DE102020104604A1 - ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES - Google Patents

Abstract

An organic electroluminescent material is disclosed. The organic electroluminescent material are novel compounds having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole or the like, which can be used as charge transport materials, charge injection materials and charge generation materials in electroluminescent devices. These novel compounds can greatly improve the performance, such as voltage and lifetime, of organic electroluminescent devices. An electroluminescent device and compound formulation are also disclosed.

Description

AREA

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

TECHNICAL BACKGROUND

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

In 1987 Tang and Van Slyke of Eastman Kodak reported a two-layer organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinolatoaluminum layer as the electron and emissive layer ( Applied Physics Letters, 1987, 51 (12): 913-915 ). Once a bias was applied to the device, the device emitted a green light. With this disclosure the cornerstone for the development of modern organic light-emitting diodes (OLEDs) was laid. Prior art OLEDs can include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more emitting layers between the cathode and anode. Since the OLED is a self-emitting solid-state device, it offers enormous potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, make them well suited for certain applications, such as manufacturing on flexible substrates.

An OLED can be divided into three different types according to its emission mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. Only the singlet emission is used. The triplets generated in the device are wasted via non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of a fluorescence OLED is only 25%. This restriction hampered the marketing of OLEDs. Forrest and Thompson reported in 1997 on phosphorescent OLEDs that used triplet emission from heavy metal-containing complexes as the emitter. As a result, both singlets and triplets can be used, whereby 100% IQE is achieved. The discovery and development of phosphorescent OLEDs contributed directly to the commercialization of active matrix OLED (AMOLED) due to their high efficiency. Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap that allows the transition from triplet back to singlet. In the TADF device, the triplet excitons can go through a reverse intersystem crossing to produce singlet excitons, resulting in a high IQE.

OLEDs can also be classified as small molecule and polymer OLEDs depending on the shape of the materials used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of a small molecule can be large as long as it has a well-defined structure. Dendrimers with well-defined structures are considered to be small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant emitting groups. A small molecule OLED can become a polymer OLED if post-polymerization takes place during the manufacturing process.

There are various methods for producing OLEDs. Small molecule OLEDs are generally produced by thermal vacuum evaporation. Polymer OLEDs are made by solution processes such as spin coating, inkjet printing, and slit printing. If the material can be dissolved or dispersed in a solvent, the small molecule OLED can also be produced using the solution process.

The organic light emitting display device uses a hole injection layer and an electron injection layer to promote charge injection. The hole injection layer is a functional layer that is formed from a single material or from more than one material. Methods that use a single material generally use materials with deep LUMO levels, while methods that use more than one material are performed by doping a hole transport material with a deep P-type LUMO material. The commonality between these two methods is the use of materials with a deep LUMO level.

US20050121667 discloses the use of an organic mesomeric compound as an organic dopant for doping an organic semiconductor matrix material to change the electrical properties thereof. The mesomeric compound is a quinone or quinone derivative and has a lower volatility than F4-TCNQ under the same evaporation conditions. Include the general structures disclosed therein

This application primarily focuses on the unique properties of a quinone or quinone derivative when used as a dopant, but does not disclose or teach the properties and uses of a compound having an overall core structure similar to the present application.

However, materials with deep LUMO levels are not easy to synthesize because of their substituents with strong electron-withdrawing ability, and it is difficult to have both a deep LUMO level and a high stability and a high film-forming ability. For example, F4-TCNQ (a P-type hole injection material), although it has a deep LUMO level, has an extremely low vapor deposition temperature, which affects the deposition control and the reproducibility of the production output and the thermal stability of the device; and as another example, HATCN has problems with film formation in devices due to high crystallinity, and the LUMO level is not deep enough to be used as a P-type dopant. Since the hole injection layer has a great influence on the voltage, efficiency and life of an OLED device, it is very important and urgent for the industry to develop materials with a low LUMO level, high stability and high film-forming ability.

SUMMARY

The present invention aims to provide a variety of novel compounds having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole or the like in order to solve at least some of the above problems. The compounds can be used as charge transport materials and charge injection materials in organic electroluminescent devices. These novel compounds can significantly improve the performance, such as voltage and lifetime, of organic electroluminescent devices.

worin X und Y bei jedem Vorkommen gleich oder verschieden aus CR''R''', NR', O, S oder Se ausgewählt sind;
worin Z₁ und Z₂ bei jedem Vorkommen gleich oder verschieden aus O, S oder Se ausgewählt sind;
R, R', R'' und R''' bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe, einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso, einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und Kombinationen davon;
worin jedes R gleich oder verschieden sein kann und mindestens eines von R, R', R'' und R''' eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist; und
benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden.According to one embodiment of the present invention, a compound having the formula 1 is disclosed:

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se;
wherein Z ₁ and Z ₂ are selected identically or differently for each occurrence from O, S or Se;
R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted one or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 Koh fuel atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
wherein each R can 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; and
adjacent substituents may optionally be linked to form a ring.

worin X und Y bei jedem Vorkommen gleich oder verschieden aus CR''R''', NR', O, S oder Se ausgewählt sind;
worin Z₁ und Z₂ bei jedem Vorkommen gleich oder verschieden aus O, S oder Se ausgewählt sind;
R, R', R'' und R''' bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe, einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso, einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und Kombinationen davon;
benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden; und
worin jedes R gleich oder verschieden sein kann und mindestens eines von R, R', R'' und R''' eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist.According to yet another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the structure of Formula 1:

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se;
wherein Z ₁ and Z ₂ are selected identically or differently for each occurrence from O, S or Se;
R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted one or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 Koh fuel atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
adjacent substituents may optionally be linked to form a ring; and
wherein each R can 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.

In accordance with another embodiment of the present invention, a compound formulation comprising a compound having the structure of Formula 1 is also disclosed.

The novel compounds having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole or the like disclosed in the present invention can be used as charge transporting materials and charge injection materials in electroluminescent devices. Such novel compounds significantly improve the performance, such as voltage and lifetime, of organic electroluminescent devices.

Figure list

• 1 FIG. 11 schematically shows an organic light emitting device that may contain the compound and compound formulation disclosed herein.
• 2 Figure 12 shows schematically a tandem organic light emitting device that may contain the compound and compound formulation disclosed herein.
• 3 Figure 12 shows schematically another tandem organic light emitting device that may contain the compound and compound formulation disclosed herein.
• 4th Figure 1 shows Structural Formula 1 of the compound disclosed herein.

DETAILED DESCRIPTION

OLEDs can be produced on various types of substrates, such as glass, plastic and metal foil. 1 Fig. 3 schematically shows the organic light emitting device 100 without restriction. The figures are not necessarily shown to scale. Some of the layers in the figure can also be omitted if necessary. The device 100 can be a substrate 101 , an anode 110 , a hole injection layer 120 , a hole transport layer 130 , an electron blocking layer 140 , an emission layer 150 , a hole blocking layer 160 , an electron transport layer 170 , an electron injection layer 180 and a cathode 190 include. The device 100 can be produced by depositing the described layers in this order. The properties and functions of these various layers, as well as exemplary materials, are described in U.S. Pat. No. 7,279,704 6-10, which are incorporated herein by reference in their entirety.

More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in US Pat. No. 5,844,363 which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA, which is doped with F4-TCNQ in a molar ratio of 50: 1, as described in U.S. Patent Application No. 2003/0230980 which is incorporated herein by reference in its entirety. Examples of host materials are given in U.S. Pat. No. 6,303,238 by Thompson et al. which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen, which is doped with Li in a molar ratio of 1: 1, as described in U.S. Patent Application No. 2003/0230980 which is incorporated herein by reference in its entirety. US Pat. No. 5,703,436 and No. 5,707,745 , which are incorporated herein by reference in their entirety, disclose examples of cathodes, including composite cathodes having a thin layer of metal, such as Mg: Ag, with an overlying transparent, electrically conductive, sputtered ITO layer. The theory and use of blocking layers is described in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980 which are incorporated herein by reference in their entirety. Examples of injection layers are described in U.S. Patent Application Publication No. 2004/0174116 , which is incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004/0174116 , which is incorporated herein by reference in its entirety.

The layer structure described above is presented as a non-limiting example. Functional OLEDs can be achieved in different ways by combining the various layers described, or layers can be omitted entirely, such as an electron blocking layer. It can also include other layers that are not specifically described. A single material or a mixture of multiple materials can be used within each layer for optimal performance. Each functional layer can contain several sublayers. For example, the emitting layer can have two layers made of different emitting materials in order to achieve the desired emission spectrum.

In one embodiment, an OLED can be described as having an “organic layer” arranged between a cathode and an anode. This organic layer can comprise a single layer or multiple layers.

In one embodiment, two or more OLED units can be connected in series to form a tandem OLED. 2 Fig. 3 schematically shows the tandem organic light emitting device 500 without restriction. The device 500 can be a substrate 101 , an anode 110 , a first unit 100 , a charge generation layer 300 , a second unit 200 and a cathode 290 included, with the first unit 100 a hole injection layer 120 , a hole transport layer 130 , an electron blocking layer 140 , an emission layer 150 , a hole blocking layer 160 , an electron transport layer 170 includes and the second unit 200 a hole injection layer 220 , a hole transport layer 230 , an electron blocking layer 240 , an emission layer 250 , a hole blocking layer 260 , an electron transport layer 270 and an electron injection layer 280 includes. The charge generation layers 300 comprise an N-type charge generation layer 310 and a P-type charge generation layer 320 . The device 500 can be produced by successively depositing the layers described.

An OLED can be encapsulated by a barrier layer. 3 Fig. 3 schematically shows the organic light emitting device 600 without restriction. 3 differs from 2 in that the organic light emitting device has a barrier layer 102 contains, which is located above the cathode 290 to protect them from harmful environmental species such as moisture and oxygen. Any material that can fulfill the barrier function can be used as the barrier layer, such as glass and organic-inorganic hybrid layers. The barrier layer should be placed directly or indirectly outside the OLED device. The multilayer thin film encapsulation was in U.S. Pat. No. 7,968,146 which is incorporated herein by reference in its entirety.

Devices made in accordance with embodiments of the present disclosure can be incorporated into a variety of consumer products that include one or more electronic component modules (or units) therein. Some examples of such consumer goods are flat screens, monitors, medical monitors, televisions, posters, lights for indoor or outdoor lighting and / or signaling, head-up displays, completely or partially transparent displays, flexible displays, smartphones, tablets, phablets , wearable devices, smart watches, laptops, digital cameras, camcorders, viewfinders, microdisplays, 3D displays, vehicle displays and vehicle taillights.

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

As used herein, "top" means the greatest distance to the substrate, while "bottom" means closest to the substrate. If a first layer is described as being “arranged over” a second layer, the first layer is arranged further away from the substrate. Additional layers may be present between the first and second layers unless it is indicated that the first layer is "in contact with" the second layer. For example, a cathode can be said to be “placed over” an anode, even though there are various organic layers in between.

As used herein, "solution processable" means the ability to be dissolved, dispersed, or transported, and / or separated from, a liquid medium, either in solution or suspension form.

A ligand can be referred to as “photoactive” if it is assumed that the ligand contributes directly to the photoactive properties of an emitting material. A ligand can be called an “aid” if it is assumed that the ligand does not contribute to the photoactive properties of an emissive material, although an auxiliary ligand can change the properties of a photoactive ligand.

It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit due to delayed fluorescence. As used herein, there are two types of delayed fluorescence, namely, P-type delayed fluorescence and E-type delayed fluorescence. The P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

On the other hand, the E-type delayed fluorescence is not based on the collision of two triplets, but on the transition between the triplet states and the excited singlet states. Compounds that are capable of producing delayed E-type fluorescence must have very small singlet-triplet Have gaps in order to convert between the energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A special feature of TADF is that the delayed component increases with increasing temperature. If the rate of reverse intersystem crossing is fast enough to minimize the non-radiative decay from the triplet state, the proportion of reoccupied singlet excited states can potentially reach 75%. The total singlet fraction can be 100% and is thus well over 25% of the spin statistical limit for electrically generated excitons.

E-type delayed fluorescence properties are found in an exciplex system or in a single compound. While not wishing to be bound by theory, it is believed that the E-type delayed fluorescence requires that the luminescent material have a small singlet-triplet energy gap (ΔE _ST ). Organic, non-metallic, luminescent donor-acceptor materials may accomplish this. The emission in these materials is often characterized as donor-acceptor-charge-transfer (CT) -type emission. The spatial separation of HOMO and LUMO in these compounds of the donor-acceptor type often leads to a small ΔE _ST . These states can include CT states. Often luminescent donor-acceptor materials are made by joining an electron donor unit such as amino or carbazole derivatives and an electron acceptor unit such as N-containing six-membered aromatic rings.

Definition of the terms of the substituents

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

Alkyl - includes both straight and branched chain alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-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, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-1- methylpentyl group, 1-pentylhexyl group Butylpentyl group, 1-heptyloctyl group, 3-methylpentyl group. In addition, the alkyl group can optionally be substituted. The carbons in the alkyl chain can be replaced by other heteroatoms. Of the above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, n-pentyl group and neopentyl group are preferred.

Cycloalkyl - as used herein, includes cyclic alkyl groups. Preferred cycloalkyl groups are those having 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. In addition, the cycloalkyl group can optionally be substituted. The carbons in the ring can be replaced by other heteroatoms.

Alkenyl - as used herein, takes into account both straight and branched chain alkene groups. Preferred alkenyl groups are those with two to fifteen carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl group, 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. In addition, the alkenyl group can optionally be substituted.

Alkynyl - as used herein contemplates both straight and branched chain alkyne groups. Preferred alkynyl groups are those having two to fifteen carbon atoms. In addition, the alkynyl group can optionally be substituted.

Aryl or aromatic group - as used herein, uncondensed and condensed systems are considered. Preferred aryl groups are those having six to sixty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenals, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group can optionally be substituted. Examples of the non-condensed aryl group include phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, Biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-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-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 4'-methylbiphenylyl group, 4 "-tert-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group and m- Quarter phenyl group

Heterocyclic Group or Heterocycle - as used herein includes aromatic and non-aromatic cyclic groups. Hetero-aromatic also means heteroaryl. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms which contain at least one hetero atom such as nitrogen, oxygen and sulfur. The heterocyclic group can also be an aromatic heterocyclic group having at least one hetero atom selected from nitrogen atom, oxygen atom, sulfur atom and selenium atom.

Heteroaryl - as used herein includes uncondensed and condensed heteroaromatic groups that can contain one to five heteroatoms. Preferred heteroaryl groups are those having three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazadiazole, thiazole, triazole, oxazadiazole, thiazole, oxidiazole, thiazoliazole, oxidiazole, oxazadiazole, furan, thiophene, oxazadiazole, furan, thiophene, oxazadiazole, thiazole, oxidiazole , Pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, chinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, acridine, xanthenazine, , Phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, azine, 1,4-azine, 1,3-, benzimide, triazine Azaborine, borazine and aza analogs thereof. In addition, the heteroaryl group can optionally be substituted.

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

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

Arylalkyl - as used herein contemplates an alkyl group that has an aryl substituent. In addition, the arylalkyl group can optionally be substituted. Examples of the arylalkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-tert-butyl group, alpha-naphthylmethyl group, 1-alpha-naphthylethyl group, 2-alpha-naphthylethyl group, 1 -alpha- Naphthylisopropyl group, 2-alpha-naphthylisopropyl group, beta-naphthylmethyl group, 1-beta-naphthylethyl group, 2-beta-naphthylethyl group, 1-beta-naphthylisopropyl group, 2-beta-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group Chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, p-aminobyl group, o-hydroxybenzyl m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenyli sopropyl group and 1-chloro-2-phenylisopropyl group. Of the above, preferred are benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group and 2-phenylisopropyl group.

The term “aza” in azadibenzofuran, azadibenzothiophene, etc. means that one or more of the C-H groups in the respective aromatic fragment have been replaced by a nitrogen atom. For example, azatriphenylene includes dibenzo [f, h] quinoxaline, dibenzo [f, h] quinoline, and other analogs with two or more nitrogens in the ring system. One skilled in the art can readily envision other nitrogen analogs of the aza derivatives described above, and all such analogs are intended to be encompassed by the terms set forth herein.

It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these various methods of designating a substituent or attached fragment are considered equivalent.

In the compounds mentioned in this disclosure, the hydrogen atoms can be partially or completely replaced by deuterium. Other atoms, such as carbon and nitrogen, can also be replaced with their other stable isotopes. Replacement with other stable isotopes in the compounds may be preferred because of the improvement in device efficiency and stability.

In the compounds mentioned in this disclosure, multiple substitutions refer to a range that includes double substitution up to the maximum available substitutions. When a substitution in the compounds mentioned in this disclosure represents multiple substitutions (including di, tri, tetra substitutions, etc.), that is, the substituent can exist at a variety of available substitution positions on its connecting structure, the substituents which can be found on one There are multitudes of available substitution positions that have the same structure or different structures.

If in the present disclosure, unless otherwise defined, any term from the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted Alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, a substituted carboxylic acid group, a substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphoroso is used, this means that any group of alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, Aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid group, ester group, sulfinyl, sulfonyl and phosphoroso can be substituted with one or more groups selected from the group consisting of a us deuterium, a halogen, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms , an unsubstituted aryloxy group with 6 to 30 carbon atoms, an unsubstituted alkenyl group with 2 to 20 carbon atoms, an unsubstituted alkynyl group with 2 to 20 carbon atoms, an unsubstituted aryl group with 6 to 30 carbon atoms, an unsubstituted heteroaryl group with 3 to 30 carbon atoms, an unsubstituted alkylsilyl group 3 to 20 carbon atoms, 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 , an ester group, a cyano group, an isocyano group, a thiol group, a sulfinoyl group, a sulfonyl group and a phosphoroso group, and combinations thereof.

In the compounds recited in the present disclosure, adjacent substituents in the compounds need not be joined to form a ring unless expressly defined otherwise, e.g., adjacent substituents may optionally be joined to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents may optionally be linked to form a ring, both in the case that adjacent substituents may be linked to form a ring and in the event that adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be linked to form a ring, the ring formed can be monocyclic or polycyclic as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In such a term, adjacent substituents may refer to substituents attached to the same atom, substituents attached to carbon atoms attached directly to each other, or substituents attached to carbon atoms farther apart. Preferably, adjacent substituents refer to substituents attached to the same carbon atom and to substituents attached to carbon atoms attached directly to each other.

The expression that adjacent substituents may optionally be linked to form a ring is also intended to mean that two substituents attached to the same carbon atom are chemically bonded to one another to form a ring, as indicated by the following Formula can be illustrated:

The expression that adjacent substituents may optionally be linked to form a ring is also intended to mean that two substituents attached to carbon atoms that are directly linked to one another are chemically bonded to one another to form a ring which can be illustrated by the following formula:

In addition, the expression that adjacent substituents may optionally be linked to form a ring is also intended to mean that in the event that one of the two substituents attached to carbon atoms that are directly bonded to one another represents hydrogen, the second substituent is attached to a position where the hydrogen atom is attached, thereby forming a ring. This is illustrated by the following formula:

worin X und Y bei jedem Vorkommen gleich oder verschieden aus CR''R''', NR', O, S oder Se ausgewählt sind;
worin Z₁ und Z₂ bei jedem Vorkommen gleich oder verschieden aus O, S oder Se ausgewählt sind; R, R', R'' und R''' bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe, einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso, einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und Kombinationen davon;
worin jedes R gleich oder verschieden sein kann und mindestens eines von R, R', R'' und R''' eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist; und
benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden.According to one embodiment of the present invention, a compound having the formula 1 is disclosed:

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se;
wherein Z ₁ and Z ₂ are selected identically or differently for each occurrence from O, S or Se; R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group of 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group of 3 to 30 aryl group Carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20K carbon atoms and combinations thereof;
wherein each R can 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; and
adjacent substituents may optionally be linked to form a ring.

In the present embodiment, R, R ', R "and R"' are selected identically or differently in each occurrence from the group of substituents. It is obvious to those skilled in the art to confirm that two substituents with the same number (e.g., R, R ', R "or R"') appearing simultaneously in Formula 1 are selected from the same substituent or different substituents can.

According to one embodiment of the present invention, X and Y are selected identically or differently for each occurrence from CR "R" "or NR", where R ', R "and R"' are groups with at least one electron-withdrawing group.

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

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

According to one embodiment of the present invention, X and Y are selected identically or differently for each occurrence from O, S or Se, and all R are groups with 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 the Hammett constant of the electron withdrawing group is 0.3, or the Hammett constant of the electron withdrawing group is 0.5.

The electron-withdrawing group of the present invention has a value of the Hammett's substituent constant of 0.05, preferably 0.3, more preferably 0.5, and thus has a strong electron-withdrawing ability which can significantly reduce the LUMO energy level of the compound can improve cargo mobility.

Note that the value of the Hammett's substituent constant includes the Hammett's substituent constant of the para position and / or that of the meta position. As long as either of the para position constant and the meta position constant is equal to or greater than 0.05, the group is preferred for the present invention.

According to one embodiment of the present invention, the electron-withdrawing group is selected from the group consisting of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso , an aza-aromatic ring group, and any of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms and an arylsilyl group with 6 to 20 carbon atoms, the substitute ert is with one or more of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, and an aza-aromatic ring group, and combinations thereof .

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

worin R₁ bei jedem Vorkommen gleich oder verschieden ausgewählt ist aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe,
einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso,
einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und
Kombinationen davon;
worin V und W bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus CR_VR_W, NR_v, O, S oder Se;
worin Ar bei jedem Vorkommen gleich oder verschieden ausgewählt ist aus einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen oder einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen;
worin A, R_a, R_b, R_c, R_d, R_e, R_f, R_g, R_h, R_v und R_w bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe, einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso, einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und Kombinationen davon;
worin A eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist, und für jede der Strukturen, wenn eines oder mehrere von R_a, R_b, R_c, R_d, R_e, R_f, R_g, R_h, R_v und R_w vorhanden ist (sind), mindestens eine von ihnen eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist.According to one embodiment of the present invention, X and Y are selected identically or differently for each occurrence from the group consisting of the following structures:

wherein R ₁ is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group,
an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso,
a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 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 su substituted or unsubstituted arylsilyl group with 6 to 20 carbon atoms and
Combinations thereof;
wherein V and W are selected identically or differently for each occurrence from CR _V R _W , NR _v , O, S or Se;
wherein Ar is selected identically or differently at each occurrence 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 selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen , Nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted ode r unsubstituted alkynyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group with 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group with 6 bisilyl 20 carbon atoms and combinations thereof;
wherein A is a group having at least one electron withdrawing group, and for each of the structures when one or more of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , R _v and R _w is (are) present, at least one of them is a group with at least one electron withdrawing group.

In the present embodiment, “*” indicates the position at which the groups X and Y are bonded to the dehydrobenzodioxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the present invention, R _{1 is} selected identically or differently for each occurrence from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl , Tetrafluoropyridyl, pyrimidinyl, triazinyl, and combinations thereof.

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

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

In the present embodiment, “*” indicates the position at which the groups X and Y are bonded to the dehydrobenzodioxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the present invention, R is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , Boranyl, sulfinyl, sulfonyl, phosphoroso, an unsubstituted alkyl group with 1 to 20 carbon atoms, an unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, an unsubstituted alkoxyl group with 1 to 20 carbon atoms, an unsubstituted alkenyl group with 2 to 20 carbon atoms, an unsubstituted aryl group to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, and any of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group m it 6 to 30 carbon atoms and a heteroaryl group with 3 to 30 carbon atoms, which is substituted with one or more groups selected from the group consisting of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl and phosphoroso and combinations thereof.

According to one embodiment of the present invention, R is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, methyl, isopropyl, NO ₂ , SO ₂ CH ₃ , SCF ₃ , C ₂ F ₅ , OC ₂ F ₅ , OCH ₃ , diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, vinyl substituted with one or more of CN and CF ₃ , ethynyl substituted with one of CN and CF ₃ , Dimethylphosphoroso, Diphenylphosphoroso, F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetra-phenyl, 4-cyano-tetra-phenyl Biphenyl substituted with one or more of F, CN and CF ₃ , tetrafluoropyridyl, pyrimidinyl, triazinyl, diphenylboranyl, oxaboraanthryl, and combinations thereof.

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

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

‟ die Position, bei der die Gruppe R an den Dehydrobenzodioxazolring, den Dehydrobenzodithiazolring oder den Dehydrobenzodiselenazolring in Formel 1 angebunden ist.In the present embodiment, "

‟The position in which the group R is attached to the dehydrobenzodioxazole ring, the dehydrobenzodithiazole ring or the dehydrobenzodiselenazole ring in formula 1.

According to one embodiment of the present invention, R is selected identically or differently for each occurrence from the group consisting of B1 to B88. The specific structure from B1 to B88 is given in the above embodiment.

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

According to one embodiment of the present invention, the compound is selected from the group consisting of Compound 1 through Compound 1356. The specific structure of Compound 1 through Compound 1356 is set out in claim 11.

According to one embodiment of the present invention, the compound is selected from the group consisting of Compound 1 to Compound 1428. The specific structure of Compound 1 to Compound 1428 is set out in claim 11.

• eine Anode,
• eine Kathode und
• eine zwischen der Anode und der Kathode angeordnete organische Schicht, wobei die organische Schicht eine Verbindung mit der Formel 1 umfasst:

worin X und Y bei jedem Vorkommen gleich oder verschieden aus CR''R''', NR', O, S oder Se ausgewählt sind;
worin Z₁ und Z₂ bei jedem Vorkommen gleich oder verschieden aus der Gruppe bestehend aus O, S oder Se ausgewählt sind;
R, R', R'' und R''' bei jedem Vorkommen gleich oder verschieden ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Deuterium, Halogen, Nitroso, Nitro, Acyl, Carbonyl, einer Carbonsäuregruppe, einer Estergruppe, Cyano, Isocyano, SCN, OCN, SF₅, Boranyl, Sulfinyl, Sulfonyl, Phosphoroso, einer substituierten oder unsubstituierten Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Cycloalkylgruppe mit 3 bis 20 Ringkohlenstoffatomen, einer substituierten oder unsubstituierten Heteroalkylgruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylalkylgruppe mit 7 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Aryloxygruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkenylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkinylgruppe mit 2 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe mit 6 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Heteroarylgruppe mit 3 bis 30 Kohlenstoffatomen, einer substituierten oder unsubstituierten Alkylsilylgruppe mit 3 bis 20 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylsilylgruppe mit 6 bis 20 Kohlenstoffatomen und Kombinationen davon;
worin jedes R gleich oder verschieden sein kann und mindestens eines von R, R', R'' und R''' eine Gruppe mit mindestens einer elektronenziehenden Gruppe ist; und
benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden.According to an embodiment of the present invention, an electroluminescent device is also disclosed, comprising:

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

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se;
wherein Z ₁ and Z _{2 are selected} identically or differently for each occurrence from the group consisting of O, S or Se;
R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted one or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 Koh fuel atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof;
wherein each R can 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; and
adjacent substituents may optionally be linked to form a ring.

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

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

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

According to one embodiment of the present invention, the electroluminescent device comprises a plurality of stacks arranged between the anode and the cathode, the stacks comprising a first light-emitting layer and a second light-emitting layer, the first stack comprising a first light-emitting layer and the second stack comprising a second light-emitting layer Layer, and a charge generating layer is disposed between the first stack and the second stack, the charge generating layer comprising a p-type charge generating layer and an n-type charge generating layer; wherein the organic layer comprising the compound represented by Formula 1 is the p-type charge generating layer.

According to one embodiment of the present invention, the p-type charge generating layer further comprises at least one hole transport material and is formed by doping the compound with the at least one hole transport material, the hole transport material being a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, a An oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, wherein the molar doping ratio of the compound to the hole transport material is 10,000: 1 to 1: 10,000.

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

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

In accordance with another embodiment of the present invention, a compound formulation comprising a compound represented by Formula 1 is also disclosed. The specific structure of the compound is shown in each of the preceding embodiments.

Combination with other materials

The materials described herein as being suitable for a particular layer in an organic light emitting device can be used in combination with a variety of other materials present in the device. The combinations of these materials are described in more detail in U.S. Patent Application No. 20160359122 in paragraphs 0132-0161, which are incorporated by reference in their entirety. The materials described or the disclosure of which is referred to are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one skilled in the art can readily consult the literature to identify other materials that may can be useful in combination.

The materials described herein as being useful for a particular layer in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The combination of these materials is described in paragraphs 0080-0101 of U.S. Patent Application No. 20150349273 A1 which is incorporated by reference in its entirety. The materials described or the disclosure of which is referred to are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one skilled in the art can readily consult the literature to identify other materials that may can be useful in combination.

In the embodiments of the material synthesis, all reactions were carried out under nitrogen protection, unless otherwise stated. All reaction solvents were anhydrous and were used as obtained from commercial sources. Synthetic products have been structurally validated and their properties tested using one or more conventional devices in the art (including, but not limited to, nuclear magnetic resonance device from BRUKER, liquid chromatograph from SHIMADZU, liquid chromatography mass spectrometer from SHIMADZU, gas chromatography mass spectrometer from SHIMADZU, differential scanning calorimeter from SHIMADZU, SHANGHAI LENGGUANG TECH. Fluorescence spectrophotometer, WUHAN CORRTEST electrochemical workstation, and ANHUI BEQ sublimation apparatus, etc.) by methods well known to those skilled in the art. In the embodiments of the apparatus, the characteristics of the apparatus were also tested with conventional equipment in the art (including, but not limited to, evaporators from ANGSTROM ENGINEERING, the optical test system made by SUZHOU FATAR, the life test system made by SUZHOU FATAR, and that made by BEIJING ELLITOP manufactured ellipsometers, etc.) according to methods well known to those skilled in the art. Since those skilled in the art are aware of the above equipment uses, test methods, and other related matters, the inherent data of the sample can be obtained with certainty and without influence, so the above related matters will not be further described in this patent.

• Ohne das Verfahren zur Herstellung der Verbindungen der vorliegenden Erfindung beschränken zu wollen, veranschaulichen die folgenden Verbindungen typische, aber nicht einschränkende Beispiele. Deren Syntheseweg und Herstellungsmethode sind wie folgt:

Synthesis examples of the materials:

• Without wishing to limit the process for preparing the compounds of the present invention, the following compounds illustrate typical but non-limiting examples. Their synthetic route and manufacturing method are as follows:

Synthesis Example 1: Synthesis of Compound 56

Step 1: Synthesis of [Intermediate 1-a]

DMSO (150 mL) was placed in a 500 mL three-necked flask and nitrogen was flushed through for half an hour. HC (OEt) ₃ (22.2 g, 150 mmol) and Y (OTf) ₃ (2.15 g, 4 mmol) were added in succession and rinsing was carried out for a further 5 minutes. 2,5-diamino-3,6-dibromobenzene-1,4-diol (8.94 g, 30 mmol) was added and the mixture was warmed to 60 ° C. After 20 minutes the solution turned brown or khaki and was stirred overnight. After the reaction had ended, DCM / PE (1: 1, 500 mL) was added. A solid was collected by filtration and it was washed with acetone and filtered to give 1-a as an off-white solid (7.2 g, 75% yield). 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 and nitrogen was flushed through for 15 minutes. Pd (OAc) ₂ (225 mg, 10 mol%, 1.0 mmol) and XPhos (1.0 g, 2.1 mmol) were added with stirring. After stirring for 10 minutes, 1-a (3.18 g, 10 mmol), p-trifluoromethoxyphenylboronic acid (8.24 g, 40 mmol) and potassium carbonate (8.34 g, 60 mmol) were added sequentially. The reaction was warmed to 110 ° C, refluxed and stirred overnight under a nitrogen atmosphere. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane, and isolated on silica gel column chromatography to give 1-b as a white solid (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]

Intermediate 1-b (4.36 g, 9.1 mmol) was added to THF (114 mL, 0.08M) under a nitrogen atmosphere. The mixture was cooled to -94 ° C. (in an acetone / liquid nitrogen cold bath). n-Butyllithium (13.8 mL, 20.93 mmol, 1.6 M in n-hexane) was slowly added dropwise. The reaction was held at this temperature for 1 h, then slowly warmed to -78 ° C. (in a cold bath made of acetone / dry ice) and reacted for 8 h. A solution of elemental iodine (6.93 g, 27.3 mmol) in THF (15 mL) was added. After the addition, the mixture was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 3: 1-1: 1) to give product 1-c as a white solid (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]

Malononitrile (2.78 g, 42 mmol) was added to anhydrous DMF (70 mL) under a nitrogen atmosphere. NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 1-c (5.08 g, 7 mmol) and Pd (PPh ₄ ) ₃ (1.62 g, 1.4 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24-36 h . After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give 4.38 g of yellow solid. The solid was then washed twice with dichloromethane and filtered to give 1-d as a yellow solid (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

1-d (3.04 g, 5 mmol) was added to DCM (150 mL) under a nitrogen atmosphere. The mixture was cooled to 0 ° C and PIFA (6.45 g, 15 mmol) was added in portions. After stirring at room temperature for 3 days, the solution was purple black. n-Hexane (450 mL) was added to the reaction solution and the mixture was stirred for 10 minutes and then filtered to give a dark green solid. The solid was washed twice with DCM / PE (2: 1-1: 1) to give compound 56 as a dark green solid (2.5 g, 83% yield). 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 placed in a 250 mL two neck flask and nitrogen was purged for 15 minutes. Pd (OAc) ₂ (360 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added with stirring. After stirring for 10 minutes, 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) were added sequentially . The mixture was warmed to 110 ° C., heated to reflux and stirred overnight under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled, filtered through Celite, washed with dichloromethane, and isolated on silica gel column chromatography to give 2-a as a white solid (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]

2-a (6.2 g, 10.6 mmol) was added to THF (212 mL, 0.05 M) under a nitrogen atmosphere. The mixture was cooled to -94 ° C (in an acetone / liquid nitrogen cold bath) (the temperature of the reaction system must not exceed -94 ° C). n-Butyllithium (15.2 mL, 24.4 mmol, 1.6 M in n-hexane) was slowly added dropwise. The reaction was held at this temperature for 1 h, then slowly warmed to -78 ° C. (in a cold bath made of acetone / dry ice) and reacted for 8 h. A solution of elemental iodine (8.07 g, 31.8 mmol) in THF (20 mL) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 6: 1-2: 1) to give product 2-b as a white solid (4.7 g, 53% yield). ¹ HNMR (400 MHz, CDCl ₃ ) δ = 8.69 (s, 4H), 8.01 (s, 2H).

Step 3: Synthesis of [Intermediate 2-c]

Malononitrile (1.56 g, 23.7 mmol) was added to anhydrous DMF (55 mL, 0.1 M) under a nitrogen atmosphere. NaH (948 mg, 23.7 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 2-b (3.3 g, 3.95 mmol) and Pd (PPh ₄ ) ₃ (456 mg, 0.39 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24-36 h. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give 2.98 g of yellow solid. The solid was then washed twice with solvent (DCM / PE = 2: 1, 200 mL) and filtered to give 2-c as a yellow solid (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

Under a nitrogen atmosphere, 2-c (2.85 g, 4.0 mmol) was divided into 3 portions (0.95 g / portion) and placed in three two-necked flasks and DCM (200 mL) was added to each. After cooling to 0 ° C., PIFA (1.73 g, 4.0 mmol) was then added in portions. After stirring at room temperature for 3 days, the solution was purple black. Then the solution in the three flasks was collected in a 1 L single neck flask and the solution was evaporated to approximately 50 mL on a rotary evaporator. n-Hexane (450 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a dark green solid. The solid was washed twice with DCM / PE (2: 1, 200 mL) to give compound 68 as a dark green solid (2.4 g, 85% yield). 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 placed in a 250 mL two neck flask and nitrogen was purged for 15 minutes. Pd (OAc) ₂ (360 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added with stirring. After stirring for 10 minutes, 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) were added sequentially . The reaction was warmed to 110 ° C, heated to reflux, and stirred under nitrogen overnight. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane, and isolated through silica gel column chromatography to obtain 4-a as a white solid (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]

4-a (6.4 g, 11 mmol) was added to THF (150 mL) under a nitrogen atmosphere. The mixture was cooled to -94 ° C. (in an acetone / liquid nitrogen cold bath). n-Butyllithium (15.8 mL, 25.3 mmol, 1.6 M in n-hexane) was slowly added dropwise. The reaction was held at this temperature for 1 h, then slowly warmed to -78 ° C. (in a cold bath made of acetone / dry ice) and reacted for 8 h. A solution of elemental iodine (8.4 g, 33 mmol) in THF (20 mL) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 10: 1-2: 1) to give product 4-b as a white solid (6.89 g, 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]

Malononitrile (2.14 g, 32 mmol) was added to anhydrous DMF (60 mL) under a nitrogen atmosphere. NaH (1.40 g, 35 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 4-b (4.51 g, 5.4 mmol) and Pd (PPh ₄ ) ₃ (1.15 g, 1.0 mmol) were then added and the mixture was warmed to 90 ° C and lasted for 24-36 h implemented. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give 2.98 g of yellow solid. The solid was then washed twice with dichloromethane and filtered to give 4-c as a yellow solid (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, 4-c (2.92 g, 4.1 mmol) was divided into 3 portions (1 g / portion) and placed in three two-necked flasks and DCM (100 mL) was added to each. After cooling to 0 ° C., PIFA (1.8 g, 4.2 mmol) was then added in portions. After stirring at room temperature for 3 days, the solution was purple black. Then the solution in the three flasks was collected in a 1 L one-neck flask and the solution was concentrated to about 50 mL. n-Hexane (450 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a purple solid. The solid was washed twice with DCM / PE (2: 1, 200 mL) to give compound 70 as a purple solid (2.0 g, 70% yield). 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 (50 mL), 1,4-phenylenediamine (17.0 g, 157 mmol) and hydrochloric acid (30.7 mL, 125 mmol) were placed in a 500 mL two-necked flask. The mixture was warmed to 50 ° C and NH ₄ SCN (48.4 g, 636 mmol) was added. The mixture was further heated to 95 ° C. and stirred for 24 h. After the completion of the reaction, the reaction mixture was cooled, filtered and washed with ethanol to give Compound 5-a as a gray solid (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 (15 g, 66.5 mmol) and chloroform (100 ml) were added successively to a 500 ml three-necked flask. The mixture was warmed to 50 ° C and a solution of bromine (8 mL, 309 mmol) in chloroform (100 mL) was added dropwise very slowly. After the addition, the mixture was refluxed for 24-36 h. After the completion of the reaction, it was cooled to 0 ° C and filtered. The filter cake was washed three times with chloroform. A solid was collected, washed with saturated sodium thiosulfate solution and filtered. A solid was collected, washed with methanol and dichloromethane separately and then filtered to give 5-b as a brown solid (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 (500 mL) was added to a 1 L three neck flask and nitrogen was purged for 20 minutes. Compound 5-b (11 g, 50 mmol), iodine (76 g, 300 mmol) and tBuONO (20.6 g, 200 mmol) were then added sequentially. The mixture was reacted at 70 ° C. for 24 hours. After the completion of the reaction, the reaction mixture was cooled and evaporated under reduced pressure to remove acetonitrile. 200 mL dichloromethane was then added. The mixture was filtered and washed with petroleum ether to give 5-c as a brick red solid (11 g, 50% yield). ¹ HNMR (400 MHz, d ₆ -DMSO) δ = 8.74 (s, 2H).

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

Malononitrile (5.35 g, 81 mmol) was added to anhydrous DMF (135 mL) under a nitrogen atmosphere. NaH (3.24 g, 81 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. Compound 5-c (6.08 g, 13.5 mmol) and Pd (PPh ₄ ) ₃ (3.12 g, 2.7 mmol) were then added and the mixture was warmed to 90 ° C and left for 24- 36 h implemented. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of brown solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give a brown solid (4.2 g). The solid was then washed twice with dichloromethane and filtered to give 5-d as a brown solid (4.02 g, 93% yield). LCMS (ESI): m / z 319 [MH] ^- .

Step 5: synthesis of compound 101 :

Compound 5-d (3.20 g, 10 mmol) was added to DCM (1 L) under a nitrogen atmosphere. The mixture was cooled to 0 ° C and PIFA (12.9 g, 30 mmol) was added in portions. After stirring at room temperature for 3 days, the solution was purple black. When the reaction was complete, the solution was rotary evaporated to approximately 100 mL. n-Hexane (450 mL) was then added to the reaction solution and the mixture was stirred for 10 minutes and filtered to give a purple-black solid. The solid was washed twice with dichloromethane to give compound 101 as a purple black solid (3.0 g, 94% yield). LCMS (ESI): m / z 317 [MH] ^- .

Synthesis Example 5: Synthesis of Compound 69

Step 1: Synthesis of [Intermediate 6-a]

In a 250 mL two-necked flask, 2,5-di (trifluoromethyl) bromobenzene (18.5 g, 63 mmol) and super-dry THF (100 mL) were added under a nitrogen atmosphere. After cooling to -78 ° C, a solution of isopropylmagnesium chloride-lithium chloride complex (54 mL, 69 mmol, 1.3 M in THF) was slowly added dropwise, and after the addition the reaction was continued at -78 ° C for 1 h , and then the reaction was brought to room temperature over 4 hours. A solution of ZnCl ₂ (35 mL, 69.3 mmol, 2.0 M in 2-methyl-THF) was slowly added dropwise below room temperature and the mixture was stirred for 1 h at room temperature after the addition. Pd (OAc) ₂ (337 mg, 1.5 mmol), XPhos (1.43 g, 3.0 mmol) and 1-a (5.0 g, 15.7 mmol) were added in one portion under N ₂ - Protection added and after stirring for 10 min the mixture was refluxed for 24 h. After the reaction was complete, the reaction was cooled, _{quenched with a small amount of saturated NH 4} Cl solution, filtered through Celite, washed with DCM, and isolated via silica gel column chromatography to give 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]

6-a (4.23 g, 7.2 mmol) was added to THF (200 mL) under a nitrogen atmosphere. The mixture was cooled to -94 ° C. n-Butyllithium (10.4 mL, 16.6 mmol, 1.6 M in n-hexane) was slowly added dropwise. The reaction was kept at this temperature for 1 h, then slowly warmed to -78 ° C. and reacted for 8 h. A solution of elemental iodine (5.49 g, 21.6 mmol) in THF (30 mL) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 10: 1-1: 1) to give product 6-b as a light yellow solid (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]

Malononitrile (792 mg, 12 mmol) was added to anhydrous DMF (20 mL) under a nitrogen atmosphere. NaH (480 mg, 12 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 6-b (1.70 g, 2 mmol) and Pd (PPh ₄ ) ₃ (277 mg, 0.24 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24-36 h. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give 1.5 g of yellow solid. The solid was then washed twice with dichloromethane and filtered to give 6-c as a yellow solid (1.4 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

Under a nitrogen atmosphere, 6-c (1.4 g, 2 mmol) and DCM (200 ml) were placed in a 500 ml two-necked flask. After cooling to 0 ° C., PIFA (1.72 g, 4.0 mmol) was then added in portions. After stirring at room temperature for 7 days, the solution was purple black. Then the solution was concentrated to about 20 mL. n-Hexane (450 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a gray-black solid. The solid was washed twice with DCM / PE (2: 1, 100 mL) to give compound 69 as a gray-black solid (1.2 g, 85% yield). 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 placed in a 250 ml two-necked flask and N _{2 was} flushed through for 15 min. Pd (OAc) ₂ (293 mg, 1.3 mmol) and SPhos (1.12 g, 2.73 mmol) were added with stirring. After stirring for an additional 10 min, 3-a (15.8 g, 65 mmol), B ₂ pin ₂ (23 g, 91 mmol) and KOAc (12.7 g, 130 mmol) were added sequentially and the mixture was increased Warmed up to 110 ° C., heated to reflux and _{stirred overnight under N 2} protection. After the reaction was complete, the reaction was cooled, filtered through Celite, washed with DCM, and isolated on silica gel column chromatography to give 3-b as a white solid (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 placed in a 250 mL two neck flask and nitrogen was purged for 15 minutes. Pd (OAc) ₂ (293 mg, 1.3 mmol) and XPhos (1.34 g, 2.8 mmol) were added with stirring. After stirring for an additional 10 minutes, 1-a (4.1 g, 13 mmol), 3-b (15.0 g, 52 mmol), and cesium fluoride (9.5 g, 62.4 mmol) were added sequentially. The reaction was warmed to 110 ° C, heated to reflux and stirred overnight under a nitrogen atmosphere. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane and isolated on silica gel column chromatography to give 3-c as a white solid (4.4 g, 70% yield). 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]

3-c (8.1 g, 16.7 mmol) was added to THF (250 mL) under a nitrogen atmosphere. The mixture was cooled to -94 ° C. (in an acetone / liquid nitrogen cold bath). n-Butyllithium (24 mL, 38.4 mmol, 1.6 M in n-hexane) was slowly added dropwise. The reaction was held at this temperature for 1 h, then slowly warmed to -78 ° C. (in a cold bath made of acetone / dry ice) and reacted for 8 h. A solution of elemental iodine (12.73 g, 50.1 mmol) in THF (20 mL) was added. After the addition, the mixture was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified on silica gel column chromatography to give 3-d as a white solid (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]

Malononitrile (1.58 g, 24 mmol) was added to anhydrous DMF (40 mL) under a nitrogen atmosphere. NaH (960 mg, 24 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 3-d (3.0 g, 4 mmol) and Pd (PPh ₄ ) ₃ (462 mg, 0.4 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24-36 h. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give 2.8 g of yellow solid. The solid was then washed twice with dichloromethane and filtered to give 3-e as a yellow solid (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 (2.4 g, 4 mmol) was placed in a 500 mL single neck flask and DCM (200 mL) was added. The mixture was cooled to 0 ° C and PIFA (3.44 g, 8 mmol) was added in portions. After stirring at room temperature for 3 days, the solution was purple black. The solution was then placed in a 1 L one-neck flask and the solution was evaporated to about 50 mL on a rotary evaporator and n-hexane (450 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a black solid to surrender. The solid was washed twice with DCM / PE (2: 1, 200 mL) to give 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]

THF (130 mL) and deionized water (130 mL) were placed in a 500 mL two-necked flask and nitrogen was flushed through for 15 minutes. Pd (PPh ₃ ) ₄ (1.73 g, 1.5 mmol), 7-a (13.0 g, 50 mmol), 3,5-bis (trifluoromethyl) phenylboronic acid (14.2 g, 55 mmol) and Cesium fluoride (11.1 g, 72 mmol) were added sequentially. The mixture was stirred under a nitrogen atmosphere overnight. After the completion of the reaction, the mixture was extracted with dichloromethane, dried and isolated on silica gel column chromatography to give 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 placed in a 250 mL two-necked flask and N ₂ was flushed through for 15 min. Pd (OAc) ₂ (113 mg, 0.5 mmol) and SPhos (431 mg, 1.05 mmol) were added with stirring. After stirring for an additional 10 min, 7-b (7.8 g, 20 mmol), B ₂ pin ₂ (7.1 g, 28 mmol) and KOAc (3.92 g, 40 mmol) were added sequentially and the mixture was added warmed to 110 ° C, heated to reflux and _{stirred overnight under N 2} protection. After the reaction was complete, the reaction was cooled, filtered through Celite, washed with DCM, and isolated on silica gel column chromatography to give 7-c as a white solid (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]

THF (1 L) was added to a 2 L two-necked flask and nitrogen was purged for 15 minutes. Pd (OAc) ₂ (141 mg, 0.625 mmol) and XPhos (646 mg, 1.38 mmol) were added with stirring. After stirring for an additional 10 minutes, 1-a (4.0 g, 12.5 mmol), 7-c (22.2 g, 46 mmol) and cesium fluoride (10.5 g, 68.8 mmol) were added sequentially. The mixture was warmed to 110 ° C., heated to reflux and stirred overnight under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled, filtered through Celite, washed with THF, and isolated on silica gel column chromatography to give 7-d as a white solid (11.6 g, 83% yield). 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]

7-d (6.02 g, 6.9 mmol) was added to THF (250 mL) under a nitrogen atmosphere. The mixture was cooled to -72 ° C. 2,2,6,6-Tetramethylpiperidinyl magnesium chloride-lithium chloride complex (16.6 mL, 16.6 mmol, 1.0 M solution) was slowly added dropwise. The reaction was kept at this temperature for 1 hour, then slowly warmed to -20 ° C. and reacted at this temperature for 2 hours. Then the The mixture was cooled again to -78 ° C. and a solution of elemental iodine (7.11 g, 28 mmol) in THF (20 ml) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified on silica gel column chromatography to give 7-e as a white solid product (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]

Malononitrile (1.35 g, 20.4 mmol) was added to anhydrous DMF (40 mL) under a nitrogen atmosphere. NaH (820 mg, 20.4 mmol, 60% content) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes. 7-e (3.82 g, 3.4 mmol) and Pd (PPh ₄ ) ₃ (393 mg, 0.34 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24-36 h. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. A large amount of solid precipitated out after vigorous stirring. The mixture was filtered to collect a solid. The solid was washed with dichloromethane and filtered to give 3.3 g of an off-white solid. The solid was then washed twice with solvent (DCM, 200 mL) and filtered to give 7-f as an off-white solid (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 a nitrogen atmosphere, 7-f (3.2 g, 3.2 mmol) was placed in a 500 mL one-neck flask and DCM (200 mL) was added. After cooling to 0 ° C., PIFA (2.92 g, 6.8 mmol) was added in portions admitted. After stirring at room temperature for 5 days, the solution was purple black. The solution was then placed in a 1 L single neck flask and the solution was evaporated to approximately 50 mL on a rotary evaporator. n-Hexane (450 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a black solid. The solid was washed twice with DCM / PE (1: 1, 200 mL) to give compound 72 as a black solid (2.8 g, 88% yield). 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 placed in a 500 mL two-necked flask and nitrogen was flushed through for 15 minutes. Pd (OAc) ₂ (423 mg, 1.6 mmol) and XPhos (1.53 g, 3.2 mmol) were added with stirring. After stirring for an additional 10 minutes, 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) were successively admitted. The reaction was warmed to 110 ° C, heated to reflux and stirred under nitrogen overnight. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane and isolated on silica gel column chromatography to give 8-b as a white solid (6.7 g, 45% yield).

Step 2: Synthesis of [Intermediate 8-c]

8-b (6.5 g, 6.85 mmol) was added to THF (325 mL) under a nitrogen atmosphere. The mixture was cooled to -78 ° C. LDA (9.7 mL, 15.7 mmol) was slowly added dropwise. The reaction was held at this temperature for 10 min, then slowly warmed to -15 ° C. and the color of the solution was red-black. After 2 h, a solution of elemental iodine (5.22 g, 20.56 mmol) in THF (20 mL) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was started with a small amount of a saturated aqueous ammonium chloride solution quenched and celite added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 10: 1-2: 1) to give 8-c as a white solid product (5.1 g, 62% yield).

Step 3: Synthesis of [Intermediate 8-d]

Malononitrile (2.06 g, 31.2 mmol) was added to anhydrous DMF (100 mL) under a nitrogen atmosphere. NaH (1.22 g, 30.3 mmol) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes and the solution appeared light yellow. 8-c (5.0 g, 4.16 mmol) and Pd (PPh ₄ ) ₃ (0.89 g, 0.77 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24 h . After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give a yellow solid. The solid was heated in toluene at 90 ° C for 1.5 h and filtered to give 8-d as a yellow solid (4.3 g, 95% yield).

Step 4: Synthesis of Compound 54

Under a nitrogen atmosphere, 8-d (4.3 g, 3.97 mmol) was placed in a two-necked flask and DCM (430 mL, 0.01M) was added. After cooling to 0 ° C., PIFA (1.79 g, 4.17 mmol) was then added in portions. After stirring at room temperature for 1 day, the solution was purple black. The solution was then placed in a 1 L one-neck flask and the solution was concentrated to about 50 mL. n-Hexane (250 mL) was added and the mixture was stirred for 10 minutes and then filtered. Then the solid was washed twice with DCM / PE (1: 1, 200 mL) to give compound 54 as a purple-black To give solid (3.0 g, 70% yield). The product was confirmed as the target product with a molecular weight of 1,074.

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 purged for 15 minutes. Pd (OAc) ₂ (1.27 g, 5.66 mmol) and XPhos (5.62 g, 11.8 mmol) were added with stirring. After stirring for an additional 10 minutes, 1-a (15.0 g, 47.18 mmol), 2-phenyl-phenylboronic acid (39.2 g, 198.1 mmol) and cesium fluoride (33.25 g, 240.6 mmol ) added one after the other. The reaction was warmed to 110 ° C, heated to reflux and stirred under nitrogen overnight. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane and isolated on silica gel column chromatography to give 9-a as a white solid (5.0 g, 23% yield).

Step 2: Synthesis of [Intermediate 9-b]

9-a (4.92 g, 10.59 mmol) was added to THF (120 mL) under a nitrogen atmosphere. The mixture was cooled to -78 ° C. LDA (15.0 mL, 24.36 mmol, 1.6 M solution) was slowly added dropwise. The reaction was held at this temperature for 10 min, then slowly warmed to -15 ° C. After 2 h a solution of elemental iodine (8.07 g, 31.77 mmol) in THF (20 mL) was added. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 10: 1-2: 1) to give 9-b as a white solid product (6.2 g, 81% yield).

Step 3: Synthesis of [Intermediate 9-c]

Malononitrile (4.28 g, 64.9 mmol) was added to anhydrous DMF (86 mL) under a nitrogen atmosphere. NaH (2.52 g, 63.1 mmol) was added in portions at 0 ° C. The mixture was stirred at 0 ° C for 10 minutes and at room temperature for 20 minutes and the solution appeared light yellow (or reddish). 9-b (6.2 g, 8.65 mmol) and Pd (PPh ₄ ) ₃ (1.84 g, 1.6 mmol) were then added and the mixture was warmed to 90 ° C and reacted for 24 h. After the conversion was complete, the reaction mixture was poured into ice water and the pH adjusted to <1 with dilute 4N hydrochloric acid. After vigorous stirring, a large amount of yellow solid precipitated. The mixture was filtered to collect a solid. The solid was washed with dichloromethane to give a yellow solid. The solid was then washed with toluene at 90 ° C for 1.5 h and filtered to give 9-c as a yellow solid (4.81 g, 93% yield).

Step 4: Synthesis of Compound 1367

Under a nitrogen atmosphere, 9-c (4.81 g, 8, .12 mmol) was placed in a two-necked flask and DCM (480 mL) was added. After cooling to 0 ° C., PIFA (3.67 g, 8.53 mmol) was then added in portions. After stirring at room temperature for 1 day, the solution was then placed in a 1 L one-neck flask and the solution was concentrated to about 50 mL. n-Hexane (400 mL) was added and the mixture was stirred for 10 minutes and then filtered to give a purple-black solid. Then the solid was washed twice with DCM / PE (1: 1, 200 mL) to give compound 1367 as a purple-black solid (4.1 g, 85% yield). The product was confirmed as the target product with a molecular weight of 590.

Synthesis Example 10: Synthesis of Compound 43

Step 1: Synthesis of [Intermediate 10-b]

Dioxane (160 mL) was placed in a 250 mL two-necked flask and nitrogen was flushed through for 15 minutes. Pd (OAc) ₂ (0.282 g, 1.26 mmol) and XPhos (1.2 g, 2.52 mmol) were added with stirring. After stirring for an additional 10 minutes, 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 added sequentially admitted. The reaction was warmed to 80 ° C for reaction and stirred under nitrogen overnight. After the completion of the reaction, the reaction mixture was cooled, filtered through Celite, washed with dichloromethane, and isolated through silica gel column chromatography to give 10-b as a white solid (13 g, 93.6% yield).

Step 2: Synthesis of [Intermediate 10-c]

Under a nitrogen atmosphere, 10-b (12 g, 21.7 mmol) and THF (240 mL) were added to a dry 500 mL Schlenk flask. The mixture was cooled to -30 ° C. 2,2,6,6-Tetramethylpiperidinyl magnesium chloride-lithium chloride complex (54 mL, 54 mmol, 1.0 M solution) was slowly added dropwise. The mixture then reacted at -30 ° C. for 2 h, and the complete lithiation was checked by sampling and HPLC. A solution of elemental iodine (16.55 g, 65.1 mmol) in THF (50 mL) was added at -30 ° C. After the addition, the reaction was slowly warmed to room temperature and reacted overnight. The reaction was quenched with a small amount of saturated aqueous ammonium chloride solution and Celite was added directly. The mixture was purified by silica gel column chromatography (PE: DCM = 10: 1-2: 1-1: 1), and washed with PE: DCM = 10: 1 to give 10-c as a white solid (12 g , 69% yield).

Step 3: Synthesis of [Intermediate 10-d]

Under a nitrogen atmosphere, NaH (2.98 g, 74.4 mmol) and super-dry DMF (80 mL) were added to a dry 1 L three-necked flask. Malononitrile (4.95 g, 75 mmol) was added at 0 ° C. The mixture was stirred at room temperature for 0.5 h and 10-c (10 g, 12.4 mmol) and Pd (PPh ₄ ) ₃ (0.718 g, 0.62 mmol) were then added and the mixture was increased to 80 ° C warmed up and implemented for 18 h. After the completion of the reaction, 100 mL of 2N HCl was added dropwise and the mixture was filtered to give the crude product. The crude product was refluxed with acetone to remove water, dissolved clear with acetone, insoluble material filtered off and the filtrate evaporated to dryness and crystallized to give 10-d as a white (light yellow) solid (8.5 g, 91% yield).

Step 4: Synthesis of Compound 43

Under a nitrogen atmosphere, 10-d (8.5 g, 12.5 mmol) and DCM (750 mL) were placed in a 2 L three-necked flask. Then, a solution of PIFA (5.91 g, 13.75 mmol) was added dropwise at 0 ° C, and the mixture was reacted for 20 hours. The solution was then placed in a 2 L single neck flask and the solution was rotary evaporated to approximately 100 mL. n-Hexane (500 mL) was added and the mixture was stirred for 10 minutes, then filtered to give a purple-black solid. The solid was washed twice with DCM / PE (2: 1, 200 mL) to give compound 43 as a purple-black solid (7.5 g, 88% yield). The product was confirmed as the target product with a molecular weight of 678.

Those skilled in the art should know that the above production process is only an illustrative example, and those skilled in the art can obtain the structure of other compounds of the present invention by modifying the above production process.

Device example 1

Device example 1.1:

A glass substrate with a 80 nm thick, transparent indium tin oxide (ITO) electrode was subjected to an oxygen plasma and a UV-ozone treatment. The cleaned glass substrate was dried in a glove box on a hot plate before deposition. The following materials were sequentially deposited on the surface of the glass at a rate of 0.2-2 Angstroms / s under a vacuum of about 10 ^-8 Torr. First, the compound 56 of the present invention was deposited on the surface of the glass substrate to form a 10 nm thick layer that served as a hole injection layer (HIL). Next, Compound HT1 was deposited on the layer obtained above to form a 120 nm thick layer that served as a hole transport layer (HTL). Next, Compound EB1 was deposited on the layer obtained above to form a 5 nm thick layer which served as an electron barrier layer (EBL). Next, Compound BH and Compound BD (in a weight ratio of 96: 4) were co-deposited on the layer obtained above to form a 25 nm thick layer which served as an emitter layer (EML). Next, Compound HB1 was deposited on the layer obtained above to form a 5 nm thick layer which served as a hole blocking layer (HBL). Then, 8-hydroxyquinolinolato-lithium (Liq) and the compound ET1 (in a weight ratio of 60:40) were co-deposited on the layer obtained above to form a 30 nm thick layer which served as an electron transport layer (ETL). Finally, Liq was deposited to form a 1 nm thick layer that served as an electron injection layer (EIL), and 120 nm thick Al was deposited to form a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorbent to complete the device.

Device example 1.2:

Device Example 1.2 was made in the same manner as Device Example 1.1, except that Compound 68 was used in place of Compound 56 to serve as an HIL.

Device example 1.3:

Device Example 1.3 was made in the same manner as Device Example 1.1, except that Compound 70 was used in place of Compound 56 to serve as an HIL.

Device example 1.4:

Device Example 1.4 was fabricated in the same manner as Device Example 1.3, except that Compound 70 was used to form a 5 nm thick layer to serve as an HIL.

Device example 1.5:

Device Example 1.5 was fabricated in the same manner as Device Example 1.3, except that Compound 70 was used to form a 2 nm thick layer to serve as an HIL.

Device example 1.6:

Device Example 1.6 was manufactured in the same manner as Device Example 1.3, except that HT2 was used in place of HT1 to serve as an HTL.

Device example 1.7:

Device Example 1.7 was fabricated in the same manner as Device Example 1.6, except that Compound 70 was used to form a 2 nm thick layer to serve as an HIL.

Device example 1.8:

Device Example 1.8 was fabricated in the same manner as Device Example 1.6, except that Compound 70 was used to form a 1 nm thick layer to serve as an HIL.

Device comparison example 1.1:

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

Device comparison example 1.2:

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

Details of the layer structure and thickness of the devices are shown in the table below. Layers in which more than one material is used are obtained by doping different compounds in the weight ratios described therein. Table 1 Device structures of examples and comparative examples of devices Device ID HIL HTL EBL EML HBL ETL Device example 1.1 Compound 56 (10 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.2 Compound 68 (10 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.3 Compound 70 (10 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.4 Compound 70 (5 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.5 Compound 70 (2 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.6 Compound 70 (10 nm) Connection HT2 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.7 Connection 70 (2nm) Connection HT2 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 1.8 Connection 70 (1nm) Connection HT2 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device comparison example 1.1 Compound HI 1 (10 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40: 60.30 nm) Device comparison example 1.2 no Connection HT2 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm)

Structure of the materials used in the devices is shown below:

The above devices were measured for IVL characteristics at 10 mA / cm ² , and their voltage (V), power efficiency (PE) and life (LT95) were recorded and shown in Table 2. Table 2 Device data Number device Voltage (V) PE (lm / W) LT95 (h) Device example 1.1 4.22 4.64 183 Device example 1.2 4.56 4.87 1204 Device example 1.3 4.18 4.70 292 Device example 1.4 4.08 4.97 601 Device example 1.5 4.07 5.25 643 Device example 1.6 4.12 4.49 1572 Device example 1.7 4.11 5.15 1615 Device example 1.8 4.12 5.25 1596 Device comparison example 1.1 4.72 4.22 30th Device comparison example 1.2 8.34 4.02 93

Discussion 1:

As can be seen from the above table, when a single material was used as the hole injection layer, in 8 preferred examples of the present invention and comparative examples, the preferred examples were superior to the comparative examples in terms of voltage, power efficiency and durability. The voltage was reduced by about 0.5 V, the power efficiency was improved and multiplied in terms of service life. Even when the thickness of the hole injection layer was reduced to 5 nm and 2 nm, and even to 1 nm, the voltage, efficiency and durability were still excellent. In particular, with no hole injection layer, the voltage of the device was up to 8.34 V, and power efficiency and lifetime were also lower than those of devices with a hole line layer. From this it can be seen that the compounds of the present invention, when used alone as a hole injection layer, were a better choice than comparative compounds and produced a completely unexpected improvement.

Device example 2

Device example 2.1:

A glass substrate with a 80 nm thick, transparent indium tin oxide (ITO) electrode was subjected to an oxygen plasma and a UV-ozone treatment. The cleaned glass substrate was dried in a glove box on a hot plate before deposition. The following materials were sequentially deposited on the surface of the glass at a rate of 0.2-2 Angstroms / s under a vacuum of about 10 ^-8 Torr. First, Compound 56 (as a dopant) of the present invention was deposited together with Compound HT1 (in a weight ratio of 3:97) on the surface of the glass substrate to form a 10 nm thick layer that served as a hole injection layer (HIL). Next, Compound HT1 was deposited on the layer obtained above to form a 120 nm thick layer that served as a hole transport layer (HTL). Next, Compound EB1 was deposited on the layer obtained above to form a 5 nm thick layer which served as an electron barrier layer (EBL). Next, Compound BH and Compound BD (in a weight ratio of 96: 4) were co-deposited on the layer obtained above to form a 25 nm thick layer which served as an emitter layer (EML). Next, Compound HB1 was deposited on the layer obtained above to form a 5 nm thick layer which served as a hole blocking layer (HBL). Then, 8-hydroxyquinolinolato-lithium (Liq) and the compound ETI (in a weight ratio of 60:40) were co-deposited on the layer obtained above to form a 30 nm thick layer which served as an electron transport layer (ETL). Finally, Liq was deposited to form a 1 nm thick layer that served as an electron injection layer (EIL), and 120 nm thick Al was deposited to form a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorbent to complete the device.

Device example 2.2:

Device Example 2.2 was made in the same manner as Device Example 2.1, except that in the HIL, compound 68 was used in place of compound 56 to serve as a dopant.

Device example 2.3:

Device Example 2.3 was made in the same manner as Device Example 2.1, except that in the HIL, compound 70 was used in place of compound 56 to serve as a dopant.

Device example 2.4:

Device Example 2.4 was made in the same manner as Device Example 2.1, except that Compound HT2 was used in place of Compound HT1 to co-co-co-co-co-co-co-co-deposit with Compound 56 (in a weight ratio of 97: 3) to serve as an HIL and Compound HT2 was used in place of compound HT1 to serve as an HTL.

Device example 2.5:

Device Example 2.5 was fabricated in the same manner as Device Example 2.4, except that in the HIL, compound 68 was used in place of compound 56 to serve as a dopant.

Device example 2.6:

Device Example 2.6 was made in the same manner as Device Example 2.4, except that in the HIL, compound 69 was used in place of compound 56 to serve as a dopant.

Device example 2.7:

Device Example 2.7 was made in the same manner as Device Example 2.4, except that Compound HT2 and Compound 42 were co-deposited (in a weight ratio of 98: 2) to serve as an HIL.

Device example 2.8:

Device Example 2.8 was fabricated in the same manner as Device Example 2.7, except that compound 72 was used in place of compound 42 in the HIL to serve as a dopant.

Device example 2.9:

Device Example 2.9 was fabricated in the same manner as Device Example 2.7, except that in the HIL, compound 54 was used in place of compound 42 to serve as a dopant.

Device example 2.10:

Device Example 2.10 was made in the same manner as Device Example 2.7, except that in the HIL compound 1367 was used in place of compound 42 to serve as a dopant.

Device example 2.11:

Device Example 2.11 was fabricated in the same manner as Device Example 2.7, except that Compound 43 was used in place of Compound 42 in the HIL to serve as a dopant.

Device comparison example 2:

Device Comparative Example 2 was fabricated in the same manner as in Device Example 2.1, except that in the HIL, compound HI1 was used in place of compound 56 to serve as a dopant.

The specific structure of the connections employed in the devices is as shown in Device Example 1.

Details of the layer structure and thickness of the devices are shown in the table below. Layers in which more than one material is used are obtained by doping different compounds in the weight ratios described therein. Table 3 Device structures of device examples and comparative examples Device ID HIL HTL EBL EML HBL ETL Device example 2.1 Connection 56: Connection HT1 (3:97, 10 nm) Connection HT1 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.2 Connection 68: Connection HT1 (3:97, 10 nm) Connection HT1 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.3 Connection 70: Connection HT1 (3:97, 10 nm) Connection HT1 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.4 Connection 56: Connection HT2 (3:97, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.5 Connection 68: Connection HT2 (3:97, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.6 Connection 69: Connection HT2 (3:97, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.7 Connection 42: Connection HT2 (2:98, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.8 Connection 72: Connection HT2 (2:98, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.9 Connection 54: Connection HT2 (2:98, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.10 Connection 1367: Connection HT2 (2:98, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device example 2.11 Connection 43: Connection HT2 (2:98, 10 nm) Connection HT2 (120 nm) Connection EB 1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB 1 (5nm) Compound ET1: Liq (40:60, 30 nm) Device comparison example 2 Connection HI1: Connection HT1 (3:97, 10 nm) Connection HT1 (120 nm) Connection EB1 (5nm) Connection BH: Connection BD (96: 4, 25 nm) Connection HB1 (5nm) Compound ET1: Liq (40:60, 30 nm)

The specific structure of new compounds used in the devices are shown below:

The above devices were measured for IVL characteristics at 10 mA / cm ² , and their voltage (V), power efficiency (PE) and life (LT95) were recorded and shown in Table 4. Table 4 Device data Device ID Voltage (V) PE (lm / W) LT95 (h) Device example 2.1 4.18 5.55 94 Device example 2.2 4.17 5.65 980 Device example 2.3 4.03 5.64 250 Device example 2.4 4.09 5.49 328 Device example 2.5 4.11 5.60 1820 Device example 2.6 4.00 5.45 617 Device example 2.7 4.01 5.55 967 Device example 2.8 3.97 5.61 1248 Device example 2.9 3.99 5.62 1560 Device example 2.10 4.07 5.37 1759 Device example 2.11 3.97 5.45 779 Device comparison example 2 8.57 2.74 6th

Discussion 2:

As can be seen from the above table, when compounds of the 11 preferred examples of the present invention and the comparative examples were used as the dopant in HT1 or HT2 as the hole injection layer, the two types of materials are very different in terms of device performance. First, in terms of voltage, the voltage of the comparative example was as high as 8.57 volts, while the voltage of the preferred examples was only about 4.18 volts, which is a reduction of half. The power efficiency of the examples was also twice or higher than that of the comparative example. In particular, the life of the preferred examples was ten times that of the comparative example. The life of the preferred examples and that of the comparative example were not of the same order of magnitude. Therefore, the compounds disclosed in the present invention, when used as a dopant, were a class of hole injection materials superior to the comparative compound. The compounds of the present invention produced totally unexpected improvements in improving device performance, particularly in reducing voltage and increasing life, and had overwhelming benefits.

Device example 3

Device example 3.1

A glass substrate with a 80 nm thick, transparent indium tin oxide (ITO) electrode was subjected to an oxygen plasma and a UV-ozone treatment. The cleaned glass substrate was dried in a glove box on a hot plate before deposition. The following materials were sequentially deposited on the surface of the glass at a rate of 0.2-2 Angstroms / s under a vacuum of about 10 ^-8 Torr. First, the compound 56 was deposited on the surface of the glass substrate to form a 10 nm thick layer as a hole injection layer (HIL). Next, Compound HT1 was deposited on the layer obtained above to form a 35 nm thick layer that served as a hole transport layer (HTL). Next, Compound EB2 was deposited on the layer obtained above to form a 5 nm thick layer which served as an electron barrier layer (EBL). Next, Compound EB2, Compound HB2 and Compound GD (in a weight ratio of 46: 46: 8) were co-deposited on the layer obtained above to form a 40 nm thick layer which served as an emitter layer (EML). Next, Compound HB2 was deposited on the layer obtained above to form a 5 nm thick layer which served as a hole blocking layer (HBL). Then, 8-hydroxyquinolinolato-lithium (Liq) and the compound ET2 (in a weight ratio of 60:40) were co-deposited on the layer obtained above to form a 35 nm thick layer which served as an electron transport layer (ETL). Finally, Liq was deposited to form a 1 nm thick layer that served as an electron injection layer (EIL), and 120 nm thick Al was deposited to form a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorbent to complete the device.

Device example 3.2:

Example 3.2 was prepared in the same manner as in Example 3.1, except that Compound 56 (as a dopant) and Compound HT1 (in a weight ratio of 3:97) were co-evaporated to replace Compound 56 as a hole injection layer (HIL) serve.

Device example 3.3:

Example 3.3 was prepared in the same manner as Example 3.1, except that Compound 70 was used in place of Compound 56 to serve as a hole injection layer (HIL) and Compound HT2 was used to serve as HTL in place of Compound HT1.

Device example 3.4:

Example 3.4 was prepared in the same manner as in Example 3.3, except that Compound 70 (as a dopant) and Compound HT2 (in a weight ratio of 3:97) were co-evaporated to replace Compound 70 as a hole injection layer (HIL) serve.

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

Details of the layer structure and thickness of the devices are shown in the table below. Layers in which more than one material is used are obtained by doping different compounds in the weight ratios described therein. Table 5 Device Structure of Device Examples Device ID HIL HTL EBL EML HBL ETL Device example 3.1 Compound 56 (10 nm) Connection HT1 (35 nm) Connection EB2 (5nm) Connection EB2: Connection HB2: Connection GD (46: 46: 8, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 3.2 Connection 56: Connection HT1 (3:97, 10 nm) Connection HT1 (35 nm) Connection EB2 (5nm) Connection EB2: Connection HB2: Connection GD (46: 46: 8, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 3.3 Compound 70 (10 nm) Connection HT2 (35 nm) Connection EB2 (5nm) Connection EB2: Connection HB2: Connection GD (46: 46: 8, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 3.4 Connection 70: Connection HT2 (3:97, 10 nm) Connection HT2 (35 nm) Connection EB2 (5nm) Connection EB2: Connection HB2: Connection GD (46: 46: 8, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm)

The above devices were measured for IVL characteristics at 10 mA / cm ² , and their voltage (V), power efficiency (PE) and life (LT95) were recorded and shown in Table 6. Table 6 Device data Device ID Voltage (V) PE (lm / W) LT95 (h) Device example 3.1 3.56 71.15 1245 Device example 3.2 3.51 76.77 859 Device example 3.3 3.53 72.29 1343 Device example 3.4 3.51 77.05 1097

Discussion 3:

As can be seen from the green light emitting device, when compound 56 and compound 70 were used alone as the hole injection layer, excellent stress, efficiency, and durability values were obtained. When compound 56 and compound 70 were used as dopants in a hole injection layer, the voltage was similar to Example 3.1 and Example 3.3, and the efficiency was slightly higher, while longer life was achieved when compound 56 and compound 70 were used alone as the hole injection layer were.

Device example 4

Device example 4.1

A glass substrate with a 80 nm thick, transparent indium tin oxide (ITO) electrode was subjected to an oxygen plasma and a UV-ozone treatment. The cleaned glass substrate was dried in a glove box on a hot plate before deposition. The following materials were sequentially deposited on the surface of the glass at a rate of 0.2-2 Angstroms / s under a vacuum of about 10 ^-8 Torr. First, the compound 56 was deposited on the surface of the glass substrate to form a 10 nm thick layer as a hole injection layer (HIL). Next, Compound HT1 was deposited on the layer obtained above to form a 40 nm thick layer that served as a hole transport layer (HTL). Next, Compound EB2 was deposited on the layer obtained above to form a 5 nm thick layer which served as an electron barrier layer (EBL). Next, Compound RH and Compound RD (in a weight ratio of 98: 2) were co-deposited on the layer obtained above to form a 40 nm thick layer which served as an emitter layer (EML). Next, Compound HB2 was deposited on the layer obtained above to form a 5 nm thick layer which served as a hole blocking layer (HBL). Then, 8-hydroxyquinolinolato-lithium (Liq) and the compound ET2 (weight ratio 60:40) were co-deposited on the layer obtained above to form a 35 nm thick layer which served as an electron transport layer (ETL). Finally, Liq was deposited to form a 1 nm thick layer that served as an electron injection layer (EIL), and 120 nm thick Al was deposited to form a cathode. The device was then placed back in the glovebox transferred and encapsulated with a glass lid and a moisture absorbent to complete the device.

Device example 4.2:

Example 4.2 was prepared in the same manner as in Example 4.1, except that Compound 56 (as a dopant) and Compound HT1 (in a weight ratio of 3:97) were evaporated together on the surface of a glass substrate to form a 10 nm thick layer to serve as a hole injection layer (HIL).

Device example 4.3:

Example 4.3 was prepared in the same manner as Example 4.1, except that Compound 70 was used in place of Compound 56 to serve as a hole injection layer (HIL) and Compound HT2 was used to serve as HTL in place of Compound HT1.

Device example 4.4:

Example 4.4 was prepared in the same manner as in Example 4.3, except that Compound 70 (as a dopant) and Compound HT2 (in a weight ratio of 3:97) were co-evaporated to replace Compound 70 as a hole injection layer (HIL) serve.

The specific structure of the connections used in the devices are shown below:

Details of the layer structure and thickness of the devices are shown in the table below. Layers in which more than one material is used are obtained by doping different compounds in the weight ratios described therein. Table 7 Device Structure of Device Examples Device ID HIL HTL EBL EML HBL ETL Device example 4.1 Compound 56 (10 nm) Connection HT1 (40 nm) Connection EB2 (5nm) Connection RH: Connection RD (98: 2, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 4.2 Connection 56: Connection HT1 (3:97, 10 nm) Connection HT1 (40 nm) Connection EB2 (5nm) Connection RH: Connection RD (98: 2, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 4.3 Compound 70 (10 nm) Connection HT2 (40 nm) Connection EB2 (5nm) Connection RH: Connection RD (98: 2, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm) Device example 4.4 Connection 70: Connection HT2 (3:97, 10 nm) Connection HT2 (40 nm) Connection EB2 (5nm) Connection RH: Connection RD (98: 2, 40 nm) Connection HB2 (5nm) Connection Liq: ET2 (60:40, 35 nm)

The above devices were measured for IVL characteristics at 10 mA / cm ² , and their voltage (V), power efficiency (PE) and life (LT95) were recorded and shown in Table 8. Table 8 Device data Device ID Voltage (V) PE (lm / W) LT95 (h) Device example 4.1 4.37 13.33 7469 Device example 4.2 4.32 15.31 4325 Device example 4.3 4.44 12.79 4659 Device example 4.4 4.44 14.40 5200

Discussion 4:

As can also be seen from the red light-emitting device, when compound 56 and compound 70 were used alone as the hole injection layer, excellent values in terms of voltage, efficiency and life were achieved. When compound 56 and compound 70 were used as dopants in a hole injection layer, the voltage was similar and the efficiency slightly higher compared to Example 4.1 and Example 4.3, while longer life was achieved when compound 56 was used alone as the hole injection layer.

Based on the above results, it can be concluded that the dehydrobenzodioxazole derivatives, regardless of whether they are used alone as a hole injection layer or as a dopant, have excellent effects in red, green and blue light emitting devices and are rare hole injection materials.

The compounds disclosed in the present invention are dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole derivatives. Since the heteroatoms contained in the molecular skeleton are different, the lowest unoccupied molecular orbitals (LUMOs) are also different. The LUMOs of dehydrobenzodioxazole (NO compounds), dehydrobenzodithiazole (NS compounds) and dehydrobenzodiselenazole derivatives (NSe compounds) were calculated using DFT (GAUSS-09, under the condition of B3LYP / 6-311G (d)). The results are shown in the table below. Table 9 DFT calculation results NO connection LUMO (eV) NS connection LUMO (eV) NSe connection LUMO (eV) Connection 1 -5.82 Compound 89 -5.66 Compound 177 -5.58 Connection 6 -6.18 Compound 94 -6.03 Compound 182 -5.95 Connection 13 -5.57 Compound 101 -5.46 Compound 189 -5.40 Connection 15 -5.32 Compound 103 -5.24 Compound 191 -5.18 Connection 25 -5.69 Compound 113 -5.61 Compound 201 -5.56 Connection 26 -5.43 Compound 114 -5.36 Compound 202 -5.30 Connection 38 -5.68 Compound 126 -5.55 Compound 214 -5.48 Connection 43 -5.72 Compound 131 -5.63 Compound 219 -5.40 Connection 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 Connection 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 Connection 42 -5.75 Compound 130 -5.59 Compound 218 -5.53 Connection 54 -5.65 Connection 142 -5.49 Connection 230 -5.43 Connection 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

As can be seen from the results for the above devices, devices containing dehydrobenzodioxazole derivatives showed excellent performance in every aspect, and the dehydrobenzodioxazole derivatives were highly efficient hole injection materials. As can be seen from the DFT calculation results, the LUMOs of dehydrobenzodioxazole derivatives, dehydrobenzodithiazole derivatives, and dehydrobenzodiselenazole derivatives when comparing the same series of molecules were almost the same, about 0.2 eV, indicating that all three kinds of compounds have a lower LUMO Level and are extremely electron deficient. Therefore, dehydrobenzodithiazole derivatives and dehydrobenzodiselenazole derivatives have the potential to be excellent hole injection materials that can greatly improve the performance of OLEDs, e.g., enable a device to have longer life, higher efficiency and lower voltage, and have very broad industrial application prospects.

As can be seen from the above results of the devices and DFT calculations, novel compounds of the present invention having a structure of dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole are very important charge transport materials. In particular, they have unparalleled hole transport advantages and are suitable for use in various types of organic semiconductor devices including, but not limited to, fluorescent OLEDs, phosphorescent OLEDs, white OLEDs, stacked OLEDs, OTFTs, OPVs, and the like.

It should be understood that the various embodiments described herein are exemplary only and are not intended to limit the scope of the invention. The present invention as claimed may therefore include deviations from the particular examples and preferred embodiments described herein, as will be apparent to a person skilled in the art. Many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. It should be understood that various theories as to why the invention works are not intended to be limiting.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• US 20050121667 [0008]
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• US 2003/0230980 [0017]
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Non-patent literature cited

• Applied Physics Letters, 1987, 51 (12): 913-915 [0003]

Claims (17)

Connection with Formula 1:

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se; wherein Z ₁ and Z ₂ are selected identically or differently for each occurrence from O, S or Se; R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted one or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 Koh fuel atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof; wherein each R can 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; and adjacent substituents may optionally be linked to form a ring. Connection after Claim 1 wherein X and Y for each occurrence, identically or differently, are selected from CR "R""orNR", wherein R ', R "and R"' are groups having at least one electron-withdrawing group; where R, R ', R "and R"' are preferably groups with at least one electron-withdrawing group. Connection after Claim 1 wherein X and Y are selected identically or differently for each occurrence from O, S or Se and at least one of R is a group with at least one electron-withdrawing group; where preferably all R are groups with at least one electron-withdrawing group. Link to any of the Claims 1 - 3 , the Hammett constant of the electron-withdrawing group being ≥ 0.05, preferably 0.3, more preferably 0.5. Link to any of the Claims 1 - 4th , wherein the electron-withdrawing group is selected from the group consisting of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, an aza aromatic ring group and any of the following groups substituted with one or more of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso and an aza -aromatic ring group: an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 ring carbon atoms, a heteroalkyl group with 1 to 20 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, an alkoxyl group with 1 to 20 carbon atoms, an aryloxy group with 6 to 30 Carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkylsilyl group having 3 to 20 carbon atoms, and an arylsilyl group having 6 to 20 carbon atoms, and combinations thereof; where the electron-withdrawing group is preferably selected from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, pyrimidinyl, triazinyl and combinations thereof. Connection after Claim 1 , 4th or 5 , wherein X and Y are selected identically or differently for each occurrence from the group consisting of the following structures:

where R ₁ is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl , Sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 carbon atoms men, 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; where R _{1 is} preferably selected identically or differently for each occurrence from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl , Triazinyl and combinations thereof; wherein V and W are selected identically or differently for each occurrence from CR _v R _w , NR _v , O, S or Se; wherein Ar is selected identically or differently at each occurrence 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 selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen , Nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted ode r unsubstituted alkynyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group with 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group with 6 bisilyl 20 carbon atoms and combinations thereof; wherein A is a group having at least one electron withdrawing group, and for each of the structures when one or more of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , R _v and R _w is (are) present, at least one of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h , R _v and R _{w is} a group having at least one electron withdrawing group; where the group with at least one electron-withdrawing group is preferably selected from the group consisting of F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, pentafluorophenyl, 4-cyanotetrafluorophenyl, tetrafluoropyridyl, pyrimidinyl, Triazinyl and combinations thereof. Connection after Claim 1 , 4th or 5 , wherein X and Y are selected identically or differently for each occurrence from the group consisting of:

Link to any of the Claims 1 - 7th , where R is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl , Sulfonyl, phosphoroso, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted alkoxyl 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 any of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and a straight guy oaryl group with 3 to 30 carbon atoms, which is substituted with one or more groups selected from the group consisting of halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, Sulfinyl, sulfonyl and phosphoroso and combinations thereof; where preferably each of R is selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, methyl, isopropyl, NO ₂ , SO ₂ CH ₃ , SCF ₃ , C ₂ F ₅ , OC ₂ F ₅ , OCH ₃ , Diphenylmethylsilyl, phenyl, methoxyphenyl, p-methylphenyl, 2,6-diisopropylphenyl, biphenyl, polyfluorophenyl, difluoropyridyl, nitrophenyl, dimethylthiazolyl, vinyl substituted with one or more of CN and CF ₃ , ethynyl substituted with one of CN and CF ₃ , dimethylphosphoroso , Diphenylphosphoroso, F, CF ₃ , OCF ₃ , SF ₅ , SO ₂ CF ₃ , cyano, isocyano, SCN, OCN, trifluoromethylphenyl, trifluoromethoxyphenyl, bis (trifluoromethyl) phenyl, bis (trifluoromethoxy) phenyl, 4-cyanotetrafluorophenyl, phenyl substituted with one or more of F, CN and CF ₃ , tetrafluoropyridyl, pyrimidinyl, triazinyl, diphenylboranyl, oxaboraanthryl, and combinations thereof. Connection after Claim 8 where X and Y

are. Link to any of the Claims 1 to 9 , wherein R is selected identically or differently for each occurrence from the group consisting of:

where the two Rs in a compound with the formula 1 are preferably the same. Connection after Claim 10 which has the structure represented by Formula 2:

where in formula 2 the structures of the two Z are the same, the structures of the two R are the same or different, and Z, X, Y and R are selected accordingly from the atoms or groups as shown in the following table: Connection no. Z X Y R. R. Connection no. Z X Y R. R. 1 O A1 A1 B1 B1 2 O A1 A1 B2 B2 3 O A1 A1 B3 B3 4th O A1 A1 B4 B4 5 O A1 A1 B5 B5 6th O A1 A1 B6 B6 7th O A1 A1 B7 B7 8th O A1 A1 B8 B8 9 O A1 A1 B9 B9 10 O A1 A1 B10 B10 11 O A1 A1 B11 B11 12th O A1 A1 B12 B12 13th O A1 A1 B13 B13 14th O A1 A1 B14 B14 15th O A1 A1 B15 B15 16 O A1 A1 B16 B16 17th O A1 A1 B17 B17 18th O A1 A1 B18 B18 19th O A1 A1 B19 B19 20th O A1 A1 B20 B20 21st O A1 A1 B21 B21 22nd O A1 A1 B22 B22 23 O A1 A1 B23 B23 24 O A1 A1 B24 B24 25th O A1 A1 B25 B25 26th O A1 A1 B26 B26 27 O A1 A1 B27 B27 28 O A1 A1 B28 B28 29 O A1 A1 B29 B29 30th 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 An electroluminescent device comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the formula 1:

wherein X and Y for each occurrence, identically or differently, are selected from CR "R"",NR", O, S or Se; wherein Z ₁ and Z ₂ are selected identically or differently for each occurrence from O, S or Se; R, R ', R''andR''' are selected identically or differently for each occurrence from the group consisting of hydrogen, deuterium, halogen, nitroso, nitro, acyl, carbonyl, a carboxylic acid group, an ester group, cyano, isocyano, SCN, OCN, SF ₅ , boranyl, sulfinyl, sulfonyl, phosphoroso, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group with 1 to 20 carbon atoms, a substituted one or unsubstituted arylalkyl group with 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 20 Koh carbon atoms, a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 30 Carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, and combinations thereof; wherein each R can 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; and adjacent substituents may optionally be linked to form a ring. Electroluminescent device according to Claim 12 wherein the organic layer is a hole injection layer and the hole injection layer is formed from the compound alone. Electroluminescent device according to Claim 12 wherein the organic layer is a hole injection layer and the hole injection layer is formed from the compound comprising a dopant which comprises at least one hole transport material; wherein the hole transport material comprises a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, an oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex or a metal phthalocyanine complex, the molar doping ratio of the compound 100: 1 to 1 to the hole transport material Is 10,000; wherein the molar doping ratio of the compound to the hole transport material is preferably 10: 1 to 1: 100. Electroluminescent device according to Claim 12 , wherein the electroluminescent device comprises a plurality of stacks arranged between the anode and the cathode, the stacks comprising a first light-emitting layer and a second light-emitting layer, the first stack comprising a first light-emitting layer and the second stack comprising a second light-emitting layer, and a a charge generating layer is disposed between the first stack and the second stack, the charge generating layer comprising a p-type charge generating layer and an n-type charge generating layer; wherein the organic layer comprising a compound represented by Formula 1 is the p-type charge generating layer; wherein the charge generating layer of the p-type preferably further comprise at least one hole transport material and can be formed by doping the compound with the at least one hole transport material, the hole transport material being a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, an oligophenyl compound, a An oligophenylene vinyl compound, an oligofluorene compound, a porphyrin complex, or a metal phthalocyanine complex, the molar doping ratio of the compound to the hole transport material being 10,000: 1 to 1: 10,000; wherein the molar doping ratio of the compound to the hole transport material is preferably 10: 1 to 1: 100. Electroluminescent device according to Claim 15 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, the buffer layer comprising the interconnection. A compound formulation comprising the compound of any of the Claims 1 - 11 .

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