thoroughly washed with tetrahydrofuran, and separated by silica gel column chromatography to obtain 7-d (11.6 g, 83% yield) as a white solid. ¹ HNMR (400 MHz, d ₆ -acetone) δ = 9.02 (s, 2H), 8.89 (s, 2H), 8.74 (s, 2H), 8.57 (s, 4H), 8.35 (s, 2H), 8.18 (s , 2H).

Step (4): Synthesis of [Intermediate 7-e ]

In a nitrogen atmosphere, 7-d (6.02 g, 6.9 mmol) was added to THF (250 mL), cooled to -72 °C and slowly mixed with 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex (16.6 mL, 16.6 mmol, 1.0 M solution), maintain the temperature for 1 h, then slowly raise the temperature to -20 ° C and react at the temperature for 2 h. Next, the temperature was lowered to -78 ° C, a THF solution (20 mL) of pure iodine (7.11 g, 28 mmol) was added, and when the addition was completed, the temperature was slowly raised to room temperature, left overnight, and a small amount of saturated ammonium chloride aqueous solution was added. After quenching, diatomaceous earth is directly added, the sample is stirred, and purified by silica gel column chromatography to give a white solid product 7-e (6.3 g, 82% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 9.00 (s, 2H), 8.70 (s, 2H), 8.57 (s, 4H), 8.42 (s, 2H), 8.21 (s, 2H).

Step (5): Synthesis of [Intermediate 7-f ]

Under a nitrogen atmosphere, malononitrile (1.35 g, 20.4 mmol) was added to anhydrous DMF (40 mL), NaH (820 mg, 20.4 mmol, content of 60%) was added in several portions at 0 ° C, and then 0 ° C After stirring for 10 min and stirring at room temperature for 20 min, 7-e (3.82 g, 3.4 mmol) and Pd(PPh ₄ ) ₃ (393 mg, 0.34 mmol) were added, and the temperature was raised to 90 °C and reacted for 24-36 h. let it After complete conversion, it is poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, stirred sufficiently, and when a large amount of solid precipitates, it is filtered to collect the solid. Washing with dichloromethane and filtering gave 3.3 g of an off-white solid. Then, it was washed twice successively with a solvent (DCM, 200 mL) and filtered to obtain an off-white solid 7-f (3.2 g, 95% yield). ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.92 (s, 4H), 8.41 (s, 4H), 8.37 (s, 4H).

Step (6): Synthesis of Compound 72

Under nitrogen atmosphere, put 7-f (3.2g, 3.2mmol) into a 500mL one-necked flask, add DCM (200mL), cool to 0°C, and divide PIFA (2.92g, 6.8mmol) several times. After addition and stirring at room temperature for 5 days, the solution becomes purple-black. Next, the obtained solution was put into a 1 L one-necked flask, and rotary evaporation was performed until 50 mL of the solution remained, n-hexane (450 mL) was added thereto, stirred for 10 min, and filtered to obtain a black solid. Washed twice with each (DCM/PE=1:1, 200 mL) to finally obtain compound 72 (2.8 g, 88% yield) as a black solid. ¹ HNMR (400 MHz, d ₆ -acetone) δ = 8.56 (s, 8H), 8.24 (s, 4H).

Synthesis Example 8: Synthesis of Compound 54

Step (1): Synthesis of [Intermediate 8-b ]

Dioxane (300 mL) was added to a 500 mL two-necked flask and nitrogen was bubbled for 15 min, Pd(OAc) ₂ (423 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added while stirring, and so on. After stirring for 10 min, 1-a (4.1 g, 12.9 mmol), boronic acid 8-a (22.8 g, 51.9 mmol) and cesium fluoride (11.0 g, 80.0 mmol) are added sequentially. The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and silica gel column chromatography is used to obtain 8-b as a white solid (6.7g, 45% yield).

Step (2): Synthesis of [Intermediate 8-c ]

Under a nitrogen atmosphere, 8-b (6.5 g, 6.85 mmol) was added to THF (325 mL), cooled to -78 °C, slowly dripped with LDA (9.7 mL, 15.7 mmol), and the temperature was maintained for 10 min. Next, the temperature was slowly raised to -15 ° C, and the color of the solution was reddish black. After 2h, a THF solution (20mL) of pure iodine (5.22g, 20.56mmol) was added, and when the addition was complete, the temperature was slowly raised to room temperature, left overnight, and quenched by adding a small amount of saturated ammonium chloride aqueous solution, After directly adding diatomaceous earth and stirring the sample, a white solid product 8-c (5.1 g, 62% yield) was obtained by silica gel column chromatography (PE:DCM=10:1-2:1).

Step (3): Synthesis of [Intermediate 8-d ]

Under a nitrogen atmosphere, malononitrile (2.06 g, 31.2 mmol) was added to anhydrous DMF (100 mL), and NaH (1.22 g, 30.3 mmol) was added in portions at 0 °C, stirring at 0 °C for 10 min. and stirred at room temperature for 20 min, the solution turned pale yellow, and then 8-c (5.0 g, 4.16 mmol) and Pd(PPh ₄ ) ₃ (0.89 g, 0.77 mmol) were added, and the temperature was raised to 90 °C and reacted for 24 h. let it After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, sufficiently stirred, and when a large amount of yellow solid precipitated, the solid was collected by filtration. After reslurry with dichloromethane to obtain a yellow solid, it was boiled with toluene at 90° C. for 1.5 h and filtered to give a yellow solid 8-d (4.3 g, 95% yield).

Step (4): Synthesis of Compound 54

Under a nitrogen atmosphere, 8-d (4.3g, 3.97mmol) was placed in a two-necked flask, DCM (430mL, 0.01M) was added, cooled to 0 °C, and PIFA (1.79g, 4.17mmol) was added several times. Added in portions and stirred at room temperature for 1 day, the solution turned purple-black. Next, the solution was put into a 1 L one-necked flask, spun dried until the solution was 50 mL left and right, n-hexane (250 mL) was added thereto, stirred for 10 min, filtered, and then each (DCM/PE= 1:1, 200 mL) to obtain compound 54 (3.0 g, 70% yield) as a purple-black solid. The product is identified as the target product with a molecular weight of 1074.

Synthesis Example 9: Synthesis of Compound 1367

Step (1): Synthesis of [Intermediate 9-a ]

Dioxane (450 mL) was added to a 1 L two-necked flask and nitrogen was bubbled for 15 min, Pd(OAc) ₂ (1.27 g, 5.66 mmol) and XPhos (5.62 g, 11.8 mmol) were added while stirring, and so on. and stirred for 10 min, then 1-a (15.0 g, 47.18 mmol), biphenyl-2-boronic acid (39.2 g, 198.1 mmol) and cesium fluoride (33.25 g, 240.6 mmol) were sequentially added. ) is added. The temperature was raised to 110° C. to reflux and stirred overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and subjected to silica gel column chromatography to obtain 9-a as a white solid (5.0 g, 23% yield).

Step (2): Synthesis of [Intermediate 9-b ]

In a nitrogen atmosphere, 9-a (4.92 g, 10.59 mmol) was added to THF (120 mL), the temperature was lowered to -78 ° C, and LDA (15.0 mL, 24.36 mmol, 1.6 M solution) was slowly dripped, and the temperature was increased for 10 min. After maintaining for a while, the temperature was slowly raised to -15 ° C and reacted. After 2h, a THF solution (20mL) of pure iodine (8.07g, 31.77mmol) was added, and when the addition was complete, the temperature was slowly raised to room temperature, left overnight, and quenched by adding a small amount of saturated ammonium chloride aqueous solution, After directly adding diatomaceous earth and stirring the sample, a white solid product 9-b (6.2 g, 81% yield) was obtained by silica gel column chromatography (PE:DCM=10:1-2:1).

Step (3): Synthesis of [Intermediate 9-c ]

Under a nitrogen atmosphere, malononitrile (4.28 g, 64.9 mmol) was added to anhydrous DMF (86 mL), and NaH (2.52 g, 63.1 mmol) was added in portions at 0 °C, stirring at 0 °C for 10 min. and stirred at room temperature for 20 min, and the solution turned pale yellow (reddish), then 9-b (6.2 g, 8.65 mmol) and Pd(PPh ₄ ) ₃ (1.84 g, 1.6 mmol) were added, and the temperature was 90 °C. The temperature was raised to and reacted for 24 h. After complete conversion, it was poured into ice water, adjusted to pH<1 using 4N dilute hydrochloric acid, stirred sufficiently, and when a large amount of yellow solid precipitated, the solid was collected by filtration. A yellow solid was obtained by reslurry with dichloromethane, washed with toluene at 90° C. for 1.5 h, and filtered to obtain yellow solid 9-c (4.81 g, 93% yield).

Step (4): Synthesis of Compound 1367

Under nitrogen atmosphere, put 9-c (4.81 g, 8.12 mmol) in a two-necked flask, add DCM (480 mL) each, cool down to 0°C, and add PIFA (3.67 g, 8.53 mmol) in several portions. and stirred at room temperature for 1 day. Next, the solution was put into a 1 L one-necked flask, and rotary evaporation was performed until the solution remained 50 mL left and right, n-hexane (400 mL) was added thereto, stirred for 10 min, and filtered to obtain a purple-black solid, followed by each (DCM /PE=1:1, 200 mL) to give compound 1367 (4.1 g, 85% yield) as a purple-black solid. The product is identified as the target product with a molecular weight of 590.

Synthesis Example 10: Synthesis of Compound 4 3

Step (1): Synthesis of [Intermediate 10-b ]

Add dioxane (160 mL) to a 250 mL two-necked flask, bubble nitrogen for 15 min, add Pd(OAc) ₂ (0.282 g, 1.26 mmol) and XPhos (1.2 g, 2.52 mmol) while stirring, and so on. and stirred for 10 min, then 1-a (8.0 g, 25.16 mmol), 10-a (24.46 g, 75.48 mmol) and sodium hydroxide (3.52 g, 88.04 mmol) were sequentially added. React by raising the temperature to 80° C. and stir overnight under the protection of nitrogen. When the reaction is complete, the temperature is lowered, filtered through diatomaceous earth, sufficiently washed with dichloromethane, and silica gel column chromatography is used to obtain a white solid 10-b (13g, 93.6% yield).

Step (2): Synthesis of [Intermediate 10-c ]

To a dried 500 mL Schlenk flask, add 10-b (12 g, 21.7 mmol) and THF (240 mL) in a nitrogen atmosphere, cool to -30 ° C, slowly add TMPMgClLiCl (54 mL, 54 mmol, 1.0 M solution) - Reaction and sampling at 30 ° C for 2 h, complete lithiation monitored by HPLC, and then a THF solution (50 mL) of pure iodine (16.55 g, 65.1 mmol) was added at -30 ° C, and when the addition was completed, it was slowly room temperature The temperature was raised to , left overnight, quenched by adding a small amount of saturated ammonium chloride aqueous solution, directly added with diatomaceous earth, stirred the sample, and subjected to silica gel column chromatography (PE:DCM=10:1 to 2:1 to 1: 1) and reslurry using PE:DCM=10:1 to obtain 10-c (12g, 69% yield) as a white solid.

Step (3): Synthesis of [Intermediate 10-d ]

To a dried 1 L three-necked flask, add NaH (2.98 g, 74.4 mmol) and ultra-dry DMF (80 mL) under a nitrogen atmosphere, followed by malononitrile (4.95 g, 75 mmol) at 0°C. After reacting at room temperature for 0.5h , 10-c (10g, 12.4mmol) and Pd(PPh ₃ ) ₄ (0.718g, 0.62mmol) were added, heated to 80°C and reacted for 18h. After the reaction is complete, 100 mL of 2N HCL is dripped at 0°C and filtered to obtain a crude product. Water was removed by azeotrope with acetone, dissolved clearly with acetone, insolubles were filtered, and the filtrate was spin-dried and crystallized to give a white (slightly yellowish) solid 10-d (8.5 g, 91% yield) ) to get

Step (4): Synthesis of Compound 43

In a 2 L three-necked flask, 10-d (8.5 g, 12.5 mmol) and DCM (750 ml) were added in a nitrogen atmosphere, then a PIFA (5.91 g, 13.75 mmol) solution was dripped at 0 ° C and reacted for 20 h. Next, the solution was put into a 2 L one-necked flask, and rotary evaporation was performed until 100 mL of the solution remained, n-hexane (500 mL) was added thereto, stirred for 10 min, and filtered to obtain a purple-black solid. Washed twice using each (DCM/PE=2:1, 200 mL), finally obtaining a purple-black solid compound 43 (7.5 g, 88% yield). The product is identified as the target product with a molecular weight of 678.

A person skilled in the art should know that the above preparation method is only an illustrative example, and a person skilled in the art can obtain other compound structures of the present invention by improving it.

Device Example 1

Device Example 1.1:

A glass substrate having an indium tin oxide (ITO) transparent electrode having a thickness of 80 nm is treated with oxygen plasma and UV ozone. Prior to deposition, the cleaned glass substrate is dried on a hotplate in a glove box. The following materials are sequentially deposited on the glass surface at a vacuum of about 10 ⁻⁸ Torr at a rate of 0.2 to 2 Å/s. First, the compound 56 of the present invention is deposited on the surface of a glass substrate to form a film with a thickness of 10 nm to form a hole injection layer (HIL). Then, compound HT1 is deposited on the obtained film to form a 120 nm thick film as a hole transport layer (HTL). Next, compound EB1 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as an electron blocking layer (EBL). Then, on the obtained film, compound BH and compound BD (weight ratio 96:4) were co-evaporated to form a film having a thickness of 25 nm, which was used as a light emitting layer (EML). Next, compound HB1 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as a hole blocking layer (HBL). Subsequently, 8-hydroxyquinoline-lithium (Liq) and compound ET1 (weight ratio: 60:40) were co-evaporated on the obtained film to form a film with a thickness of 30 nm to serve as an electron transport layer (ETL). Finally, Liq is deposited to form a film with a thickness of 1 nm to form an electron injection layer (EIL), and aluminum to a thickness of 120 nm is deposited to form a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid and a moisture absorbent to complete the device.

Device Example 1.2:

Device Example 1.2 was prepared in the same manner as Device Example 1.1, except that compound 68 was used instead of compound 56 as the HIL.

Device Example 1.3:

Device Example 1.3 was prepared in the same manner as Device Example 1.1, except that compound 70 was used instead of compound 56 as the HIL.

Device Example 1.4:

Device Example 1.4 was prepared in the same manner as Device Example 1.3, except that a 5 nm thick film was formed using compound 70 to form an HIL.

Device Example 1.5:

Device Example 1.5 was prepared in the same manner as Device Example 1.3, except that a 2 nm thick film was formed using compound 70 to form an HIL.

Device Example 1.6:

Device Example 1.6 was prepared in the same manner as Device Example 1.3, except that compound HT2 was used instead of compound HT1 as HTL.

Device Example 1.7:

Device Example 1.7 was prepared in the same manner as Device Example 1.6, except that compound 70 was used to form a 2 nm thick film to form an HIL.

Device Example 1.8:

Device Example 1.8 was prepared in the same manner as Device Example 1.6, except that compound 70 was used to form a 1 nm thick film to form an HIL.

Device Comparative Example 1.1:

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

Device Comparative Example 1.2:

Device Comparative Example 1.2 was prepared in the same manner as Device Example 1.6, except that Compound 70 was not used and there was no hole injection layer.

The detailed device layer structure and thickness are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein. Table 1 shows device structures of device examples and comparative examples.

Device ID HIL HTL EBL EML HBL ETL Example 1.1 Compound 56 (10 nm) compound HT1
(120nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.2 Compound 68 (10 nm) compound HT1
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.3 Compound 70 (10 nm) compound HT1
(120nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.4 compound 70 (5nm) compound HT1
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.5 Compound 70 (2nm) compound HT1
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.6 Compound 70 (10 nm) compound HT2
(120nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.7 Compound 70 (2nm) compound HT2
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Example 1.8 Compound 70 (1 nm) compound HT2
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25 nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Comparative Example 1.1 Compound HI1 (10 nm) compound
HT1
(120 nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm) Comparative Example 1.2 doesn't exist compound HT2
(120nm) compound
EB1 (5 nm) Compound BH: Compound BD
(96:4, 25nm) compound
HB1 (5nm) compound
ET1:Liq (40:60, 30 nm)

The material structure used for the device is as follows:

IVL characteristics of the device were measured at 10 mA/cm ² , and the voltage (V), power efficiency (PE), and lifetime (LT95) are recorded and displayed in Table 2, respectively. Table 2 shows device data.

device number Voltage
(V) PE
(lm/W) LT95 (h) Example 1.1 4.22 4.64 183 Example 1.2 4.56 4.87 1204 Example 1.3 4.18 4.70 292 Example 1.4 4.08 4.97 601 Example 1.5 4.07 5.25 643 Example 1.6 4.12 4.49 1572 Example 1.7 4.11 5.15 1615 Example 1.8 4.12 5.25 1596 Comparative Example 1.1 4.72 4.22 30 Comparative Example 1.2 8.34 4.02 93

Discussion 1:

As can be seen from the above table, when a single material is used as the hole injection layer in the eight preferred embodiments and comparative examples of the present invention, the preferred embodiments are all superior to the comparative examples in terms of voltage, power efficiency, and lifetime. do. In terms of voltage, it can be lowered by about 0.5V, power efficiency is improved, and life expectancy is doubled. That is, even if the thickness of the hole injection layer is reduced to 5 nm and 2 nm, or even to 1 nm, the voltage, efficiency and lifetime are all very good. In particular, when the hole injection layer is not present, the voltage of the device reaches 8.34V, and both power efficiency and lifetime are inferior to those of the device having the hole injection layer. As can be seen from this, when used alone as a hole injection layer, the compounds of the present invention are a more desirable choice than comparative compounds, and the improvement thereby is completely unexpected.

Device Example 2

Device Example 2.1:

A glass substrate having an indium tin oxide (ITO) transparent electrode having a thickness of 80 nm is treated with oxygen plasma and UV ozone. Prior to deposition, the cleaned glass substrate is dried on a hotplate in a glove box. The following materials are sequentially deposited on the glass surface at a vacuum of about 10 ⁻⁸ Torr at a rate of 0.2 to 2 Å/s. First, compound 56 (dopant) and compound HT1 (weight ratio: 3:97) of the present invention are co-deposited on the surface of a glass substrate to form a 10 nm thick film as a hole injection layer (HIL). Then, compound HT1 is deposited on the obtained film to form a 120 nm thick film as a hole transport layer (HTL). Next, compound EB1 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as an electron blocking layer (EBL). Then, on the obtained film, compound BH and compound BD (weight ratio 96:4) were co-evaporated to form a film having a thickness of 25 nm, which was used as a light emitting layer (EML). Next, compound HB1 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as a hole blocking layer (HBL). Subsequently, 8-hydroxyquinoline-lithium (Liq) and compound ET1 (weight ratio: 60:40) were co-evaporated on the obtained film to form a film with a thickness of 30 nm to serve as an electron transport layer (ETL). Finally, Liq is deposited to form a film with a thickness of 1 nm to form an electron injection layer (EIL), and aluminum to a thickness of 120 nm is deposited to form a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid and a moisture absorbent to complete the device.

Device Example 2.2:

Device Example 2.2 was prepared in the same manner as Device Example 2.1, except that compound 68 was used instead of compound 56 as the dopant in the HIL.

Device Example 2.3:

Device Example 2.3 was prepared in the same manner as Device Example 2.1, except that compound 70 was used instead of compound 56 as the dopant in the HIL.

Device Example 2.4:

Device Example 2.4 was co-deposited with compound 56 using compound HT2 instead of compound HT1 as HIL (weight ratio 97:3); and, except for using compound HT2 instead of compound HT1 as HTL, device was prepared in the same manner as in Example 2.1.

Device Example 2.5:

Device Example 2.5 was prepared in the same manner as Device Example 2.4, except that compound 68 was used instead of compound 56 as the dopant in the HIL.

Device Example 2.6:

Device example 2.6 was prepared in the same manner as device example 2.4, except that compound 69 was used instead of compound 56 as the dopant in the HIL.

Device Example 2.7:

Device Example 2.7 was fabricated in the same manner as Device Example 2.4, except that as HIL, compound HT2 and compound 42 were co-deposited (weight ratio: 98:2).

Device Example 2.8:

Device Example 2.8 was prepared in the same manner as Device Example 2.7, except that Compound 72 was used instead of Compound 42 as the dopant.

Device Example 2.9:

Device Example 2.9 was prepared in the same manner as Device Example 2.7, except that Compound 54 was used instead of Compound 42 as the dopant.

Device Example 2.10:

Device Example 2.10 was prepared in the same manner as Device Example 2.7, except that Compound 1367 was used instead of Compound 42 as the dopant.

Device Example 2.11:

Device Example 2.11 was prepared in the same manner as Device Example 2.7, except that Compound 43 was used instead of Compound 42 as the dopant.

Device Comparative Example 2:

Device Comparative Example 2 was prepared in the same manner as Device Example 2.1, except that compound HI1 was used instead of compound 56 as a dopant in the HIL.

The specific structure of the compound used in the device is as shown in Device Example 1.

The detailed device layer structure and thickness are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein. Table 3 shows the device structures of device examples and comparative examples.

Device ID HIL HTL EBL EML HBL ETL Example 2.1 Compound 56: Compound HT1 (3:97, 10 nm) compound
HT1
(120nm) compound
EB1
(5nm) Compound BH: Compound BD
(96:4, 25nm) compound
HB1
(5 nm) Compound ET1:Liq
(40:60, 30 nm) Example 2.2 Compound 68: Compound HT1 (3:97, 10 nm) compound HT1
(120nm) compound
EB1
(5nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm) Example 2.3 Compound 70: Compound HT1 (3:97, 10 nm) compound HT1
(120 nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5nm) Compound ET1:Liq (40:60, 30 nm) Example 2.4 Compound 56: Compound HT2 (3:97, 10 nm) compound HT2
(120nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm) Example 2.5 Compound 68: Compound HT2 (3:97, 10 nm) compound HT2
(120 nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5nm) Compound ET1:Liq (40:60, 30 nm) Example 2.6 Compound 69: Compound HT2 (3:97, 10 nm) compound HT2
(120nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5nm) Compound ET1:Liq (40:60, 30 nm) Example 2.7 Compound 42: Compound HT2 (2:98, 10 nm) compound HT2
(120 nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm) Example 2.8 Compound 72: Compound HT2 (2:98, 10 nm) compound HT2
(120 nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5nm) Compound ET1:Liq (40:60, 30 nm) Example 2.9 Compound 54: Compound HT2 (2:98, 10 nm) compound HT2
(120 nm) compound
EB1
(5nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm) Example 2.10 Compound 1367: Compound HT2 (2:98, 10 nm) compound HT2
(120nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5nm) Compound ET1:Liq (40:60, 30 nm) Example 2.11 Compound 43: Compound HT2 (2:98, 10 nm) compound HT2
(120 nm) compound
EB1
(5 nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm) Comparative Example 2 Compound HI1: Compound HT1 (3:97, 10 nm) compound HT1
(120nm) compound
EB1
(5nm) Compound BH: Compound BD (96:4, 25 nm) compound
HB1
(5 nm) Compound ET1:Liq (40:60, 30 nm)

The specific structure of the new compound used in the device is as follows:

IVL characteristics of the device were measured at 10 mA/cm ² , and the voltage (V), power efficiency (PE), and lifetime (LT95) are recorded and displayed in Table 4, respectively. Table 4 shows device data.

device number Voltage
(V) PE
(lm/W) LT95 (h) Example 2.1 4.18 5.55 94 Example 2.2 4.17 5.65 980 Example 2.3 4.03 5.64 250 Example 2.4 4.09 5.49 328 Example 2.5 4.11 5.60 1820 Example 2.6 4.00 5.45 617 Example 2.7 4.01 5.55 967 Example 2.8 3.97 5.61 1248 Example 2.9 3.99 5.62 1560 Example 2.10 4.07 5.37 1759 Example 2.11 3.97 5.45 779 Comparative Example 2 8.57 2.74 6

Discussion 2:

As can be seen from the above table, in the 11 preferred embodiments and comparative examples of the present invention, when the dopant in HT1 or HT2 is used as the hole injection layer, the performance difference between the two materials is very large. First, in terms of voltage, the voltage of the comparative example reached 8.57V, but the voltage of the preferred embodiment was reduced by half to only 4.18V left and right. The power efficiency of the examples is also twice or more than that of the comparative examples. In particular, in terms of lifetime, the preferred embodiment is several tens of times that of the comparative example, not the same order of magnitude. Therefore, when used as a dopant, the compound disclosed in the present invention is a kind of hole injection material that is far superior to the comparative compound, and the improvement brought by the compound of the present invention to device performance, especially in terms of voltage reduction and lifetime improvement, is It is completely unexpected and has an overwhelming advantage.

Device Example 3

Device Example 3.1:

A glass substrate having an indium tin oxide (ITO) transparent electrode having a thickness of 80 nm is treated with oxygen plasma and UV ozone. Prior to deposition, the cleaned glass substrate is dried on a hotplate in a glove box. The following materials are sequentially deposited on the glass surface at a vacuum of about 10 ⁻⁸ Torr at a rate of 0.2 to 2 Å/s. First, compound 56 is deposited on the surface of a glass substrate to form a film with a thickness of 10 nm to form a hole injection layer (HIL). Then, compound HT1 is deposited on the obtained film to form a film having a thickness of 35 nm to be a hole transport layer (HTL). Next, compound EB2 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as an electron blocking layer (EBL). Then, on the obtained film, compound EB2 , compound HB2 and compound GD (weight ratio 46:46:8) were co-evaporated to form a film with a thickness of 40 nm to form a light emitting layer (EML). Next, compound HB2 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as a hole blocking layer (HBL). On the obtained film, 8-hydroxyquinoline-lithium (Liq) and compound ET2 (weight ratio: 60:40) were co-evaporated to form a film with a thickness of 35 nm to serve as an electron transport layer (ETL). Finally, Liq is deposited to form a film with a thickness of 1 nm to form an electron injection layer (EIL), and aluminum to a thickness of 120 nm is deposited to form a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid and a moisture absorbent to complete the device.

Device Example 3.2:

Device Example 3.2 was prepared in the same manner as Device Example 3.1, except that compound 56 (dopant) and compound HT1 (weight ratio: 3:97) were co-deposited instead of compound 56 as the hole injection layer (HIL). do.

Device Example 3.3:

Device Example 3.3 uses compound 70 instead of compound 56 as the hole injection layer (HIL); and, except for using compound HT2 instead of compound HT1 as HTL, a device was prepared in the same manner as Example 3.1.

Device Example 3.4:

Device Example 3.4 was prepared in the same manner as Device Example 3.3, except for using a hole injection layer (HIL) in which compound 70 (dopant) and compound HT2 (weight ratio: 3:97) were co-deposited instead of compound 70. do.

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

The detailed device layer structure and thickness are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein. Table 5 shows the device structure of the device example.

Device ID HIL HTL EBL EML HBL ETL Example 3.1 Compound 56 (10 nm) compound
HT1
(35 nm) compound
EB2
(5 nm) Compound EB2: Compound HB2: Compound GD
(46:46:8, 40 nm) compound
HB2
(5nm) Compound Liq:ET2 (60:40
, 35 nm) Example 3.2 Compound 56: Compound HT1 (3:97, 10 nm) compound HT1
(35 nm) compound
EB2
(5 nm) Compound EB2: Compound HB2: Compound GD
(46:46:8, 40nm) compound
HB2
(5 nm) Compound Liq:ET2 (60:40
, 35 nm) Example 3.3 Compound 70 (10 nm) compound
HT2
(35 nm) compound
EB2
(5nm) Compound EB2: Compound HB2: Compound GD
(46:46:8, 40 nm) compound
HB2
(5nm) Compound Liq:ET2 (60:40
, 35 nm) Example 3.4 Compound 70: Compound HT2 (3:97, 10 nm) compound HT2
(35 nm) compound
EB2
(5nm) Compound EB2: Compound HB2: Compound GD
(46:46:8, 40nm) compound
HB2
(5nm) Compound Liq:ET2 (60:40
, 35 nm)

The IVL characteristics of the device were measured at 10 mA/cm ² , and the voltage (V), power efficiency (PE), and lifetime (LT95) are recorded and displayed in Table 6, respectively. Table 6 shows device data.

device number Voltage
(V) PE
(lm/W) LT95 (h) Example 3.1 3.56 71.15 1245 Example 3.2 3.51 76.77 859 Example 3.3 3.53 72.29 1343 Example 3.4 3.51 77.05 1097

Discussion 3:

As can be seen from the green light device, when compound 56 and compound 70 are used alone as the hole injection layer, the voltage, power efficiency and lifetime are excellent. In the case of forming a hole injection layer using Compound 56 and Compound 70 as dopants, the voltage is similar and the efficiency is slightly higher than those of Examples 3.1 and 3.3, but in terms of life, Compound 56 and Compound 70 are used as hole injection layers. Relatively long when used alone.

Device Example 4

Device Example 4.1:

A glass substrate having an indium tin oxide (ITO) transparent electrode having a thickness of 80 nm is treated with oxygen plasma and UV ozone. Prior to deposition, the cleaned glass substrate is dried on a hotplate in a glove box. The following materials are sequentially deposited on the glass surface at a vacuum of about 10 ⁻⁸ Torr at a rate of 0.2 to 2 Å/s. First, compound 56 is deposited on the surface of a glass substrate to form a film with a thickness of 10 nm to form a hole injection layer (HIL). Then, compound HT1 is deposited on the obtained film to form a film having a thickness of 40 nm to serve as a hole transport layer (HTL). Next, compound EB2 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as an electron blocking layer (EBL). Then, compound RH and compound RD (weight ratio: 98:2) were co-evaporated on the obtained film to form a film having a thickness of 40 nm to form a light emitting layer (EML). Next, compound HB2 is deposited on the obtained film to form a film having a thickness of 5 nm to serve as a hole blocking layer (HBL). On the obtained film, 8-hydroxyquinoline-lithium (Liq) and compound ET2 (weight ratio: 60:40) were co-evaporated to form a film with a thickness of 35 nm to serve as an electron transport layer (ETL). Finally, Liq is deposited to form a film with a thickness of 1 nm to form an electron injection layer (EIL), and aluminum to a thickness of 120 nm is deposited to form a cathode. Next, the device is transferred back to the glove box and encapsulated using a glass lid and a moisture absorbent to complete the device.

Device Example 4.2:

Device Example 4.2 is a device embodiment, except that a film having a thickness of 10 nm is formed by co-depositing compound 56 (dopant) and compound HT1 (weight ratio: 3:97) on the surface of a glass substrate as a hole injection layer (HIL). prepared in the same way as in 4.1.

Device Example 4.3:

Device Example 4.3 uses compound 70 instead of compound 56 as the hole injection layer (HIL); and, except for using compound HT2 instead of compound HT1 as HTL, device was prepared in the same manner as Example 4.1.

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: 3:97) were co-deposited instead of compound 70 as the hole injection layer (HIL). do.

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

The detailed device layer structure and thickness are shown in the table below. Here, a layer in which two or more materials are used is obtained by doping different compounds in the weight ratios mentioned therein. Table 7 shows the device structure of the device example.

Device ID HIL HTL EBL EML HBL ETL Example 4.1 Compound 56 (10 nm) Compound HT1 (40 nm) Compound EB2 (5 nm) Compound RH: Compound RD (98:2, 40 nm) Compound HB2 (5 nm) Compound Liq:ET2 (60:40, 35 nm) Example 4.2 Compound 56: Compound HT1 (3:97, 10 nm) Compound HT1 (40 nm) Compound EB2 (5 nm) Compound RH: Compound RD (98:2, 40 nm) Compound HB2 (5 nm) Compound Liq:ET2 (60:40, 35 nm) Example 4.3 Compound 70 (10 nm) Compound HT2 (40 nm) Compound EB2 (5 nm) Compound RH: Compound RD (98:2, 40 nm) Compound HB2 (5 nm) Compound Liq:ET2 (60:40, 35 nm) Example 4.4 Compound 70: Compound HT2 (3:97, 10 nm) Compound HT2 (40 nm) Compound EB2 (5 nm) Compound RH: Compound RD (98:2, 40 nm) Compound HB2 (5 nm) Compound Liq:ET2 (60:40, 35 nm)

The IVL characteristics of the device were measured at 10 mA/cm ² , and the voltage (V), power efficiency (PE), and lifetime (LT95) are recorded and displayed in Table 8, respectively. Table 8 shows device data.

device number Voltage
(V) PE
(lm/W) LT95 (h) Example 4.1 4.37 13.33 7469 Example 4.2 4.32 15.31 4325 Example 4.3 4.44 12.79 4659 Example 4.4 4.44 14.40 5200

Discussion 4:

Similarly, as can be seen in the red light device, when compound 56 and compound 70 are used alone as the hole injection layer, the effects in terms of voltage and efficiency as well as lifetime are all very excellent. In the case of forming a hole injection layer using compound 56 and compound 70 as dopants, the voltage is similar and the efficiency is slightly higher than that of Examples 4.1 and 4.3, but in terms of lifespan, compound 56 can be used alone as a hole injection layer. relatively long when

As can be seen from the above results, the dehydrobenzodioxazole derivatives, whether used alone as a hole injection layer or as a dopant, have excellent effects in red, green, and blue devices, which is one kind. It is a very rare hole injection material.

The compounds disclosed in the present invention are dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole-based derivatives, and due to the heteroatom contained in the molecular parent nucleus being different, the lowest unoccupied molecular orbital (lowest unoccupied molecular orbital) There is a difference in molecular orbital (LUMO). Dehydrobenzodioxazole ( NO-based compound ), dehydrobenzodithiazole ( NS-based compound ), and dehydrobenzodiselenazole ( NSe-based compound )-based derivatives, calculate the LUMO of these three compounds through DFT (GAUSS -09, conditions are B3LYP/6-311G (d)), as shown in the table below. Table 9 shows the DFT calculation results:

NO based
compound LUMO
(ev) NS series
compound LUMO
(ev) NSe-based
compound LUMO
(ev) compound 1 -5.82 compound 89 -5.66 compound 177 -5.58 compound 6 -6.18 compound 94 -6.03 compound 182 -5.95 compound 13 -5.57 compound 101 -5.46 compound 189 -5.40 compound 15 -5.32 compound 103 -5.24 compound 191 -5.18 compound 25 -5.69 compound 113 -5.61 compound 201 -5.56 compound 26 -5.43 compound 114 -5.36 compound 202 -5.30 compound 38 -5.68 compound 126 -5.55 compound 214 -5.48 compound 43 -5.72 compound 131 -5.63 compound 219 -5.40 compound 56 -5.45 compound 144 -5.33 compound 232 -5.28 compound 66 -5.3 compound 154 -5.24 compound 242 -5.19 compound 67 -5.93 compound 155 -5.73 compound 243 -5.64 compound 68 -5.78 compound 156 -5.64 compound 244 -5.58 compound 69 -5.53 compound 157 -5.44 compound 245 -5.38 compound 70 -5.57 compound 158 -5.48 compound 246 -5.43 compound 71 -5.57 compound 159 -5.49 compound 247 -5.43 compound 42 -5.75 compound 130 -5.59 compound 218 -5.53 compound 54 -5.65 compound 142 -5.49 compound 230 -5.43 compound 72 -5.75 compound 160 -5.63 compound 248 -5.56 compound 1359 -5.25 compound 1381 -5.15 compound 1403 -5.11 compound 1367 -5.12 compound 1389 -5.06 compound 1411 -5.04

From the device results, it can be seen that the device results of the dehydrobenzodioxazole-based derivative are excellent in all respects, and it is a kind of highly efficient hole injection material. As can be seen from the DFT calculation results, when comparing molecules of the same series, the LUMOs of dehydrobenzodioxazole-based derivatives, dehydrobenzodithiazole-based derivatives and dehydrobenzodiselenazole-based derivatives are almost no difference. , 0.2ev, and all three compounds can have a relatively deep LUMO, and all of them are extremely deficient in electrons. Therefore, both dehydrobenzodithiazole-based derivatives and dehydrobenzodiselenazole-based derivatives have the potential to be excellent hole injection materials, and both can significantly improve OLED performance such as longer device lifetime, higher efficiency, and lower voltage. Therefore, it has a very broad industrial application prospect.

As can be seen from the above device results and DFT calculations, dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole and novel compounds with similar structures of the present invention are very important charge transfer materials, especially It has incomparable advantages in hole transport, and is applied to different types of organic semiconductor devices, including but not limited to fluorescent OLEDs, phosphorescent OLEDs, white light OLEDs, stacked OLEDs, OTFTs, OPVs, and the like.

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

Claims (25)

In the compound having formula (1),

where X and Y are identically or differently selected from CR"R"' each time they occur;
wherein Z ₁ and Z ₂ are identically or differently selected from O or S each time they occur;
Each time R and R"' appear identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , Boranyl group, sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkyl group having 3 to 20 ring carbon atoms Unsubstituted cycloalkyl group, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted 1 to 20 carbon atoms Cyclic alkoxy group, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted akinyl 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;
R″ is selected from cyano groups;
Here, 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;
A compound characterized in that adjacent substituents can be optionally linked to form a ring. According to claim 1,
X and Y are identically or differently selected from CR"R"' each time they occur, and R" and R"' are groups having at least one electron withdrawing group. According to claim 2,
A compound characterized in that R, R" and R"' are groups having at least one electron withdrawing group. According to claim 1,
The compound, characterized in that the Hammett constant of the electron withdrawing group is 0.05 or more. According to claim 1,
The compound, characterized in that the Hammett constant of the electron withdrawing group is 0.3 or more. According to claim 1,
The compound, characterized in that the Hammett constant of the electron withdrawing group is 0.5 or more. According to claim 1,
The electron attractor,
halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group; sulfinyl group; sulfonyl group; a phosphoroso group; aza aromatic ring; And halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group, phosphoroso group (phosphoroso), any one of the following groups substituted with one or a plurality of azaaromatic rings: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms , heteroalkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 30 carbon atoms, alkene having 2 to 20 carbon atoms Nyl group, akinyl group having 2 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 3 to 30 carbon atoms, alkylsilyl group having 3 to 20 carbon atoms, 6~ an arylsilyl group having 20 carbon atoms and combinations thereof; A compound characterized in that selected from the group consisting of. According to claim 1,
The electron withdrawing group is selected from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN, OCN, pyrimidyl group, triazinyl group, and combinations thereof. compound that does. According to claim 1,
Each occurrence of X and Y is identically or differently selected from the group consisting of the following structures:

Whenever R ₁ appears, identically or differently, hydrogen, deuterium, halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group (Boranyl), sulfinyl group, sulfonyl group, phosphoroso group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkyl group having 3 to 20 ring carbon atoms Cycloalkyl group, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms group, 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 akinyl group having 2 to 20 carbon atoms, A substituted or unsubstituted aryl group having 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, 6 It is selected from the group consisting of a substituted or unsubstituted arylsilyl group having ~20 carbon atoms and combinations thereof;
where V is selected identically or differently from CR _v R _w , NR _v , O, S, and Se each time it is indicated;
Here, Ar is selected identically or differently each time it appears 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 R _b is selected from cyano groups;
Each time R _a , R _v and R _w are identically or differently 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 boranyl group, a sulfinyl group, a sulfonyl group, a phosphoroso group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and 3 to 20 ring carbon atoms substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted alkoxy group, 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 group having 2 to 20 carbon atoms akinyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 3 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms. A compound characterized in that it is selected from the group consisting of an alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof. According to claim 1,
Each time X and Y appear the same or different, the structure below:

A compound characterized in that selected from the group consisting of. According to claim 1,
Each occurrence of R is, identically or differently, hydrogen; deuterium; halogen; nitroso group; nitro group; acyl group; carbonyl group; carboxylic acid group; ester group; cyano group; isocyano group; SCN; OCN; SF ₅ ; Boranyl group; sulfinyl group; sulfonyl group; a phosphoroso group; an unsubstituted alkyl group having 1 to 20 carbon atoms; an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; an unsubstituted alkoxy group having 1 to 20 carbon atoms; An unsubstituted alkenyl 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; And halogen, nitroso group, nitro group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, SCN, OCN, SF ₅ , boranyl group, sulfinyl group, sulfonyl group and phosphoroso group (phosphoroso) any one of the following groups substituted with one or a plurality of groups: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, and 1 to 20 an alkoxy group having 2 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; A compound characterized in that selected from the group consisting of. According to claim 1,
Whenever R appears identically or differently, hydrogen, deuterium, methyl group, isopropyl group, NO ₂ , SO ₂ CH ₃ , SCF ₃ , C ₂ F ₅ , OC ₂ F ₅ , OCH ₃ , diphenylmethylsilyl group, phenyl group , methoxyphenyl group, p-methylphenyl group, 2,6-diisopropylphenyl group, biphenyl group, polyfluorophenyl group, difluoropyridyl group, nitrophenyl group, dimethylthiazole group, CN or CF ₃ Substituted with one or more vinyl group, ethynyl group substituted with one of CN or CF ₃ , dimethylphosphoroso group, diphenylphosphoroso group, F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano group, isocyano group, SCN , OCN, trifluoromethylphenyl group, trifluoromethoxyphenyl group, bis(trifluoromethyl)phenyl group, bis(trifluoromethoxy)phenyl group, 4-cyanotetrafluorophenyl group, F, CN or CF ₃ Or a compound characterized in that it is selected from the group consisting of a plurality of substituted phenyl or biphenyl groups, tetrafluoropyridyl groups, pyrimidyl groups, triazinyl groups, diphenylboranyl groups, oxaboraanthryl groups, and combinations thereof. According to claim 1,
X and Y are

A compound characterized in that. According to claim 10,
A compound characterized in that each occurrence of R is identically or differently selected from the group consisting of the following structures:

15. The method of claim 14,
A compound characterized in that two R's in one compound represented by formula (1) are the same. 15. The method of claim 14,
The compound has a structure represented by formula (2),

Here, the two Z structures in formula (2) are the same, the two R structures are the same or different, and the Z, X, Y and R are each selected correspondingly from atoms or groups shown in the table below. Compounds that:

. anode,
cathode, and
An electroluminescent device comprising an organic layer disposed between the anode and the cathode, wherein the organic layer contains the compound according to any one of claims 1 to 16. 18. The method of claim 17,
The organic layer is a hole injection layer, and the hole injection layer is formed solely of the compound. 18. The method of claim 17,
the organic layer is a hole injection layer, the hole injection layer is formed of the compound containing a doping, and the doping contains at least one hole transporting material; The hole transport material is a compound containing a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylenevinyl compound, and an oligofluorene compound. An electroluminescent device comprising an oligofluorene compound, a porphyrin complex, or a metal phthalocyanine complex, wherein a morph doping ratio between the compound and the hole transport material is 10000:1 to 1:10000. According to claim 19,
The electroluminescent device, characterized in that the mol doping ratio of the compound and the hole transport material is 10: 1 to 1: 100. 18. The method of claim 17,
The electroluminescent device includes a plurality of stack layers between an anode and a cathode, and the stack layer includes a first light emitting layer and a second light emitting layer, wherein the first stack layer includes the first light emitting layer and the second stack layer includes a second light emitting layer, wherein the charge generation layer is disposed between the first stack layer and the second stack layer, wherein the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer;
Here, the organic layer containing the compound having formula (1) is a p-type charge generating layer, characterized in that the electroluminescent device. According to claim 21,
The p-type charge generating layer may further contain at least one hole transport material, and the p-type charge generating layer is formed by doping the at least one hole transport material with the compound, and the hole transport material is a tree Compounds containing arylamine units, spirobifluorene compounds, pentacene compounds, oligothiophene compounds, oligophenyl compounds, oligophenylene vinyl compounds, oligofluorene compounds, An electroluminescent device comprising a porphyrin complex or a metal phthalocyanine complex, wherein a morph doping ratio between the compound and the hole transport material is 10000:1 to 1:10000. According to claim 21,
The electroluminescent device, characterized in that the mol doping ratio of the compound and the hole transport material is 10: 1 to 1: 100. According to claim 21,
The charge generating layer further comprises a buffer layer disposed between the p-type charge generating layer and the n-type charge generating layer, and the buffer layer contains the compound. A compound preparation containing a compound according to any one of claims 1 to 16.

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