Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. A composition comprising a first compound and a second compound is described. The composition may be a mixture of a first compound having a structure according to Formula I, # imgabs 0 # and a second compound having a structure according to Formula II, # imgabs 1 #. The composition may also be a mixture of a first compound having a structure according to Formula III, # imgabs2 # and a second compound having a structure according to Formula IV, # imgabs3 #. Also described are devices, such as OLEDs, comprising the compositions for Formula I and Formula II or Formula III and Formula IV, as well as methods of making the devices.

Description

[0001] This application is a divisional application of the invention patent application with application date of July 9, 2015, application number 201510401460.X, and name “Organic electroluminescent materials and devices”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application is a non-provisional application of U.S. Patent Application No. 62 / 022,300 filed on July 9, 2014; U.S. Patent Application No. 62 / 038,925 filed on August 19, 2014; U.S. Patent Application No. 62 / 060,192 filed on October 6, 2014; and U.S. Patent Application No. 62 / 083,490 filed on November 24, 2014, the entire contents of which are incorporated herein by reference.

[0004] Parties to a Joint Research Agreement

[0005] The claimed invention was made by, on behalf of, and / or in conjunction with one or more of the following parties to a joint university-corporate research agreement: The Regents of the University of Michigan, Princeton University, the University of Southern California, and Universal Display Corporation. Said agreement was in effect on and before the date on which the claimed invention was made, and the claimed invention was made as a result of activities performed within the scope of said agreement. Technical Field

[0006] The present invention relates to compounds useful as hosts, blocking materials and electron transport materials, and devices including the compounds, such as organic light emitting diodes. Background Art

[0007] Optical electronic devices utilizing organic materials are becoming increasingly popular for several reasons. Many of the materials used to make such devices are relatively inexpensive, so organic optical electronic devices have the potential to gain cost advantages over inorganic devices. In addition, the inherent properties of organic materials (such as their flexibility) can make them very suitable for specific applications, such as manufacturing on flexible substrates. Examples of organic optical electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength of light emitted by the organic emissive layer can generally be easily adjusted with appropriate dopants.

[0008] OLEDs utilize organic thin films that emit light when voltage is applied to the device. OLEDs are becoming an increasingly attractive technology for use in applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0009] One application of phosphorescent emitting molecules is full color displays. Industry standards for such displays require pixels adapted to emit specific colors (referred to as "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates, which are well known in the art.

[0010] An example of a green emitting molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)3, which has the following structure:

[0011]

[0012] In this figure and in subsequent figures herein, the coordinate bond from nitrogen to the metal (here, Ir) is depicted as a straight line.

[0013] As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials, which can be used to make organic optical electronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" may actually be quite large. In some cases, a small molecule may include a repeating unit. For example, the use of a long chain alkyl group as a substituent does not remove the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example as side groups on a polymer backbone or as part of a backbone. Small molecules can also serve as the core portion of a dendritic polymer, which consists of a series of chemical shells built on the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small molecule emitter. A dendritic polymer can be a "small molecule", and it is believed that all dendritic polymers currently used in the field of OLEDs are small molecules.

[0014] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed" "on" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, other layers may be present between the first and second layers. For example, a cathode may be described as being "disposed" "on" an anode even though various organic layers are present between the cathode and the anode.

[0015] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0016] A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive property of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive property of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.

[0017] As used herein, and as will be generally understood by one skilled in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, the vacuum energy level is at the top, and the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0018] As used herein, and as will be generally understood by one skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are typically measured as negative numbers relative to the vacuum energy level, this means that the "higher" work function is more negative. On a conventional energy level diagram, the vacuum energy level is at the top, and the "higher" work function is illustrated as being farther away from the vacuum energy level in a downward direction. Therefore, the definition of HOMO and LUMO energy levels follows a different convention than that of work functions.

[0019] More details regarding OLEDs and the definitions set forth above may be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety. Summary of the invention

[0020] According to one embodiment, a material composition is provided, which includes a first compound. The first compound has the formula: In formula I:

[0021] G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene;

[0022] L 1 , L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof;

[0023] G 4 Selected from the group consisting of phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, and combinations thereof;

[0024] G 2 , G 3 and G 5 each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof;

[0025] G 2 , G 3 , G 4 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof;

[0026] m is an integer from 0 to 7,

[0027] n is an integer from 0 to 4;

[0028] When m or n is greater than 1, each G 4 or G 5 Can be the same or different;

[0029] When n is 0, m is equal to or greater than 1, and each G 4 all selected from the group consisting of phenyl and biphenyl;

[0030] When n is equal to or greater than 1, L 1 is not a direct key; and

[0031] When m and n are both 0, L 1 It's biphenyl.

[0032] According to another embodiment of the present invention, there is provided a material composition comprising The first compound of the structure. In the structure of formula III,

[0033] L A and L B selected from the group consisting of: a direct bond, a phenyl group, a biphenyl group, a pyridine group, and combinations thereof;

[0034] G A and G B is selected from the group consisting of phenyl, biphenyl, pyridine, dibenzothiophene, dibenzofuran, dibenzoselenophene, and fluorene; and

[0035] G Aand G B Each is optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof.

[0036] According to another aspect of the present invention, a device is also provided, which includes one or more organic light-emitting devices. At least one of the one or more organic light-emitting devices may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a composition comprising a compound according to the structure of Formula I or Formula III or any of the variations thereof described herein.

[0037] In yet another aspect of the present invention, a method for manufacturing an organic light-emitting device is provided. The organic light-emitting device may include a first electrode, a second electrode, and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer includes a first composition, the first composition including a mixture of a first compound and a second compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 An organic light-emitting device is demonstrated.

[0039] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated.

[0040] Figure 3 Formula I as disclosed herein is shown.

[0041] Figure 4 Formula II as disclosed herein is shown.

[0042] Figure 5 Formula III as disclosed herein is shown.

[0043] Figure 6 Formula IV as disclosed herein is shown. DETAILED DESCRIPTION

[0044] In general, an OLED comprises at least one organic layer disposed between an anode and a cathode and electrically connected to the anode and the cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are confined to the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes via a photoemission mechanism, light is emitted. The exciton can be confined to an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0045] The first OLEDs used emissive molecules that emitted light from a singlet state ("fluorescence"), as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0046] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, Vol. 395, pp. 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, pp. 4-6 (1999) (Baldo-II), which are incorporated by reference in their entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, incorporated by reference.

[0047] Figure 1 An organic light emitting device 100 is shown. The figure is not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The anode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be manufactured by depositing the described layers in sequence. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0048] There are more examples of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive materials and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0049] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be manufactured by depositing the described layers in order. Because the most common OLED configuration has a cathode disposed on the anode, and device 200 has cathode 215 disposed under anode 230, device 200 can be referred to as an "inverted" OLED. In the corresponding layers of device 200, materials similar to those described with respect to device 100 can be used. Figure 2 One example is provided of how some layers may be omitted from the structure of device 100 .

[0050] Figure 1 and 2The simple layered structure illustrated in is provided as a non-limiting example, and it should be understood that embodiments of the present invention can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or several layers can be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials different from the materials specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it should be understood that a combination of materials (e.g., a mixture of a host and a dopant) or, more generally, a mixture may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may include a single layer, or may further include, for example, Figure 1 and 2 Multiple layers of different organic materials are described.

[0051] Structures and materials not specifically described may also be used, such as OLEDs containing polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may be separated from Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0052] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (e.g., as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (e.g., as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP) (e.g., as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and OVJD. Other methods may also be used. The material to be deposited may be modified to make it compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, which may be branched or unbranched and preferably contain at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons may be used, and 3-20 carbons are a preferred range. Materials having asymmetric structures may have better solution processability than materials having symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0053] The device manufactured according to the embodiment of the present invention may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from being damaged by exposure to harmful substances (including moisture, steam and / or gas, etc.) in the environment. The barrier layer can be deposited on a substrate, an electrode, deposited under a substrate, an electrode, or deposited beside a substrate, an electrode, or deposited on any other part (including the edge) of the device. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques, and may include a composition having a single phase and a composition having multiple phases. Any suitable material or material combination may be used for the barrier layer. The barrier layer may be incorporated with an inorganic compound or an organic compound or both. A preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098, and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymeric material and non-polymeric material constituting the barrier layer should be deposited under the same reaction conditions and / or at the same time. The weight ratio of polymeric material to non-polymeric material can be in the range of 95:5 to 5:95. The polymeric material and non-polymeric material can be produced from the same precursor material. In one example, the mixture of polymeric material and non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0054] Devices manufactured according to embodiments of the present invention can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc. that can be utilized by end-user product manufacturers. Such electronic component modules may optionally include drive electronics and / or power supplies. Devices manufactured according to embodiments of the present invention can be incorporated into a variety of consumer products, which have one or more electronic component modules (or units) incorporated therein. Such consumer products should include any kind of product containing one or more light sources and / or some type of visual display. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablet computers, tablet phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, vehicles, large area walls, theater or stadium screens, or signage. Various control mechanisms can be used to control devices manufactured according to the present invention, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18 degrees Celsius to 30 degrees Celsius, and more preferably at room temperature (20-25 degrees Celsius), but can be used outside this temperature range (e.g., -40 degrees Celsius to +80 degrees Celsius).

[0055] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices such as organic transistors can use the materials and structures.

[0056] As used herein, the term "halo," "halogen," or "halo" includes fluorine, chlorine, bromine, and iodine.

[0057] As used herein, the term "alkyl" encompasses both straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. In addition, the alkyl group may be optionally substituted.

[0058] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, and the like. In addition, the cycloalkyl group may be optionally substituted.

[0059] As used herein, the term "alkenyl" encompasses straight and branched alkenyls. Preferred alkenyls are alkenyls containing two to fifteen carbon atoms. In addition, alkenyls may be optionally substituted.

[0060] As used herein, the term "alkynyl" encompasses both straight and branched chain alkynyl groups. Preferred alkynyl groups are those containing two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.

[0061] As used herein, the terms "aralkyl" or "arylalkyl" are used interchangeably and encompass an alkyl group having an aromatic group as a substituent. Additionally, the aralkyl group may be optionally substituted.

[0062] As used herein, the term "heterocyclyl" encompasses aromatic and non-aromatic cyclic groups. Aromatic heterocyclyl also means heteroaryl. Preferred non-aromatic heterocyclyls are heterocyclyls containing 3 or 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. In addition, the heterocyclyl may be optionally substituted.

[0063] As used herein, the term "aryl" or "aromatic group" encompasses monocyclic groups and polycyclic systems. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. In addition, aryl may be optionally substituted.

[0064] As used herein, the term "heteroaryl" encompasses monocyclic heteroaromatic groups that may include one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, etc. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. In addition, heteroaryl may be optionally substituted.

[0065] The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclyl, aryl and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino and combinations thereof.

[0066] As used herein, "substituted" means that a substituent other than H is bonded to the relevant position, e.g., carbon. Thus, for example, in R 1 When replaced by a single, then an R 1 must not be H. Similarly, in R 1 When disubstituted, the two R 1 must not be H. Similarly, in R 1 When not replaced, R 1 Hydrogen for all available positions.

[0067] The "aza" designation in the fragments described herein (i.e., aza-dibenzofuran, aza-dibenzothiophene, etc.) means that one or more CH groups in the respective fragment can be replaced by a nitrogen atom, for example and without any limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0068] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0069] The emission layer (EML) of an OLED device that exhibits good lifetime and efficiency often requires more than two components (e.g., 3 or 4 components). Fabricating such an EML using a vacuum thermal evaporation (VTE) process requires evaporating 3 or 4 evaporation source materials in a separate VTE sublimation crucible, which is very complex and costly compared to a standard two-component EML with a single host and emitter, which requires only two evaporation sources.

[0070] Premixing two or more materials and evaporating them from one VTE sublimation crucible can reduce the complexity of the manufacturing process. However, the coevaporation must be stable and produce an evaporated film whose composition remains constant throughout the evaporation process. Compositional variations of the film may adversely affect device performance. In order to obtain stable coevaporation from a mixture of compounds under vacuum, it would be assumed that the materials must have the same evaporation temperature under the same conditions. However, this may not be the only parameter that must be considered. When two compounds are mixed together, they can interact with each other and the evaporation properties of the mixture may be different from their individual properties. On the other hand, materials with slightly different evaporation temperatures can form a stable coevaporated mixture. Therefore, it is extremely difficult to obtain a stable coevaporated mixture. To date, there are very few examples of stable coevaporated mixtures. The "evaporation temperature" of a material in a vacuum deposition tool is typically between 1×10 -7 Support to 1×10 -8 Under constant pressure between The deposition rate is measured on a surface located at a set distance from the evaporation source of the evaporated material (e.g., a sublimation crucible in a VTE tool). As will be appreciated by one of ordinary skill in the art, it is expected that the various measurements disclosed herein (e.g., temperature, pressure, deposition rate, etc.) have nominal variations due to the tolerances expected in the measurements that produce these quantitative values.

[0071] Many factors other than temperature can promote the ability to obtain stable co-evaporation, such as the miscibility of different materials and the phase transition temperature of different materials. The inventors found that when two materials have similar evaporation temperatures and similar mass loss rates or similar vapor pressures, the two materials can co-evaporate consistently. The "mass loss rate" of a material is defined as the percentage of mass lost over time ("percentage / minute" or "% / min") and is measured by measuring the time taken for the first 10% of the mass of the sample of the lost material, as measured by thermogravimetric analysis (TGA) for a given material under given experimental conditions at a given constant temperature after reaching a stable evaporation state. The given constant temperature is a temperature point selected so that the mass loss rate value is between about 0.05% / min and 0.50% / min. Those skilled in the art will appreciate that in order to compare the two parameters, the experimental conditions should be consistent. The method for measuring mass loss rate and vapor pressure is well known in the art and can be found, for example, in Bull et al. Material Science (Mater. Sci.) 2011, 34, 7.

[0072] In the OLED device of the prior art level, the EML may be composed of three or more components. In one example, the EML may be composed of two host compounds and an emitter combination (e.g., a hole transport co-host (h host), an electron transport co-host (e host), and a compound capable of acting as an emitter in an OLED at room temperature). In another example, the EML may be composed of a host compound and two emitter compounds (e.g., a host compound and two compounds each capable of acting as an emitter in an OLED at room temperature). Conventionally, in order to manufacture such an EML having three or more components using a VTE process, three or more evaporation sources are required, one for each component. Because the concentration of the component is crucial for device performance, the deposition rate of each component is usually measured individually during the deposition process. This makes the VTE process complex and costly. Therefore, it is necessary to pre-mix at least two of the components of such an EML to reduce the number of VTE evaporation sources.

[0073] If any two of the three or more components of the EML can be premixed and form a stable mixture of co-evaporation sources, the number of evaporation sources required for EML layer fabrication will be reduced. In order for the materials to be premixed into the evaporation sources, they should be co-evaporated and uniformly deposited without changing the ratio. The ratio of the components in the mixture should be the same as the ratio of the components in the film deposited from these premixed materials. Therefore, the concentration of the two components in the deposited film is controlled by their concentration in the premixed evaporation source.

[0074] This invention describes a new class of h-hosts and e-hosts that can be premixed and stably co-evaporated from a single source.

[0075] According to one embodiment, a material composition is disclosed, which includes a first compound. The first compound has the formula: In formula I:

[0076] G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene;

[0077] L 1 , L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof;

[0078] G 4 Selected from the group consisting of phenyl, biphenyl, terphenyl, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, and combinations thereof;

[0079] G 2 , G 3 and G5 each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof;

[0080] G 2 , G 3 , G 4 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof;

[0081] m is an integer from 0 to 7,

[0082] n is an integer from 0 to 4;

[0083] When m or n is greater than 1, each G 4 or G 5 Can be the same or different;

[0084] When n is 0, m is equal to or greater than 1, and each G 4 All are selected from the group consisting of phenyl and biphenyl;

[0085] When n is equal to or greater than 1, L 1 is not a direct key; and

[0086] When m and n are both 0, L 1 It's biphenyl.

[0087] In some embodiments, L 1 , L 2 and L 3 One or more of may be a direct bond, and the direct bond may be a single bond or a double bond. 1 When it is a direct key, n=0.

[0088] In some embodiments, n is 0, while in other embodiments n is equal to or greater than 1. In some embodiments, m and n are both 0. In some embodiments, m is equal to or greater than 1.

[0089] In some embodiments, G 4 Having a structure selected from the group consisting of:

[0090] In some embodiments, G 1 Having a structure selected from the group consisting of: in:

[0091] X is selected from the group consisting of O, S and Se;

[0092] R B1 and R B2 are independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, halogen, and combinations thereof; and

[0093] R B1 and R B2 Optionally linked to form a ring.

[0094] In some embodiments, 3

[0095] Freedom to choose Groups composed of.

[0096] In some embodiments, G 2 , G 3 and G 5 Independently selected from the group consisting of:

[0097]

[0098] in

[0099] R B1 and R B2 are independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, halogen, and combinations thereof; and

[0100] R B1 and R B2 Optionally linked to form a ring.

[0101] In some embodiments, G 2 , G 3 , G 4 and G 5 At least one of them is substituted by at least one fluorine atom.

[0102] In some embodiments, the first compound has the formula: wherein X is selected from the group consisting of O, S and Se.

[0103] In some embodiments, the first compound is selected from the group consisting of:

[0104] Compounds A1 to A3, each of which is the following: Compounds A4 to A6, each of which is the following: Compounds A7 to A9, each of which is

[0105] Compounds A10 to A12, each of which is a compound A13 to A15, each of which is a compound A16 to A18, each of which is

[0106] Compounds A19 to A21, each of which is a compound A22 to A24, each of which is a compound A25 to A27, each of which is

[0107] Compounds A28 to A30, each of which is a compound A31 to A33, each of which is a compound A34 to A36, each of which is

[0108] Compounds A37 to A39, each of which is a compound A40 to A42, each of which is a compound A43 to A45, each of which is

[0109] Compounds A46 to A48, each of which is a compound A49 to A51, each of which is a compound A52 to A54, each of which is

[0110] Compounds A55 to A57, each of which is a compound A58 to A60, each of which is a compound A61 to A63, each of which is

[0111] Compounds A64 to A66, each of which is a compound A67 to A69, each of which is a compound A70 to A72, each of which is

[0112] Compounds A73 to A75, each of which is a compound A76 to A78, each of which is a compound A79 to A81, each of which is

[0113] Compounds A82 to A84, each of which is a compound A85 to A87, each of which is a compound A88 to A90, each of which is

[0114] Compounds A91 to A93, each of which is a compound A94 to A96, each of which is a compound A97 to A99, each of which is

[0115] Compounds A100 to A102, each of which is a compound A103 to A105, each of which is a compound A106 to A108, each of which is

[0116] Compounds A109 to A111, each of which is a compound A112 to A114, each of which is a compound A115 to A117, each of which is

[0117]

[0118] In some embodiments, n is 0, m is 1, and G 4 -G 1 Having a structure selected from the group consisting of:

[0119]

[0120]

[0121] In some embodiments, the first compound is selected from the group consisting of:

[0122] Compounds C1 to C3, each of which is the following: Compounds C4 to C6, each of which is the following: Compounds C7 to C9, each of which is the following:

[0123] Compounds C10 to C12, each of which is a compound C13 to C15, each of which is a compound C16 to C18, each of which is a

[0124] Compounds C19 to C21, each of which is a compound C22 to C24, each of which is a compound C25 to C27, each of which is a

[0125] Compounds C28 to C30, each of which is a compound C31 to C33, each of which is a compound C34 to C36, each of which is a

[0126] Compounds C37 to C39, each of which is a compound C40 to C42, each of which is a compound C43 to C45, each of which is

[0127] Compounds C46 to C48, each of which is a compound C49 to C51, each of which is a compound C52 to C54, each of which is a

[0128] Compounds C55 to C57, each of which is a compound C58 to C60, each of which is a compound C61 to C63, each of which is a

[0129] Compounds C64 to C66, each of which is a compound C67 to C69, each of which is a compound C70 to C72, each of which is a

[0130] Compounds C73 to C75, each of which is a compound C76 to C78, ​​each of which is a compound C79 to C81, each of which is

[0131] Compounds C82 to C84, each of which is a compound C85 to C87, each of which is a compound C88 to C90, each of which is a

[0132] Compounds C91 to C93, each of which is a compound C94 to C96, each of which is a compound C97 to C99, each of which is a

[0133] Compounds C100 to C102, each of which Compounds C103 to C105, each of which Compounds C106 to C108, each of which

[0134] Compounds C109 to C111, each of which Compounds C112 to C114, each of which Compounds C115 to C117, each of which

[0135] Compounds C118 to C120, each of which Compounds C121 to C123, each of which Compounds C124 to C126, each of which

[0136] Compounds C127 to C129, each of which Compounds C130 to C132, each of which

[0137]

[0138] Compounds C133 to C135, each of which Compounds C136 to C138, each of which Compounds C139 to C141, each of which

[0139] Compounds C142 to C144, each of which Compounds C145 to C147, each of which Compounds C148 to C150, each of which

[0140] Compounds C151 to C153, each of which Compounds C154 to C156, each of which Compounds C157 to C159, each of which

[0141] Compounds C160 to C162, each of which Compounds C163 to C165, each of which Compounds C166 to C168, each of which

[0142] Compounds C169 to C171, each of which Compounds C172 to C174, each of which

[0143]

[0144] Compounds C175 to C177, each of which Compounds C178 to C180, each of which Compounds C181 to C183, each of which

[0145] Compounds C184 to C186, each of which Compounds C187 to C189, each of which Compounds C190 to C192, each of which

[0146] Compounds C193 to C195, each of which Compounds C196 to C198, each of which Compounds C199 to C201, each of which

[0147] Compounds C202 to C204, each of which Compounds C205 to C207, each of which Compounds C208 to C210, each of which

[0148] Compounds C211 to C213, each of which Compounds C214 to C216, each of which Compounds C217 to C219, each of which

[0149] Compounds C220 to C222, each of which Compounds C223 to C225, each of which Compounds C226 to C228, each of which

[0150] Compounds C229 to C231, each of which Compounds C232 to C234, each of which Compounds C235 to C237, each of which

[0151] Compounds C238 to C240, each of which Compounds C241 to C243, each of which Compounds C244 to C246, each of which

[0152] Compounds C247 to C249, each of which compounds C250 to C252, each of which compounds C253 to C255, each of which

[0153]

[0154] In some embodiments, the first compound has the formula: Where L 1 It's biphenyl.

[0155] In some embodiments, the first compound is selected from the group consisting of:

[0156]

[0157]

[0158] In some embodiments, the composition comprises a compound having Formula II: The second compound of the structure. In the structure of formula II:

[0159] Ar 1 Selected from the group consisting of triphenylene and aza-triphenylene;

[0160] Ar 2 Selected from the group consisting of: a direct bond, phenyl, biphenyl, terphenyl, naphthalene, pyridine, dibenzofuran, dibenzothiophene, dibenzoselenophene, aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene, and combinations thereof;

[0161] Ar 3 is selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, pyridine, dibenzofuran, dibenzothiophene, dibenzoselenophene, aza-dibenzofuran, aza-dibenzothiophene, aza-dibenzoselenophene, carbazole, aza-carbazole, and combinations thereof; and

[0162] Ar 1 ,Ar 2 and Ar 3 Each independently, optionally further substituted with one or more substitutions selected from the group consisting of deuterium, halogen, alkyl, aryl, heteroaryl, and combinations thereof.

[0163] In some embodiments, the second compound is selected from A group consisting of:

[0164] X is selected from the group consisting of O, S and Se;

[0165] R 1 and R 4 Each independently represents mono-, di- or tri-substituted, or unsubstituted;

[0166] R 2 , R 3 , R 5 and R 6 Each independently represents mono-, di-, tri- or tetra-substituted, or unsubstituted; and

[0167] R 1 to R 6 Each is independently selected from the group consisting of hydrogen, deuterium, benzene, biphenyl, terphenyl, naphthalene, fluorene, triphenylene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, and combinations thereof.

[0168] In some embodiments, the second compound is selected from the group consisting of:

[0169] Compounds E1 to E3, each of which is the following: Compounds E4 to E6, each of which is the following: Compounds E7 to E9, each of which is the following:

[0170] Compounds E10 to E12, each of which is a compound E13 to E15, each of which is a compound E16 to E18, each of which is

[0171] Compounds E19 to E21, each of which is a compound E22 to E24, each of which is a compound E25 to E27, each of which is

[0172]

[0173] In some embodiments, the mixture of the first compound and the second compound is selected from the group consisting of:

[0174]

[0175]

[0176] In some embodiments, the mixture of the first compound and the second compound is selected from the group consisting of:

[0177]

[0178] In some embodiments, the composition comprises a second compound, wherein the second compound is a phosphorescent emissive Ir complex having at least one substituent selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

[0179] According to another embodiment of the present invention, a material composition is disclosed, which comprises The first compound of the structure. In the structure of formula III,

[0180] L A and L B selected from the group consisting of: a direct bond, a phenyl group, a biphenyl group, a pyridine group, and combinations thereof;

[0181] G A and G B is selected from the group consisting of phenyl, biphenyl, pyridine, dibenzothiophene, dibenzofuran, dibenzoselenophene, and fluorene; and

[0182] G A and G BEach is optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof.

[0183] In some embodiments, L A and L B One or more of may be a direct bond, and the direct bond may be a single bond or a double bond.

[0184] In some embodiments, the first compound is selected from the group consisting of:

[0185] Compounds F6 to F8, each of which is a compound F9 to F11, each of which is a compound F12 to F14, each of which is

[0186]

[0187] In some embodiments, the evaporation temperature T1 of the first compound is 150° C. to 350° C.; the evaporation temperature T2 of the second compound is 150° C. to 350° C.; the absolute value of T1-T2 is less than 20° C.; the first compound has a concentration C1 in the mixture and is deposited in a vacuum deposition tool at a temperature between 1×10 -6 Support to 1×10 -9 Under constant pressure between A film formed by evaporating the mixture on a surface located at a predetermined distance from the evaporated mixture at a deposition rate has a concentration C2; and an absolute value of (C1-C2) / C1 is less than 5%.

[0188] In some embodiments, the vapor pressure P1 of the first compound at T1 is 1 atm, the vapor pressure P2 of the second compound at T2 is 1 atm; and the ratio of P1 / P2 is in a range of 0.90 to 1.10.

[0189] In some embodiments, the first compound has a first mass loss rate and the second compound has a second mass loss rate, wherein a ratio between the first mass loss rate and the second mass loss rate is in a range of 0.90 to 1.10.

[0190] In some embodiments, the first compound and the second compound are each more than 99% pure as determined by high pressure liquid chromatography.

[0191] In some embodiments, the composition further comprises a third compound. In some embodiments, the chemical structure of the third compound is different from the first and second compounds. In some embodiments, the third compound has a third mass loss rate, and the ratio between the first mass loss rate and the third mass loss rate is in the range of 0.90 to 1.10. In some embodiments, the evaporation temperature T3 of the third compound is 150°C to 350°C, and the absolute value of T1-T3 is less than 20°C.

[0192] In some embodiments, the composition is in liquid form at a temperature less than T1 and T2.

[0193] In some embodiments, the composition comprises a second compound, wherein the second compound has Formula IV It has the structure: In such embodiments, Ar 4 is selected from the group consisting of aryl, heteroaryl, alkyl, cycloalkyl, and combinations thereof; L 11 and L 12 Each is independently selected from the group consisting of: a direct bond, an aryl group, a heteroaryl group, an alkyl group, an alkoxy group, and combinations thereof; p is an integer from 0 to 20; when p is greater than 1, each G 7 Can be the same or different; R 11 , R 13 , R 15 and R 16 Each independently represents mono-, di-, tri- or tetra-substituted, or unsubstituted; R 12 and R 14 Each independently represents mono-, di- or tri-substituted, or unsubstituted; R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, silyl, carbonyl, alkoxy, nitrile, isonitrile, aryl, heteroaryl, and combinations thereof; and L 11 , L 12 and Ar 4 Each is independently, optionally further substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, silanyl, carbonyl, alkoxy, nitrile, isonitrile, aryl, heteroaryl, and combinations thereof.

[0194] In some embodiments, the second compound is selected from Groups composed of.

[0195] In some embodiments, the second compound is selected from the group consisting of:

[0196]

[0197] Compounds G25 to G27, each of which is a compound G28 to G30, each of which is a

[0198]

[0199]

[0200] Compounds G31 to G33, each of which is a compound G34 to G36, each of which is a compound G37 to G39, each of which is

[0201] Compounds G40 to G42, each of which is a compound G43 to G45, each of which is a compound G46 to G48, each of which is

[0202] Compounds G49 to G51, each of which is a compound G52 to G54, each of which is a compound G55 to G57, each of which is

[0203] Compounds G58 to G60, each of which is a compound G61 to G63, each of which is a compound G64 to G66, each of which is

[0204]

[0205] In some embodiments, the mixture of the first compound and the second compound is selected from the group consisting of:

[0206]

[0207] In some embodiments, the mixture of the first compound and the second compound is

[0208] In some embodiments, the evaporation temperature T1 of the first compound is 150°C to 350°C, the evaporation temperature T2 of the second compound is 150°C to 350°C, or both. In some embodiments, the absolute value of T1-T2 is less than 20°C. The first compound has a concentration C1 in the mixture and is deposited in a vacuum deposition tool at a temperature between 1×10 -6 Support to 1×10 -9 Under constant pressure between A film formed by evaporating the mixture on a surface located a predetermined distance from the evaporated mixture at a deposition rate has a concentration C2. In some embodiments, the absolute value of (C1-C2) / C1 is less than 5%.

[0209] In some embodiments, the vapor pressure P1 of the first compound at T1 is 1 atm, the vapor pressure P2 of the second compound at T2 is 1 atm; and the ratio of P1 / P2 is in a range of 0.90 to 1.10.

[0210] In some embodiments, the first compound has a first mass loss rate and the second compound has a second mass loss rate, wherein a ratio between the first mass loss rate and the second mass loss rate is in a range of 0.90 to 1.10.

[0211] In some embodiments, the first compound and the second compound are each more than 99% pure as determined by high pressure liquid chromatography.

[0212] In some embodiments, the composition further comprises a third compound, wherein the chemical structure of the third compound is different from the first and second compounds. In some embodiments, the evaporation temperature T3 of the third compound is 150° C. to 350° C., and wherein the absolute value of T1-T3 is less than 20° C. In some embodiments, the third compound has a third mass loss rate, and the ratio between the first mass loss rate and the third mass loss rate is in the range of 0.90 to 1.10.

[0213] In some embodiments, the composition is in liquid form at a temperature less than T1 and T2.

[0214] According to another aspect of the present invention, a device is also provided, which includes one or more organic light-emitting devices. At least one of the one or more organic light-emitting devices may include an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer may include a composition comprising a compound according to the structure of Formula I or Formula III or any of the variations thereof described herein.

[0215] In some embodiments, the organic layer is an emissive layer and the composition comprises a host.

[0216] In some embodiments, the organic layer further comprises a phosphorescent dopant. In some embodiments, the phosphorescent dopant is a transition metal complex having at least one ligand or a portion of the ligand when the ligand is bidentate or higher, the ligand being selected from the group consisting of:

[0217]

[0218]

[0219] in:

[0220] Each X 1 To X 13 independently selected from the group consisting of carbon and nitrogen;

[0221] X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R" and GeR'R";

[0222] R' and R" are optionally fused or linked to form a ring;

[0223] Each R a , R b , R c and R d It can represent a single substitution to the maximum possible number of substitutions or no substitution;

[0224] R', R", R a , R b , R c and R d each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0225] R a , R b , R c and R d Any two adjacent substituents are optionally fused or linked to form a ring or to form a multidentate ligand.

[0226] In some embodiments, the organic layer is a blocking layer and the composition is a blocking material in the organic layer. In some embodiments, the organic layer is an electron transporting layer and the composition is an electron transporting material in the organic layer.

[0227] In some embodiments, the first device is selected from the group consisting of: a consumer product, an electronic component module, an organic light emitting device, and a lighting panel.

[0228] In some embodiments, R a , R b , R c and R dAt least one of is selected from the group consisting of alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially or fully fluorinated variants thereof, and combinations thereof.

[0229] In yet another aspect of the present invention, a method for manufacturing an organic light-emitting device is provided. The organic light-emitting device may include a first electrode, a second electrode, and a first organic layer disposed between the first electrode and the second electrode, wherein the first organic layer includes a first composition, the first composition including a mixture of a first compound and a second compound.

[0230] In some embodiments, the method comprises: providing a substrate having a first electrode disposed thereon; depositing a first composition over the first electrode; and depositing a second electrode over the first organic layer. In some embodiments, the first composition is selected from the group consisting of Formulation I and Formulation II, wherein Formulation I comprises a first compound of Formula I and a second compound of Formula II, and wherein Formulation II comprises a first compound of Formula III and a second compound of Formula IV.

[0231] Combination with other materials

[0232] The materials described herein as being useful for specific layers in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0233] HIL / HTL:

[0234] The hole injection / transport material used in the present invention is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having conductive dopants; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes, and cross-linkable compounds.

[0235] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the following general structures:

[0236]

[0237]

[0238] Ar 1 To Ar 9 Each of the compounds is selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, letrozole, perylene, and azulene; and the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolooxazole, The invention also comprises a group consisting of oxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, dibenzopyran, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups, and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. wherein each Ar is further substituted with a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0239] In one aspect, Ar 1 To Ar 9 Independently selected from the group consisting of:

[0240]

[0241] Where k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 The same groups as defined above.

[0242] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0243]

[0244] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0245] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. On the other hand, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a relative pressure of less than about 0.6 V to Fc + / Fc pair in solution state with minimum oxidation potential.

[0246] main body:

[0247] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Although the following table classifies the host materials preferred for devices emitting various colors, any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0248] Examples of metal complexes used as hosts preferably have the following general formula:

[0249]

[0250] Where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 is independently selected from C, N, O, P and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0251] In one aspect, the metal complex is:

[0252]

[0253] wherein (ON) is a bidentate ligand having a metal coordinated to O and N atoms.

[0254] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0255] Examples of organic compounds used as hosts are selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, letrozole, perylene, and azulene; and the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoloxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, dibenzopyran, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups, and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. wherein each group is further substituted with a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0256] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0257]

[0258] Where R 101 to R 107is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition to that of Ar above. k is an integer from 0 to 20 or from 1 to 20; k'' is an integer from 0 to 20. X 101 To X 108 is selected from C (including CH) or N. Z 101 and Z 102 Selected from NR 101 , O or S.

[0259] HBL:

[0260] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can produce substantially higher efficiencies than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of an OLED.

[0261] In one aspect, the compound used in HBL contains the same molecule or the same functional group used as the host described above.

[0262] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0263]

[0264] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0265] ETL:

[0266] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0267] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0268]

[0269] Where R 101is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to that of Ar above. Ar 1 To Ar 3 has the same definition as Ar above. k is an integer from 1 to 20. 101 To X 108 is selected from C (including CH) or N.

[0270] In another aspect, the metal complex used in the ETL includes, but is not limited to, the following general formula:

[0271]

[0272] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0273] In any of the above compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specific listed substituents (such as, but not limited to, methyl, phenyl, pyridyl, etc.) encompass their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) also encompass their non-deuterated, partially deuterated, and fully deuterated forms.

[0274] In addition to and / or in combination with the materials disclosed herein, a number of hole injection materials, hole transport materials, host materials, dopant materials, exciton / hole blocking layer materials, electron transport materials, and electron injection materials can also be used in OLEDs. Non-limiting examples of materials that can be used in OLEDs in combination with the materials disclosed herein are listed in Table A below. Table A lists non-limiting classes of materials, non-limiting examples of compounds of each class, and references that disclose the materials.

[0275] Table A

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300] experiment

[0301] Synthesis Example

[0302] The chemical abbreviations used throughout this document are as follows:

[0303] SPhos is dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine,

[0304] Pd2(dba)3 is tris(dibenzylideneacetone)dipalladium(0),

[0305] Pd(PPh3)4 is tetrakis(triphenylphosphine)palladium(0),

[0306] DCM is dichloromethane,

[0307] EtOAc is ethyl acetate,

[0308] DME is dimethoxyethane, and

[0309] THF is tetrahydrofuran.

[0310] Synthesis of Compound A5

[0311] Synthesis of 4-(3-bromo-5-chlorophenyl)dibenzo[b,d]thiophene

[0312]

[0313] Dibenzo[b,d]thiophene-4-ylboronic acid (3.0 g, 13.15 mmol) and 1,3-dibromo-5-chlorobenzene (10.67 g, 39.5 mmol) were dissolved in toluene (150 ml) in a 250 mL two-necked round-bottom flask purged with nitrogen under a nitrogen atmosphere to obtain a colorless solution. K2CO3 (7.27 g, 52.6 mmol) in an aqueous solution (50 mL) was added to the reaction mixture, followed by Pd(PPh3)4 (0.304 g, 0.263 mmol). The reaction mixture was then heated to reflux under nitrogen for overnight (about 12 hours). After cooling to room temperature (about 22 ° C), the organic phase was separated, the solvent was evaporated, and unreacted 1,3-dibromo-5-chlorobenzene was distilled off under reduced pressure. The residue was subjected to column chromatography on silica gel with heptane / DCM (9 / 1, v / v) as eluent to afford 4-(3-bromo-5-chlorophenyl)dibenzo[b,d]thiophene (3.5 g, 71.2%) as a white solid.

[0314] Synthesis of 4-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)dibenzo[b,d]thiophene

[0315]

[0316] A solution of 4-(3-bromo-5-chlorophenyl)dibenzo[b,d]thiophene (4.0 g, 10.70 mmol), [1,1'-biphenyl]-4-ylboronic acid (2.120 g, 10.70 mmol), K2CO3 (3.0 g, 21.4 mmol) and Pd(PPh3)4 (0.37 g, 0.32 mmol) in toluene (150 ml) and water (50 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the organic layer was separated and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1, v / v) as eluent, and 4-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)dibenzo[b,d]thiophene (1.4 g 29%) was isolated as a white solid.

[0317] Synthesis of 2-(5-(dibenzo[b,d]thiophen-4-yl)-[1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetrakis Methyl-1,3,2-dioxaborolane

[0318]

[0319] A mixture of 4-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)dibenzo[b,d]thiophene (1.40 g, 3.13 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (1.59 g, 6.26 mmol), potassium acetate (0.92 g, 9.40 mmol), SPhos (0.25 g, 0.61 mmol) and Pd2(dba)3 (0.11 g, 0.12 mmol) in dioxane (150 ml) was prepared. Under nitrogen, reflux overnight (about 12 hours). After cooling to room temperature (about 22 ° C), the reaction mixture was diluted with EtOAc, washed with brine and water, and dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / EtOAc (9 / 1, v / v) as eluent to obtain 2- (5- (dibenzo [b, d] thiophene -4- bases) -[1,1': 4', 1 "- terphenyl] -3- bases) -4,4,5,5- tetramethyl -1,3,2- dioxaborolane (1.1 g, 65%) as a white solid.

[0320] Synthesis of Compound A5

[0321]

[0322] 2-Chloro-4,6-diphenyl-1,3,5-triazine (1.84 g, 6.87 mmol), 2-(5-(dibenzo[b,d]thiophen-4-yl)-[1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.70 g, 6.87 mmol), Pd(PPh3)4 (0.16 g, 0.137 mmol) and K2CO3 (2.8 A solution of 1-(4 ...

[0323] Synthesis of compound A11

[0324] Synthesis of 4-(5-chloro-[1,1'-biphenyl]-3-yl)-6-phenyldibenzo[b,d]thiophene

[0325]

[0326] A solution of 3-bromo-5-chloro-1,1'-biphenyl (10 g, 37.4 mmol), (6-phenyldibenzo [b, d] thiophene-4-yl) boronic acid (11.37 g, 37.4 mmol), Pd(PPh3)4 (0.432 g, 0.374 mmol) and K2CO3 (10.33 g, 74.8 mmol) in toluene (150 ml) and water (30 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the organic phase was separated and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1, v / v) as eluent to obtain 4-(5-chloro-[1,1'-biphenyl]-3-yl)-6-phenyldibenzo [b, d] thiophene (12.1 g, 72.4%) as a white solid.

[0327] Synthesis of 4,4,5,5-tetramethyl-2-(5-(6-phenyldibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3- 1,3,2-dioxaborolane

[0328]

[0329] A solution of 4-(5-chloro-[1,1'-biphenyl]-3-yl)-6-phenyldibenzo[b,d]thiophene (13.0 g, 29.1 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (14.77 g, 58.2 mmol), Pd2(dba)3 (0.20 g, 0.22 mmol), SPhos (0.35 g, 0.85 mmol) and potassium acetate (8.56 g, 87 mmol) in dioxane (200 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the reaction solution was quenched with water and extracted with EtOAc. The combined organic extracts were dried over Na2SO4, and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / EtOAc (9 / 1, v / v) as eluent to give 4,4,5,5-tetramethyl-2-(5-(6-phenyldibenzo[b,d]thiophen-4-yl)-[1,1′-biphenyl]-3-yl)-1,3,2-dioxaborolane (13.2 g, 84%) as a white solid.

[0330] Synthesis of compound A11

[0331]

[0332] A solution of 4,4,5,5-tetramethyl-2-(5-(6-phenyldibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-1,3,2-dioxaborolane (3.55 g, 6.59 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.765 g, 6.59 mmol), Pd(PPh3)4 (0.152 g, 0.132 mmol) and K2CO3 (1.822 g, 13.18 mmol) in toluene (100 ml), DME (100 ml) and water (50 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the organic layer was separated, filtered through a short plug of silica gel, and concentrated. The precipitate was collected, washed successively with heptane, ethanol and heptane to give compound A11 (3.9 g, 92%) as a white solid.

[0333] Synthesis of compound A14

[0334] Synthesis of compound A14

[0335]

[0336] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.44 g, 7.44 mmol), 2-(5-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (2.92 g, 6.95 mmol), Pd2(dba)3 (0.159 g, 0.174 mmol), SPhos (0.4 g, 0.976 mmol) and K3PO4 (4.80 g, 20.9 mmol) in toluene (125 ml), DME (100 ml) and water (25 ml) was refluxed under nitrogen for 18 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration, dissolved in boiling toluene (800 ml) and filtered through a short plug of silica gel. After evaporating the solvent, compound A14 (3.50 g, 70%) was recrystallized from toluene to give a white solid.

[0337] Synthesis of Compound A17

[0338] Synthesis of Compound A17

[0339]

[0340] A solution of 2-(6-([1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.51 g, 7.60 mmol), 2-(5-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (2.9 g, 6.91 mmol), Pd2(dba)3 (0.190 g, 0.207 mmol), SPhos (.5 g, 1.220 mmol) and K3PO4 (4.77 g, 20.7 mmol) in toluene (125 ml), DME (100 ml) and water (20 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration, dissolved in boiling toluene (800 ml) and filtered through a short plug of silica gel. After evaporating the solvent, compound A17 (3.75 g, 76%) was recrystallized from toluene to give a white solid.

[0341] Synthesis of compound A32

[0342] Synthesis of 4-(5-chloro-[1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophene

[0343]

[0344] A solution of 3-bromo-5-chloro-1,1'-biphenyl (14.8 g, 55.3 mmol), dibenzo[b, d]thiophene-4-ylboronic acid (12.62 g, 55.3 mmol), Pd(PPh3)4 (0.639 g, 0.553 mmol) and K2CO3 (15.29 g, 111 mmol) in toluene (150 ml) and water (30 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the organic phase was separated. After evaporating the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (85 / 15, v / v) as eluent to obtain 4-(5-chloro-[1,1'-biphenyl]-3-yl)dibenzo[b, d]thiophene (15.4 g, 70%) as a white solid.

[0345] Synthesis of 2-(5-(dibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane

[0346]

[0347] A solution of 4-(5-chloro-[1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophene (11.88 g, 32.0 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (16.27 g, 64.1 mmol), Pd2(dba)3 (280 mg), SPhos (0.32 g, 0.78 mmol) and potassium acetate (9.43 g, 96 mmol) in dioxane (200 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the reaction mixture was quenched with water and extracted with EtOAc. After evaporating the solvent, the residue was purified by column chromatography on silica gel with heptane / EtOAc (9 / 1, v / v) as eluent and recrystallized from heptane to give 2-(5-(dibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.1 g, 74.9%) as a white solid.

[0348] Synthesis of compound A32

[0349]

[0350] A solution of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2.24 g, 6.52 mmol), 2-(5-(dibenzo[b,d]thiophene-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.01 g, 6.52 mmol), Pd(PPh3)4 (0.151 g, 0.130 mmol) and K2CO3 (1.801 g, 13.03 mmol) in toluene (180 ml), DME (30 ml) and water (30 ml) was refluxed under nitrogen for 12 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration and washed successively with ethanol, water and ethanol. The crude product was recrystallized from toluene to give compound A32 (2.7 g, 64%) as a white solid.

[0351] Synthesis of compound A35

[0352] Synthesis of compound A35

[0353]

[0354] A solution of 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (3.0 g, 7.14 mmol) and 2-(5-(dibenzo[b,d]thiophene-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.30 g, 7.14 mmol), Pd(PPh3)4 (0.164 g, 0.14 mmol) and K2CO3 (1.975 g, 14.29 mmol) in toluene (100 ml), DME (100 ml) and water (50 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the solid was collected by filtration and washed successively with ethanol, water, ethanol and heptane. The crude product was dissolved in hot toluene, filtered through a short plug of silica gel, and recrystallized from toluene to give Compound A35 (3.7 g, yield 72%) as a white solid.

[0355] Synthesis of Compound A38

[0356] Synthesis of 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine

[0357]

[0358] At room temperature (about 22 ° C) by nitrogen in anhydrous THF (100 ml) 2-bromo-9,9-dimethyl-9H-fluorene (19.33 g, 70.8 mmol) and Mg (2.58 g, 106 mmol) refluxed for 2 hours to prepare the Grignard reagent solution was transferred dropwise to a solution of 2,4-dichloro-6-phenyl-1,3,5-triazine (8.0 g, 35.4 mmol) in anhydrous THF (50 ml). The reaction mixture was stirred overnight (about 12 hours) under nitrogen, quenched with concentrated HCl solution, and extracted with EtOAc. The organic phase was separated and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM (9 / 1, v / v) as eluent and recrystallized from heptane to give 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine (11 g, 81%) as yellow crystals.

[0359] Synthesis of Compound A38

[0360]

[0361] A solution of 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine (3.0 g, 7.82 mmol), 2-(5-(dibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.61 g, 7.82 mmol), Pd(PPh3)4 (0.18 g, 0.156 mmol) and K2CO3 (2.16 g, 15.63 mmol) in toluene (100 ml), DME (100 ml) and water (50 ml) was refluxed under nitrogen for 12 h. After cooling to room temperature (about 22° C.), the organic phase was separated and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM (6 / 4, v / v) as eluent and triturated with heptane to give compound A38 (4.3 g, 80%) as a white solid.

[0362] Synthesis of Compound A41

[0363] Synthesis of Compound A41

[0364]

[0365] A solution of 4,4,5,5-tetramethyl-2-(5-(6-phenyldibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-1,3,2-dioxaborolane (1.98 g, 3.68 mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (1.264 g, 3.68 mmol), Pd(PPh3)4 (0.085 g, 0.074 mmol) and K2CO3 (1.016 g, 7.35 mmol) in DME (150 ml) and water (5 ml) was refluxed under nitrogen for 12 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration, washed successively with ethanol, water, ethanol and heptane, then dissolved in boiling toluene and filtered through a short plug of silica gel. After evaporating the solvent, compound A41 (2.3 g, 87%) was recrystallized from toluene to give a white solid.

[0366] Synthesis of Compound A47

[0367] Synthesis of Compound A47

[0368]

[0369] A solution of 4,4,5,5-tetramethyl-2-(5-(6-phenyldibenzo[b,d]thiophen-4-yl)-[1,1'-biphenyl]-3-yl)-1,3,2-dioxaborolane (3.18 g, 5.91 mmol), 2-chloro-4-(9,9-dimethyl-9H-fluorene-2-yl)-6-phenyl-1,3,5-triazine (2.267 g, 5.91 mmol), Pd(PPh3)4 (0.136 g, 0.118 mmol) and potassium carbonate (1.632 g, 11.81 mmol) in toluene (30 ml), DME (100 ml) and water (20 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22°C), the organic layer was separated and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent to give compound A47 (2.1 g, 47%) as a white solid.

[0370] Synthesis of compound A110

[0371] Synthesis of compound A110

[0372]

[0373] A solution of 2-(5-(dibenzo[b,d]thiophene-4-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.70 g, 3.68 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (1.43 g, 3.68 mmol), Pd(PPh3)4 (0.085 g, 0.074 mmol) and K2CO3 (1.02 g, 7.35 mmol) in DME (120 ml) and water (20 ml) was refluxed under nitrogen for 14 hours. After cooling to room temperature (about 22° C.), the precipitate was collected by filtration and washed successively with ethanol, water, ethanol and heptane to give compound A110 (2.1 g, 89% yield) as a white solid.

[0374] Synthesis of compound A113

[0375] Synthesis of compound A113

[0376]

[0377] A solution of 2-(5-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (3.4 g, 8.10 mmol), 2-(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.28 g, 8.50 mmol), Pd2(dba)3 (0.222 g, 0.243 mmol), SPhos (0.199 g, 0.486 mmol) and K2CO3 (3.36 g, 24.29 mmol) in toluene (16 ml), DME (48 ml) and water (16 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration and triturated with ethanol. The crude product was dissolved in boiling toluene, then filtered through a short plug of silica gel and recrystallized from toluene to give compound A113 (4.25 g, 82%) as a white solid.

[0378] Synthesis of compound A116

[0379] Synthesis of 2-(3-bromo-5-chlorophenyl)-9,9-dimethyl-9H-fluorene

[0380]

[0381] A solution of (9,9-dimethyl-9H-fluorene-2-yl)boric acid (5.0 g, 21.0 mmol), 1,3-dibromo-5-chlorobenzene (14.19 g, 52.5 mmol), (PPh3)4 (0.49 g, 0.42 mmol) and K2CO3 (5.80 g, 42.0 mmol) in toluene (200 ml) and water (50 ml) was refluxed under nitrogen for 18 hours. After cooling to room temperature (about 22 ° C), the organic layer was separated, and excess 1,3-dibromo-5-chlorobenzene was distilled off. The residue was purified by column chromatography on silica gel with heptane / DCM (9 / 1, v / v) as eluent to obtain 2-(3-bromo-5-chlorophenyl)-9,9-dimethyl-9H-fluorene (6.2 g, 77%) as a colorless crystalline solid.

[0382] Synthesis of 4-(3-chloro-5-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)dibenzo[b,d]thiophene

[0383]

[0384] A solution of 2-(3-bromo-5-chlorophenyl)-9,9-dimethyl-9H-fluorene (7.7 g, 20.07 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (4.58 g, 20.07 mmol), Pd(PPh3)4 (0.464 g, 0.401 mmol) and K2CO3 (5.55 g, 40.1 mmol) in DME (150 ml) and water (20 ml) was refluxed under nitrogen for 12 hours. After cooling to room temperature (about 22° C.), the organic phase was separated and the solvent was evaporated. The crude product was purified by column chromatography on silica gel with heptane / DCM (9 / 1 to 4 / 1, v / v) as eluent to give 4-(3-chloro-5-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)dibenzo[b,d]thiophene (9.0 g, 92%) as a white crystalline solid.

[0385] Synthesis of 2-(3-(dibenzo[b,d]thiophen-4-yl)-5-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)-4,4,5, 5-Tetramethyl-1,3,2-dioxaborolane

[0386]

[0387] A solution of 4-(3-chloro-5-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)dibenzo[b,d]thiophene (9.5 g, 19.51 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (9.91 g, 39.0 mmol), Pd2(dba)3 (0.268 g, 0.293 mmol), SPhos (0.240 g, 0.585 mmol) and potassium acetate (5.74 g, 58.5 mmol) in dioxane was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic extracts were filtered and evaporated. The crude product was purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent to afford 2-(3-(dibenzo[b,d]thiophen-4-yl)-5-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.8 g, 69.1%) as a white crystalline solid.

[0388] Synthesis of compound A116

[0389]

[0390] A solution of 2-(3-(dibenzo[b,d]thiophene-4-yl)-5-(9,9-dimethyl-9H-fluorene-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.84 g, 10.09 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.70 g, 10.09 mmol), Pd(PPh3)4 (0.233 g, 0.202 mmol) and K2CO3 (3.49 g, 25.2 mmol) in DME (100 ml), toluene (100 ml) and water (50 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the precipitate was collected by filtration and then washed successively with water, ethanol and heptane to give compound A116 (5.5 g, 80%) as a white solid.

[0391] Synthesis of compound B3

[0392] Synthesis of compound B3

[0393]

[0394] A solution of 2-(5-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3 g, 5.47 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.464 g, 5.47 mmol), Pd(PPh3)4 (0.126 g, 0.109 mmol) and K2CO3 (1.512 g, 10.94 mmol) in toluene (75 ml), DME (75 ml) and water (20 ml) was refluxed under nitrogen for 6 hours. After cooling to room temperature (about 22°C), the precipitate was collected by filtration and then washed successively with water, ethanol, heptane and ethanol to give compound B3 (2.8 g, 78%) as a white solid.

[0395] Synthesis of compound B6

[0396] Synthesis of 2-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)-9,9-dimethyl-9H-fluorene

[0397]

[0398] A solution of 2-(3-bromo-5-chlorophenyl)-9,9-dimethyl-9H-fluorene (5 g, 13.03 mmol), [1,1'-biphenyl]-4-ylboronic acid (2.58 g, 13.03 mmol), Pd(PPh3)4 (0.301 g, 0.261 mmol) and K2CO3 (5.40 g, 39.1 mmol) in DME (150 ml) and water (25 ml) was refluxed under nitrogen for 12 hours. After cooling to room temperature (about 22° C.), the organic phase was separated and the solvent was evaporated. The crude product was purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent and recrystallized from heptane to give 2-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)-9,9-dimethyl-9H-fluorene (3.6 g, 60.5%) as colorless crystals.

[0399] Synthesis of 2-(5-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetrakis Methyl-1,3,2-dioxaborolane

[0400]

[0401] 2-(5-chloro-[1,1':4',1"-terphenyl]-3-yl)-9,9-dimethyl-9H-fluorene (6.8 g, 14.88 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (7.56 g, 29.8 mmol), Pd2(dba)3 (0.273 g, 0.298 mmol), SPhos (0.244 g, 0.595 mmol) and potassium acetate (2.92 g, 29.8 mmol) were added to dioxane. In alkane (100ml) and DME (100ml) solution in refluxed under nitrogen for 16 hours.After cooling to room temperature (about 22 DEG C), solid is filtered out.After evaporating off solvent, by carrying out column chromatography as eluent with heptane / DCM (1 / 1, v / v) on silica gel to purify residue, obtain 2- (5- (9,9- dimethyl -9H- fluorenes -2- bases) -[1,1 ': 4 ', 1 "- terphenyl] -3- bases) -4,4,5,5- tetramethyl -1,3,2- dioxaborolane (5.0g, 61.3%) in white solid.

[0402] Synthesis of compound B6

[0403]

[0404] 2-(5-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.17 g, 9.43 mmol), 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine (3.62 g, 9.43 mmol), Pd(PPh3) A solution of 4 (0.218 g, 0.189 mmol) and potassium carbonate (2.61 g, 18.85 mmol) in DME (75 ml), toluene (75 ml) and water (10 ml) was refluxed under nitrogen for 15 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration and then washed with ethanol, water, ethanol and heptane successively to give compound B6 (4.2 g, 58%) as a white crystalline solid.

[0405] Synthesis of compound B7

[0406] Synthesis of compound B7

[0407]

[0408] A solution of 2-(3,5-bis(9,9-dimethyl-9H-fluorene-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 g, 6.80 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.819 g, 6.80 mmol), Pd(PPh3)4 (0.079 g, 0.068 mmol) and K2CO3 (1.878 g, 13.59 mmol) in DME (75 ml), toluene (75 ml) and water (10 mL) was refluxed under nitrogen for 18 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration and then washed with ethanol, water, ethanol and heptane successively to give compound B7 (3.5 g, 74%) as a white crystalline solid.

[0409] Synthesis of compound C21

[0410] Synthesis of 2-(dibenzo[b,d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0411]

[0412] A solution of sec-butyl lithium (23.79 ml, 33.3 mmol) was added dropwise to a solution of dibenzo [b, d] selenophene (7 g, 30.3 mmol) in anhydrous THF (151 ml) at -78 ° C. The resulting mixture was stirred for 2 hours at this temperature and warmed to room temperature (about 22 ° C). After the mixture was cooled to -78 ° C, the mixture was quenched with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.72 ml, 37.9 mmol) by a syringe over about 1 minute, then gradually warmed to room temperature (about 22 ° C) and stirred overnight (about 12 hours). The resulting mixture was quenched with methanol, and the solvent was removed in vacuo. The crude product was purified by column chromatography on silica gel with heptane / DCM (4 / 1 to 1 / 1, v / v) as eluent to give 2-(dibenzo[b,d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 g, 65%) as a yellow oil.

[0413] Synthesis of 4-phenyldibenzo[b,d]selenophene

[0414]

[0415] A solution of 2-(dibenzo[b, d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 g, 19.60 mmol), iodobenzene (2.62 ml, 23.52 mmol), Pd(PPh3)4 (0.453 g, 0.392 mmol) and K2CO3 (8.13 g, 58.8 mmol) in THF (78 ml) and water (19.60 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22 ° C), the reaction mixture was partitioned with ethyl acetate and water. The organic phase was separated, then washed with brine and dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (9 / 1, v / v) as eluent to give 4-phenyldibenzo[b, d]selenophene (5.3 g, 88%) as a colorless oil.

[0416] Synthesis of 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]selenophene-4-yl)-1,3,2-dioxaborolane

[0417]

[0418] A solution of 4-phenyldibenzo[b,d]selenophene (5.3g, 17.25mmol) in THF (108ml) was cooled to -78°C and slowly treated with a 1.4M solution of sec-butyllithium in cyclohexane (16.63ml, 23.29mmol). The resulting mixture was stirred at -78°C for 1 hour and then allowed to warm to room temperature (about 22°C). The dark red solution was cooled to -78°C and quenched with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.28ml, 25.9mmol) via a syringe. The reaction mixture was gradually warmed to room temperature (about 22°C) and stirred for 16 hours. The resulting mixture was quenched with methanol and the solvent was subsequently removed in vacuo. The residue was dissolved in DCM, washed with water and brine, and then dried over Na2SO4. After evaporation of the solvent, the crude product was recrystallized from heptane to give 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]selenophene-4-yl)-1,3,2-dioxaborolane (5 g, 67%) as a light yellow solid.

[0419] Synthesis of compound C21

[0420]

[0421] A solution of 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]selenophene-4-yl)-1,3,2-dioxaborolane (2.0 g, 4.62 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (1.882 g, 4.85 mmol), Pd(PPh3)4 (0.160 g, 0.139 mmol) and K2CO3 (1.914 g, 13.85 mmol) in DME (28 ml), toluene (9 ml) and water (9 ml) was refluxed under nitrogen for 8 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration, then washed with water and ethanol, dissolved in boiling toluene, and finally filtered through a short silica gel plug. After evaporation of the solvent, compound C21 (2.6 g, 74%) was recrystallized from toluene as a white solid.

[0422] Synthesis of compound C23

[0423] Synthesis of compound C23

[0424]

[0425] A solution of 4,4,5,5-tetramethyl-2-(3-(6-phenyldibenzo[b,d]thiophen-4-yl)phenyl)-1,3,2-dioxaborolane (3.0 g, 6.49 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2.454 g, 7.14 mmol), Pd(PPh3)4 (0.375 g, 0.324 mmol) and K2CO3 (2.69 g, 19.46 mmol) in toluene (13 ml), DME (39 ml) and water (13 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration, then triturated with ethanol, dissolved in boiling toluene, and filtered through a short plug of silica gel. After evaporation of the solvent, compound C23 (3.78 g, 91%) was recrystallized from toluene as a white solid.

[0426] Synthesis of compound C29

[0427] Synthesis of compound C29

[0428]

[0429] A solution of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.75 g, 8.00 mmol), 6-phenyl-dibenzo[b,d]thiophene-4-ylboronic acid (2.68 g, 8.80 mmol), Pd2(dba)3 (0.20 g, 0.22 mmol), SPhos (0.40 g, 0.98 mmol), and K3PO4 (5.52 g, 24.00 mmol) in toluene (150 ml), DME (125 ml), and water (30 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the precipitate was collected by filtration and washed with water and DCM, then dissolved in boiling toluene and filtered through a short silica gel plug. After evaporation of the solvent, compound C29 (2.42 g, 53%) was recrystallized from toluene to give a white solid.

[0430] Synthesis of compound C47

[0431] Synthesis of compound C47

[0432]

[0433] A suspension of 4,4,5,5-tetramethyl-2-(3-(6-phenyldibenzo[b,d]thiophen-4-yl)phenyl)-1,3,2-dioxaborolane (3.09 g, 6.69 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.3 g, 6.69 mmol), Pd2(dba)3 (0.123 g, 0.134 mmol), SPhos (0.110 g, 0.268 mmol) and K3PO4 (4.26 g, 20.07 mmol) in toluene (20 ml), DME (30 ml) and water (10 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22 °C), the solid was collected by filtration and then dissolved in boiling toluene, filtered through a short plug of silica gel, and recrystallized from toluene to give Compound C47 (3.51 g, 81%) as a white solid.

[0434] Synthesis of compound C56

[0435] Synthesis of compound C56

[0436]

[0437] A solution of 4,4,5,5-tetramethyl-2-(4-(6-phenyldibenzo[b,d]thiophen-4-yl)phenyl)-1,3,2-dioxaborolane (3.5 g, 7.57 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.169 g, 6.31 mmol), Pd2(dba)3 (0.17 g, 0.19 mmol), SPhos (0.23 g, 0.57 mmol) and K3PO4 (4.02 g, 18.9 mmol) in toluene (100 ml), DME (100 ml) and water (10 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the reaction mixture was filtered through a plug of silica gel. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (9 / 1 to 4 / 1, v / v) as eluent and recrystallization from DCM to give compound C56 (2.2 g, 54%) as a white solid.

[0438] Synthesis of compound C65

[0439] Synthesis of compound C65

[0440]

[0441] A mixture solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.75 g, 8.11 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.61 g, 9.73 mmol), Pd2(dba)3 (0.149 g, 0.162 mmol), SPhos (0.266 g, 0.649 mmol) and potassium phosphate hydrate (3.74 g, 16.22 mmol) in toluene (90 mL) and water (10 mL) was refluxed overnight (about 12 hours) under nitrogen. After completion, toluene was evaporated, and the mixture (not completely soluble) was extracted with dichloromethane and washed with brine and water. The organic layers were combined, dried over Na2SO4, and concentrated under vacuum. The crude material was triturated with ethanol and then toluene. Compound C65 (3.0 g, 65%) was obtained as a light yellow solid.

[0442] Synthesis of compound C68

[0443] Synthesis of compound C68

[0444]

[0445] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 g, 8.65 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2.75 g, 8.00 mmol), Pd(PPh3)4 (0.28 g, 0.24 mmol) and K2CO3 (3.31 g, 24 mmol) in toluene (125 ml), DME (100 ml) and water (25 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22°C), the precipitate was collected by filtration and then rinsed with toluene. The crude product was triturated successively with toluene and methanol and then sublimed under vacuum to give compound C68 (4.25 g, 83%) as a white solid.

[0446] Synthesis of compound C71

[0447] Synthesis of compound C71

[0448]

[0449] A suspension of 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (2.1 g, 6.11 mmol), 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.82 g, 6.11 mmol), Pd(PPh3)4 (0.141 g, 0.122 mmol) and K2CO3 (2.53 g, 18.32 mmol) in DME (150 ml) and water (20 ml) was refluxed under nitrogen for 3 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration and subsequently washed with water and ethanol. The solid was dissolved in boiling toluene and filtered through a short plug of silica gel. After evaporation of the solvent, the crude product was recrystallized from toluene to give compound C71 (2.9 g, 74%) as a light yellow solid.

[0450] Synthesis of compound C73

[0451] Synthesis of compound C73

[0452]

[0453] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 g, 9.41 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.46 g, 10.07 mmol), Pd2(dba)3 (0.258 g, 0.282 mmol), SPhos (0.463 g, 1.129 mmol) and K3PO4 (6.49 g, 28.2 mmol) in toluene (125 ml), DME (100 ml) and water (25 ml) was refluxed under nitrogen for 18 hours. After cooling to room temperature (about 22 °C), the solid was collected by filtration, dissolved in boiling toluene, filtered through a short plug of silica gel, and recrystallized from toluene to give Compound C73 (4.5 g, 76%) as a white solid.

[0454] Synthesis of compound C74

[0455] Synthesis of compound C74

[0456]

[0457] A solution of 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (2.64 g, 6.07 mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromodibenzo[b,d]thiophene (2.53 g, 6.10 mmol), Pd2(dba)3 (0.139 g, 0.152 mmol), SPhos (0.187 g, 0.455 mmol) and K3PO4 (2.146 g, 10.11 mmol) in toluene (75 ml), DME (75 ml) and water (7.50 ml) was refluxed under nitrogen overnight (about 12 hours). After cooling to room temperature (about 22°C), the solid was collected by filtration, purified by column chromatography on silica gel with heptane / DCM (4 / 1 to 7 / 3, v / v) as eluent and recrystallization from heptane to give compound C74 (2.0 g, 61%) as a white solid.

[0458] Synthesis of compound C75

[0459] Synthesis of 4-([1,1'-biphenyl]-4-yl)dibenzo[b,d]selenophene

[0460]

[0461] A solution of 4-iodo-dibenzo[b, d]selenophene (10 g, 28.0 mmol), [1,1'-biphenyl]-4-ylboronic acid (8.32 g, 42.0 mmol), Pd(PPh3)4 (1.624 g, 1.400 mmol) and K2CO3 (7.74 g, 56.0 mmol) in DME (200 ml) and water (40 ml) was refluxed under nitrogen for 24 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration, washed with water and heptane, then dissolved in boiling toluene, and filtered through a short silica gel plug. After evaporation of the solvent, 4-([1,1'-biphenyl]-4-yl)dibenzo[b, d]selenophene (8.0 g, 74%) was recrystallized as a white solid from toluene.

[0462] Synthesis of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane

[0463]

[0464] To a solution of 4-([1,1'-biphenyl]-4-yl)dibenzo[b,d]selenophene (5.5 g, 14.35 mmol) in THF (150 ml) was added dropwise a solution of sec-butyllithium (18.45 ml, 25.8 mmol) at -78 °C. The resulting mixture was stirred at -78 °C for 5 hours, followed by the addition of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.12 ml, 25.1 mmol) in one portion. The reaction mixture was gradually warmed to room temperature (about 22 °C) and stirred for 16 hours, followed by quenching with water. The resulting mixture was extracted with ethyl acetate and then dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1 to 3 / 2, v / v) as eluent to give 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.6 g, 36%) as a white solid.

[0465] Synthesis of compound C75

[0466]

[0467] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]selenophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.62 g, 5.15 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (2 g, 5.15 mmol), Pd(PPh3)4 (0.179 g, 0.155 mmol) and K2CO3 (1.424 g, 10.30 mmol) in DME (150 ml), toluene (50 ml) and water (40 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration, washed successively with water and heptane, then dissolved in boiling toluene and filtered through a short plug of silica gel. The crude product was further purified by consecutive recrystallization from heptane and toluene to give compound C75 (2.1 g, 59%) as white crystals.

[0468] Synthesis of compound C83

[0469] Synthesis of compound C83

[0470]

[0471] A suspension of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.409 g, 7.01 mmol), 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.7 g, 5.84 mmol), Pd2(dba)3 (0.107 g, 0.117 mmol), SPhos (0.096 g, 0.234 mmol) and K2CO3 (2.421 g, 17.52 mmol) in toluene (20 ml), DME (65 ml) and water (15 ml) was refluxed under nitrogen overnight (about 12 hours). After cooling to room temperature (about 22° C.), the reaction mixture was diluted with water. The solid was collected by filtration, washed with water and ethanol, redissolved in hot toluene, and filtered through a short plug of silica gel.After evaporation of the solvent, the residue was recrystallized from EtOAc to give compound C83 (3.2 g, 85%) as a white solid.

[0472] Synthesis of compound C101

[0473] Synthesis of compound C101

[0474]

[0475] A solution of 2-(6-([1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.03 g, 8.73 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.50 g, 7.27 mmol), Pd2(dba)3 (0.20 g, 0.22 mmol), SPhos (0.27 g, 0.65 mmol) and K3PO4 (4.63 g, 21.8 mmol) in toluene (100 ml), DME (100 ml) and water (10 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the reaction mixture was diluted with DCM and filtered through a plug of silica gel. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1 to 3 / 2, v / v) as eluent and recrystallization from DCM to give compound C101 (1.6 g, 43%) as a white solid.

[0476] Synthesis of compound C110

[0477] Synthesis of compound C110

[0478]

[0479] A suspension of 2-(6-([1,1'-biphenyl]-3-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.1 g, 6.70 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.54 g, 7.37 mmol), Pd2(dba)3 (0.123 g, 0.134 mmol), and SPhos (0.110 g, 0.268 mmol) and K3PO4 (4.27 g, 20.11 mmol) in toluene (20.00 ml), DME (30.0 ml) and water (10 ml) was refluxed overnight under nitrogen. After cooling to room temperature, it was diluted with water, and the solid was collected by filtration and washed with ethanol. The crude product was dissolved in boiling toluene and filtered through a short plug of silica gel. After evaporating the solvent, compound C110 (4.2 g, 97%) was recrystallized from toluene as a white solid.

[0480] Synthesis of compound C119

[0481] Synthesis of compound C119

[0482]

[0483] A solution of (6-phenyldibenzo[b, d]thiophene-4-yl)boronic acid (3.14 g, 10.32 mmol), 2-chloro-4-(9,9-dimethyl-9H-fluorene-2-yl)-6-phenyl-1,3,5-triazine (3.6 g, 9.38 mmol), Pd(PPh3)4 (0.217 g, 0.188 mmol) and K2CO3 (3.89 g, 28.1 mmol) in DME (180 ml) and water (50 ml) was refluxed under nitrogen for 14 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration, washed with methanol, water, ethanol, ethyl acetate and heptane continuously, then dissolved in dichloromethane and filtered through a short silica gel plug. After evaporation of the solvent, the crude product was triturated with ethanol and heptane to obtain compound C119 (4.0 g, 70%) as a white solid.

[0484] Synthesis of compound C131

[0485] Synthesis of 2-(4-chlorophenyl)-4,6-bis(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine

[0486]

[0487] A solution of 2,4-dichloro-6-(4-chlorophenyl)-1,3,5-triazine (5 g, 19.19 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (9.14 g, 38.4 mmol), Pd(PPh3)4 (0.444 g, 0.384 mmol) and K2CO3 (7.96 g, 57.6 mmol) in DME (150 ml) and water (15 ml) was refluxed under nitrogen for 13 hours. After cooling to room temperature (about 22° C.), the organic phase was separated. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1, v / v) as eluent to give 2-(4-chlorophenyl)-4,6-bis(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine (5.43 g, 49.1%) as a white solid.

[0488] Synthesis of compound C131

[0489]

[0490] A solution of 2-(4-chlorophenyl)-4,6-bis(9,9-dimethyl-9H-fluorene-2-yl)-1,3,5-triazine (5.43 g, 9.42 mmol), (6-phenyldibenzo[b, d]thiophene-4-yl)boronic acid (2.87 g, 9.42 mmol), Pd2(dba)3 (0.129 g, 0.141 mmol), SPhos (0.116 g, 0.283 mmol) and K3PO4 (4.34 g, 18.85 mmol) in DME (200 ml) and water (25 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22 ° C), the organic phase was separated and purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent to give compound C131 as a white solid.

[0491] Synthesis of compound C134

[0492] Synthesis of compound C134

[0493]

[0494] A solution of (6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophene-4-yl)boronic acid (2.25 g, 5.92 mmol), 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine (2.4 g, 6.25 mmol), Pd(PPh3)4 (0.137 g, 0.118 mmol) and K2CO3 (2.453 g, 17.75 mmol) in DME (200 ml) and water (50 ml) was refluxed under nitrogen for 14 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration, washed successively with methanol, water, ethanol, ethyl acetate and heptane, then dissolved in boiling toluene and filtered through a short plug of silica gel. After evaporating the solvent, the crude product was triturated with ethanol and heptane to give compound C134 (3.0 g, 75%).

[0495] Synthesis of compound C139

[0496] Synthesis of compound C139

[0497]

[0498] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.41 g, 9.89 mmol), 2-(3-chlorophenyl)-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine (4.25 g, 9.24 mmol), Pd2(dba)3 (0.211 g, 0.231 mmol), SPhos (0.379 g, 0.924 mmol) and K3PO4 (6.38 g, 27.7 mmol) in toluene (125 ml), DME (100 ml) and water (30 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the reaction mixture was extracted with toluene. After evaporating the solvent, the residue was purified by column chromatography on silica gel with heptane / toluene (4 / 1 to 1 / 1, v / v) as eluent to give compound C139 (4.1 g, 59.7%) as a white solid.

[0499] Synthesis of compound C173

[0500] Synthesis of 2-(2,8-diphenyldibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Pentane

[0501]

[0502] To a solution of 2,8-diphenyldibenzo[b,d]thiophene (7.45 g, 22.14 mmol) in anhydrous THF was added dropwise a solution of sec-butyllithium in cyclohexane (28.5 ml, 39.9 mmol) at -78 °C. The reaction mixture was stirred at -78 °C for 2 hours while 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.21 g, 38.8 mmol) was added at a rate of 1 mL / min. The reaction mixture was gradually warmed to room temperature (about 22 °C) and stirred for 16 hours before being quenched with 10% NH4Cl aqueous solution. The resulting mixture was extracted with ethyl acetate. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent and subsequent recrystallization from heptane to give 2-(2,8-diphenyldibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.5 g, 53.7%) as white crystals.

[0503] Synthesis of compound 173

[0504]

[0505] A solution of 2-(2,8-diphenyldibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.03 g, 6.55), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (2.54 g, 6.55 mmol), Pd2(dba)3 (0.090 g, 0.098 mmol), SPhos (0.081 g, 0.197 mmol) and K3PO4 (3.02 g, 13.11 mmol) in DME (100 ml), toluene (100 ml) and water (10 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration, washed successively with ethanol, water, ethanol and heptane, and then triturated with boiling toluene to give compound 173 (4.0 g, 95%) as a white solid.

[0506] Synthesis of compound C185

[0507] Synthesis of 2-(6,8-diphenyldibenzo[b,d]thiophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Pentane

[0508]

[0509] To a solution of 2,4-diphenyldibenzo[b,d]thiophene (10 g, 29.7 mmol) in anhydrous THF was added dropwise a solution of sec-butyllithium in cyclohexane (38.2 ml, 53.5 mmol) at -78 °C. The reaction mixture was stirred at -78 °C for 2 hours while 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10.61 ml, 52.0 mmol) was added at a rate of 1 mL / min. The reaction mixture was gradually warmed to room temperature (about 22 °C) and stirred for 16 hours before being quenched with 10% NH4Cl aqueous solution. The resulting mixture was extracted with ethyl acetate. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / DCM (4 / 1 to 0 / 1, v / v) as eluent and subsequently recrystallized from heptane to give 2-(6,8-diphenyldibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.5 g, 69%) as white crystals.

[0510] Synthesis of compound C185

[0511]

[0512] A solution of 2-(6,8-diphenyldibenzo[b,d]thiophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.29 g, 9.27 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (3 g, 7.73 mmol), Pd(PPh3)4 (0.269 g, 0.232 mmol) and K2CO3 (2.14 g, 15.45 mmol) in DME (200 ml) and water (40.0 ml) was refluxed under nitrogen for 5 hours. After cooling to room temperature (about 22° C.), the solid was collected by filtration, dissolved in boiling xylene, then filtered through a short plug of silica gel, and recrystallized from xylene to give Compound C185 (2.6 g, 52.3%) as a white solid.

[0513] Synthesis of compound C251

[0514] Synthesis of compound C251

[0515]

[0516] A solution of 2-(4'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (3.0 g, 7.14 mmol), 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.53 g, 7.64 mmol), Pd2(dba)3 (0.196 g, 0.214 mmol), SPhos (0.40 g, 0.976 mmol) and K3PO4 (4.93 g, 21.43 mmol) in DME (80 ml), toluene (160 ml) and water (25 ml) was refluxed for 18 hours. After cooling to room temperature (about 22 °C), the solid was collected by filtration, washed with water, then dissolved in boiling toluene and filtered through a short plug of silica gel, and recrystallized from toluene to give compound C251 (3.43 g, 67%) as a white solid.

[0517] Synthesis of compound C254

[0518] Synthesis of compound C254

[0519]

[0520] A solution of 2-(6-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.72 g, 5.89 mmol), 2-(3-bromophenyl)-4,6-bis(4-fluorophenyl)-1,3,5-triazine (2.5 g, 5.89 mmol), Pd2(dba)3 (0.081 g, 0.088 mmol), SPhos (0.073 g, 0.177 mmol) and K3PO4 (2.71 g, 11.79 mmol) in DME (200 ml) and water (50 ml) was refluxed under nitrogen for 18 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration and purified by column chromatography on silica gel with heptane / DCM (1 / 1, v / v) as eluent and recrystallized from heptane to give compound C254 (2.5 g, 62%) as white crystals.

[0521] Synthesis of compound D1

[0522] Synthesis of compound D1

[0523]

[0524] A solution of 2-(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.5 g, 9.06 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.43 g, 9.97 mmol), Pd2(dba)3 (0.166 g, 0.181 mmol), SPhos (0.149 g, 0.362 mmol) and K3PO4 (5.77 g, 27.2 mmol) in DME (70) and water (15 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22° C.), the reaction mixture was diluted with water. The solid was collected by filtration, washed with methanol, dissolved in hot toluene, and filtered through a short plug of silica gel. After evaporation of the solvent, compound D1 (4.20 g, 82%) was recrystallized from toluene as a white solid.

[0525] Synthesis of compound D2

[0526] Synthesis of compound D2

[0527]

[0528] A solution of 4-(4-chlorophenyl)dibenzo[b,d]thiophene (2.46 g, 8.35 mmol), 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (4.0 g, 9.19 mmol), Pd2(dba)3 (0.15 g, 0.17 mmol), SPhos (0.27 g, 0.67 mmol) and K3PO4 (2.89 g, 16.7 mmol) in DME (90 ml) and water (10 ml) was refluxed under nitrogen for 6 hours. After cooling to room temperature (about 22 ° C), the reaction mixture was diluted with water. The solid was collected by filtration, washed successively with water and methanol, redissolved in hot toluene, and filtered through a short plug of silica gel. After evaporation of the solvent, compound 248 (2.1 g, 50%) was recrystallized from toluene as a white solid.

[0529] Synthesis of compound F1

[0530] Synthesis of compound F1

[0531]

[0532] A solution of 2,4,6-tris(3-bromophenyl)-1,3,5-triazine (3 g, 5.49 mmol), [1,1'-biphenyl]-4-ylboronic acid (3.48 g, 17.58 mmol), Pd2(dba)3 (0.101 g, 0.110 mmol), SPhos (0.180 g, 0.440 mmol) and K3PO4 (2.332 g, 10.99 mmol) in toluene (54 ml) and water (6 ml) was refluxed under nitrogen for 12 hours. After cooling to room temperature (about 22 ° C), the solid was collected by filtration and washed successively with water, methanol and toluene. The crude product was purified by sublimation to give Compound F1 (1.7 g, 40%) as a white solid.

[0533] Synthesis of compound F2

[0534] Synthesis of 2-chloro-4,6-bis(3-chlorophenyl)-1,3,5-triazine

[0535]

[0536] To a solution of 2,4,6-trichloro-1,3,5-triazine (3.1 g, 16.7 mmol) in THF (50 ml) at 0 ° C, a solution of (3-chlorophenyl) magnesium bromide (50 ml, 50.0 mmol) was added dropwise. It was slowly warmed to room temperature (about 22 ° C) and stirred for 2 hours. The reaction mixture was diluted with toluene and poured into an aqueous HCl solution (1 M, 200 ml). The organic layer was separated, washed with water, and then dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel to obtain 2-chloro-4,6-bis(3-chlorophenyl)-1,3,5-triazine (2.1 g, 37%) as a light yellow solid.

[0537] Synthesis of 2-([1,1'-biphenyl]-3-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine

[0538]

[0539] A solution of 2-chloro-4,6-bis(3-chlorophenyl)-1,3,5-triazine (3.6 g, 10.7 mmol), [1,1'-biphenyl]-3-ylboronic acid (3.2 g, 16.0 mmol), K2CO3 (4.4 g, 32.1 mmol) and Pd(PPh3)4 (0.62 g, 0.54 mmol) in DME (60 ml) and water (20 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22°C), the reaction mixture was filtered through a plug of silica gel. The filtrate was evaporated and the residue was purified by column chromatography on silica gel with heptane / DCM (9 / 1 to 7 / 3, v / v) as eluent and precipitation from DCM with methanol to give 2-([1,1′-biphenyl]-3-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine (3.7 g, 76%) as a white solid.

[0540] Synthesis of compound F2

[0541]

[0542] A solution of 2-([1,1'-biphenyl]-3-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine (3.7 g, 8.1 mmol), [1,1'-biphenyl]-4-ylboronic acid (4.0 g, 20.4 mmol), Pd2(dba)3 (0.15 g, 0.16 mmol), SPhos (0.27 g, 0.65 mmol) and K3PO4 monohydrate (5.6 g, 24.4 mmol) in m-xylene (200 ml) and water (20 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22°C), the solid was collected by filtration and washed with water and toluene. The solid was then dissolved in boiling o-xylene and filtered through a short silica gel plug. After evaporation of the solvent, compound F2 (4.5 g, 80%) was recrystallized as a white solid from o-xylene.

[0543] Synthesis of compound F3

[0544] Synthesis of 2-([1,1'-biphenyl]-4-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine

[0545]

[0546] A solution of 2-chloro-4,6-bis(3-chlorophenyl)-1,3,5-triazine (0.2 g, 0.59 mmol), [1,1'-biphenyl]-4-ylboronic acid (0.14 g, 0.71 mmol), K2CO3 (0.25 g, 1.78 mmol) and Pd(PPh3)4 (0.034 g, 0.030 mmol) in DME (21 ml) and water (7 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the reaction mixture was filtered through a plug of silica gel. The organic layer was separated, washed with water, and then dried over Na2SO4. After evaporation of the solvent, the crude product was purified by column chromatography on silica gel with heptane / DCM (9 / 1 to 7 / 3, v / v) as eluent to give 2-([1,1′-biphenyl]-4-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine (0.2 g, 74%) as a white solid.

[0547] Synthesis of compound F3

[0548]

[0549] A solution of 2-([1,1'-biphenyl]-4-yl)-4,6-bis(3-chlorophenyl)-1,3,5-triazine (2.3 g, 5.1 mmol), [1,1'-biphenyl]-4-ylboronic acid (3.0 g, 15.2 mmol), Pd2(dba)3 (0.093 g, 0.10 mmol), SPhos (0.17 g, 0.41 mmol) and K3PO4 monohydrate (3.5 g, 15.2 mmol) in m-xylene (200 ml) and water (20 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the solid was collected by filtration and triturated with boiling o-xylene. The crude product was purified by sublimation to give Compound F3 (2.1 g, 60%) as a white solid.

[0550] Synthesis of compound F4

[0551] Synthesis of compound F4

[0552]

[0553] A solution of 2,4-dichloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine (2.2 g, 6.43 mmol), 2-([1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.75 g, 7.71 mmol), Pd(PPh3)4 (0.223 g, 0.193 mmol) and K2CO3 (2.67 g, 19.29 mmol) in DME (100 ml), toluene (100 ml) and water (20 ml) was refluxed under nitrogen for 16 hours. After cooling to room temperature (about 22°C), the solid was collected by filtration and then washed successively with water and toluene to give Compound F4 (1.7 g, 36%) as a white solid.

[0554] Synthesis of compound F7

[0555] Synthesis of 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine

[0556]

[0557] A solution of dibenzo[b,d]thiophene-4-ylboronic acid (5.0 g, 21.92 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (12.39 g, 54.8 mmol), Pd(PPh3)4 (1.267 g, 1.096 mmol) and K2CO3 (9.09 g, 65.8 mmol) in THF (ratio: 10.0, volume: 199 ml) and water (ratio: 1.000, volume: 19.93 ml) was refluxed overnight (about 12 hours) under nitrogen. After cooling to room temperature (about 22 ° C), the reaction solution was filtered through a short plug of silica gel. The crude product was purified by column chromatography and sublimation on silica gel to give 2-chloro-4-(dibenzo[b,d]thiophene-4-yl)-6-phenyl-1,3,5-triazine (7.1 g, 72%) as a yellow solid.

[0558] Synthesis of compound F7

[0559]

[0560] 2-([1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.359 g, 6.62 mmol), 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine (2.25 g, 6.02 mmol), Pd(PPh3)4 (0.348 g, 0.301 mmol) and K2CO3 (2.495 g, 18.05 mm A solution of 1,4-diol (2-hydroxy-1-[4-(2-hydroxy-1-ol)- ...

[0561] Synthesis of compound F13

[0562] Synthesis of 2,4-dichloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine

[0563]

[0564] To a suspension of Mg (1.6 g, 65.9 mmol) activated with iodine in THF (50 ml) was added dropwise a solution of 2-bromo-9,9-dimethyl-9H-fluorene (12.0 g, 43.9 mmol) in THF (100 ml) at 60 ° C under nitrogen. After addition, the reaction mixture was refluxed for 3 hours and then transferred to a solution of 2,4,6-trichloro-1,3,5-triazine (8.10 g, 43.9 mmol) in THF (50 ml) at 0 ° C. The reaction mixture was then warmed to room temperature (about 22 ° C) and stirred overnight (about 12 hours) and then quenched with aqueous HCl. The resulting mixture was extracted with EtOAc. The combined organic extracts were dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / EtOAc (9 / 1, v / v) as eluent to give 2,4-dichloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine (8.0 g, 53%) as a white solid.

[0565] Synthesis of 2-([1,1':4',1"-terphenyl]-3-yl)-4-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3, 5-Triazine

[0566]

[0567] A solution of 2-([1,1':4',1"-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.00 g, 11.23 mmol), 2,4-dichloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine (10.76 g, 31.4 mmol), Pd(PPh3)4 (0.259 g, 0.225 mmol) and K2CO3 (4.66 g, 33.7 mmol) in DME (150 ml) and water (50 ml) was refluxed under nitrogen. Flow 18 hours. After cooling to room temperature (about 22 ° C), the reaction mixture was diluted with water, then extracted with EtOAc, and the organic extract was dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel with heptane / EtOAc (4 / 1, v / v) as eluent to obtain 2-([1,1':4',1"-terphenyl]-3-yl)-4-chloro-6-(9,9-dimethyl-9H-fluorene-2-yl)-1,3,5-triazine (4.5 g, 8.39 mmol, 74.8% yield) as a white solid.

[0568] Synthesis of compound F13

[0569]

[0570] 2-([1,1':4',1"-terphenyl]-3-yl)-4-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine (2.7 g, 5.04 mmol), dibenzo[b,d]thiophen-4-ylboronic acid (1.72 g, 7.56 mmol), Pd(PPh3)4 (0.116 g, 0.101 mmol) and K2CO3 (2.1 g, 15.11 mmol) were added. A solution of 1,4-dihydro-2-nitropropene (2,4-dihydro-1 ...

[0571] Device Examples

[0572] All devices are placed in a high vacuum (about 10 -7 The anode electrode was 80 nm indium tin oxide (ITO). The cathode electrode consisted of 1 nm LiF followed by 100 nm Al. Immediately after fabrication, all devices were encapsulated with epoxy-sealed glass lids in a nitrogen glove box (<1 ppm H2O and O2), and a moisture absorber was incorporated inside the package.

[0573] Device Examples - Group 1. The first group of device examples has an organic stack consisting of, starting from the ITO surface, 10 nm of LG101 (from LG Chem) as a hole injection layer (HIL), 45 nm of 4,4'-bis[N-(1-naphthyl)-N-phenylaminobiphenyl (NPD) as a hole transport layer (HTL), and 30 nm of compound E8 together with 20 wt% of the compound of the invention (compound C65) or a comparative compound (CC-1) and 10 wt% of emitter GD as an emissive layer (EML). On top of the EML, 50 nm of compound C65 or CC-1 was deposited as a hole blocking layer (HBL), followed by 40 nm of tris(8-hydroxyquinolyl)aluminum (Alq3) as an electron transport layer (ETL). The structures of the compounds used are shown below.

[0574]

[0575] Table D1 below is a summary of the device data, voltage (V), external efficiency (EQE), and power efficiency (PE) for Device Example 1 recorded at 9000 nits (nit).

[0576] Table D1

[0577]

[0578] The data in Table D1 show that Device 1 using the compound of the present invention (Compound C65) as a co-host and HBL achieves higher efficiency at a lower driving voltage than Device C-1 using Comparative Compound CC-1 as a co-host and HBL.

[0579] Device Examples - Group 2. The second group of device examples had the same structure as in Device Example 1, except that the inventive compound C101 or comparative compound CC-2 doped with 15% GD was used as the two-component EML. The chemical structures of the inventive and comparative compounds used are presented below.

[0580]

[0581] Table D2 below is a summary of the relative device data recorded at 9000 nits for Device Example 2. The device lifetime LT97 is defined as the time required for the device to decay to 97% of its original luminance at an initial luminance of 9000 nits at a constant current density, and the values ​​are normalized to the values ​​for Device C-2.

[0582] Table D2

[0583] Device EML HBL color V(V) EQE(%) PE(lm / W) LT97 Device C-2 CC-2:GD CC-2 green 7.5 14.7 22 100 Device 2 C101:GD C101 green 7.6 14.7 23 130

[0584] The data in Table D2 show that Device 2 using the compound of the present invention (Compound C101) as a host and HBL achieves higher efficiency and longer lifetime than Device C-2 using Comparative Compound CC-2 as a host and HBL.

[0585] Device Examples - Group 3. The third group of device examples has the same structure as in Device Example 1. The chemical structures of the inventive and comparative compounds used are presented below.

[0586]

[0587] Table D3 below is a summary of the relative device data for Device Example 3 recorded at 1000 nits. 2 The device lifetime LT95, defined as the time required for the device to decay to 95% of its original luminance at an initial luminance of 1000 nits at a constant current density with an acceleration factor of 1.8, was calculated from the values ​​measured at a current density of , and was normalized to the lifetime of device C-3.

[0588] Table D3

[0589] Device EML HBL color LT95 Device C-3 E8:CC-3:GD CC-3 green 100 Device 3 E8:A5:GD A5 green 694 Device 4 E8:A116:GD A116 green 529 Device 5 E8:C74:GD C74 green 537

[0590] The data in Table D3 show that compounds of the invention having substitutions on the dibenzothiophene or bridged phenyl groups exhibit longer lifetimes than comparative compounds without these substitutions when used as co-hosts in EMLs with E8 and as EBLs.

[0591] Device Example - Group 4. The fourth group of devices had the same structure as in Device Example 2. The chemical structures of the inventive and comparative compounds used are presented below.

[0592]

[0593]

[0594]

[0595] Table D4 below is a summary of the relative device data for Device Example 4 recorded at 1000 nits. The device lifetime LT95 is normalized to the lifetime of Device C-4.

[0596] Table D4

[0597]

[0598]

[0599] The data in Table D4 show that OLED devices using the compounds of the present invention as hosts and HBLs have longer lifetimes than devices using comparative compounds.

[0600] Device Example - Group 5. The fifth group of devices had the same structure as in Device Example 1. The chemical structures of the inventive and comparative compounds used are presented below.

[0601]

[0602] Table D5 below is a summary of the relative device data recorded at 9000 nits for Device Example 5. The device lifetime LT97 is defined as the time required for the device to decay to 97% of its original luminance at an initial luminance of 9000 nits at a constant current density, and the values ​​are normalized to the values ​​for Device C-11.

[0603] Table D5

[0604] Device EML HBL color V(V) EQE(%) PE(lm / W) LT97 Device C-11 E8:CC-11:GD CC-11 green 8.1 13.9 19.4 100 Device 31 E8:D2:GD D2 green 7.7 14.8 21.8 123

[0605] The data in Table D5 show that device 31 using the compound of the present invention (Compound D2) as a host and HBL achieves higher efficiency and longer lifetime than device C-11 using comparative compound CC-11 as a host and HBL.

[0606] Together, the device data in Tables D1 to D5 show that the compounds of the present invention, which have unique chemical structures, outperform comparative compounds when used as hosts or co-hosts and EBLs in OLEDs. It is well recognized that the performance of OLED devices is highly dependent on material properties, which are attributable to the chemical structure of the materials.

[0607] Premix Examples

[0608] The compatibility of the selected h-host and e-host was evaluated by compositional analysis of films made from single-source co-evaporation of pre-mixtures of these two components.A first set of potential pre-mixtures of the selected h-host and e-host are presented in Table PM1.

[0609] Table PM1: Potential premixes containing selected h-hosts and e-hosts

[0610] Premix hMain e-Subject PM-A1 Compound E1 Compound C1 PM-A2 Compound E2 Compound C2 PM-A3 Compound E5 Compound C65 PM-A4 Compound E8 Compound C74 PM-A5 Compound E11 Compound C74 PM-A6 Compound E17 Compound C74 PM-A7 Compound E8 CC-1 PM-A8 Compound E8 Compound A5 PM-A9 Compound E8 Compound C17 PM-A10 Compound E17 Compound A5 PM-A11 Compound E25 CC-1 PM-A12 Compound E26 Compound C74 PM-A13 Compound E26 Compound C248 PM-A14 Compound E28 Compound C74 PM-A15 Compound E29 Compound C74 PM-A16 Compound E30 Compound C74

[0611] Premix Example - Group 1: For premix PM-A4, compound E8 and compound C74 were provided in a weight ratio of 7:3, which were then physically mixed, ground and loaded into an evaporation source. -7 Under the pressure of The premixed composition is thermally co-evaporated at a rate of and deposited onto a glass substrate. The substrate was replaced continuously after the deposition and cooling of the source without stopping the deposition and cooling the source. The composition of the film was analyzed by high performance liquid chromatography (HPLC), and the results are shown in Table 2.

[0612]

[0613] Table PM2: HPLC composition (%) of films deposited sequentially from a premix (PM-A4) containing compound E8 and compound C74 in a weight ratio of 7:3. (HPLC conditions C18, 100 45 minutes, detection wavelength 254 nm) (HPLC composition may or may not be consistent with the weight ratio due to different absorption coefficients.)

[0614] membrane Compound E8 Compound C74 Plate 1 69.5 30.5 Plate 2 68.4 31.6 Plate 3 68.2 31.8 Plate 4 68.2 31.8 Plate 5 68.4 31.6 Plate 6 69.3 30.7 Plate 7 70.6 29.4 Plate 8 71.7 28.3 Plate 9 73.0 27.0

[0615] As shown in Table PM2, the composition of the component compound E8 and compound C74 does not change significantly in plate 1 to plate 9. The minor fluctuations in concentration do not reveal any trend and can be explained by the precision of the HPLC analysis. Generally, the concentration variation before and after deposition within 5% during the entire process is considered good and suitable for commercial OLED applications.

[0616] Premix Example - Group 2: For premix PM-A12, compound E26 and compound C74 were provided in a weight ratio of 3:2, then physically mixed, ground and loaded into an evaporation source. -7 Under the pressure of The premixed composition is thermally co-evaporated at a rate of and deposited onto a glass substrate. The substrate was replaced continuously after the film was deposited without stopping the deposition and cooling the source. The composition of the film was analyzed by high performance liquid chromatography (HPLC) and the results are shown in Table PM3.

[0617]

[0618] Table PM3: HPLC composition (%) of films deposited sequentially from a premix (PM-A12) containing compound E26 and compound C74 in a weight ratio of 3:2. (HPLC conditions C18, 100 45 minutes, detection wavelength 254 nm) (Due to different absorption coefficients, the HPLC composition may or may not be consistent with the weight ratio.)

[0619] membrane Compound E26 Compound C74 Plate 1 67.1 32.9 Plate 2 67.3 32.7 Plate 3 68.4 31.6 Plate 4 69.6 30.4 Plate 5 70.8 29.2 Plate 6 71.9 28.1 Plate 7 72.9 27.1 Plate 8 73.9 26.1

[0620] Again, the results for Plates 1 to 8 show only minor variations, and would be considered good and suitable for commercial OLED applications.

[0621] Premix Example - Group 3. For premix PM-A16, compound E30 and compound C74 were provided in a 1:1 weight ratio, then physically mixed, ground and loaded into an evaporation source. -7 Under the pressure of The premixed composition is thermally co-evaporated at a rate of and deposited onto a glass substrate. The substrate was replaced continuously after the film was formed without stopping the deposition and cooling the source. The composition of the film was analyzed by high performance liquid chromatography (HPLC) and the results are shown in Table PM4.

[0622]

[0623] Table PM4: HPLC composition (%) of films deposited sequentially from a premix (PM-A16) containing compound E30 and compound C74 in a weight ratio of 1:1. (HPLC conditions C18, 100 45 minutes, detection wavelength 254 nm) (Due to different absorption coefficients, the HPLC composition may or may not be consistent with the weight ratio.)

[0624] membrane Compound E30 Compound C74 Plate 1 52.3 47.7 Plate 2 51.6 48.4 Plate 3 52.1 47.9 Plate 4 52.9 47.1 Plate 5 53.9 46.1 Plate 6 54.6 45.4 Plate 7 51.8 48.2

[0625] The data in Tables PM2, PM3 and PM4 show that the ratio of the two components in premixes PM-A4, PM-A12 and PM-A16 does not change significantly during the continuous single-source co-evaporation. The smaller fluctuations in concentration do not reveal any tendency and can be explained by the accuracy of the HPLC analysis. Generally, the concentration changes before and after the deposition within 5% during the entire process are considered good and suitable for commercial OLED applications. These experiments conclude that PM-A4, PM-A12 and PM-A16 are stable premixes for co-evaporation. It is believed that the co-evaporation stability of these premixes can be traced back to the unique chemical structure associated with these two types of materials.

[0626] A second set of potential premixes of selected h-hosts and e-hosts are presented in Table PM5.

[0627] Table PM5: Potential premixes containing selected h-hosts and e-hosts

[0628] Premix hMain e-Subject PM-B1 Compound G1 Compound F9 PM-B2 Compound G2 Compound F10 PM-B3 Compound G8 Compound F13 PM-B4 Compound G9 Compound F13 PM-B5 Compound G26 Compound F5

[0629] Example 1. For premix PM-B3, compound G8 and compound F13 were provided in a weight ratio of 9:1, which were then physically mixed, ground and loaded into an evaporation source. -7 Under the pressure of The premixed composition is thermally co-evaporated at a rate of and deposited onto a glass substrate. The substrate was replaced continuously after the film was formed without stopping the deposition or cooling the source. Deposition was stopped after the material was exhausted. The composition of the film was analyzed by high performance liquid chromatography (HPLC) and the results are shown in Table PM6.

[0630]

[0631] Table PM6: HPLC composition (%) of films deposited sequentially from a premix (PM-B3) containing compound G8 and compound F13 in a weight ratio of 9:1. (HPLC conditions C18, 100 45 minutes, detection wavelength 254 nm) (Due to different absorption coefficients, the HPLC composition may or may not be consistent with the weight ratio.)

[0632] Table PM6

[0633] membrane Compound G8 Compound F13 Plate 1 95.9 4.1 Plate 2 96.0 4.0 Plate 3 96.5 3.5 Plate 4 96.8 3.2

[0634] The composition of the component compounds G8 and F13 does not vary significantly from plate 1 to plate 4. The minor fluctuations in concentration do not reveal any trends and can be explained by the precision of the HPLC analysis. Generally, pre- and post-deposition concentration variations within 5% during the entire process are considered good and suitable for commercial OLED applications. These results demonstrate that PM3 is a stable pre-mixture for co-evaporation. It is believed that the co-evaporation stability of this pre-mixture can be traced back to the unique chemical structure associated with these two types of materials.

[0635] It should be understood that the various embodiments described herein are only examples and are not intended to limit the scope of the present invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the present invention. As will be understood by those skilled in the art, the present invention as required can therefore include the variations of the specific examples and preferred embodiments described herein. It should be understood that the various theories about why the present invention works are not intended to be restrictive.

Claims

1. A first compound, wherein the first compound has the formula: Among them G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene; Where L 1 selected from the group consisting of: a direct bond, a phenyl group, and a biphenyl group; Where L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof; Among them G 4 Selected from the group consisting of phenyl, biphenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline and isoquinoline; Among them G 2 , G 3 and G 5 each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof; Among them G 2 , G 3 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof; Among them G 4 optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silane, and combinations thereof; where m is 0 or 1, Where n is an integer from 0 to 4; in, When m or n is greater than 1, each G 4 or G 5 Can be the same or different; Where, when n is 0, m is equal to 1, and each G 4 All are selected from the group consisting of phenyl and biphenyl; When n is equal to or greater than 1, L 1 is not a direct key; and When m and n are both 0, L 1 It's biphenyl.

2. The first compound according to claim 1, wherein the first compound has the following formula: Among them G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene; Where L 1 It is a direct key; Where L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof; Among them G 4 Selected from the group consisting of phenyl, biphenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline and isoquinoline; Among them G 2 , G 3 and G 5 Each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof; Among them G 2 , G 3 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof; Among them G 4 optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silane, and combinations thereof; where m is 1, Where n is 0.

3. The first compound according to claim 1, wherein the first compound has the following formula: Among them G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene; Where L 1 It is phenyl; Where L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof; Among them G 4 Selected from the group consisting of phenyl, biphenyl, naphthalene, pyridine, pyrimidine, pyrazine, quinoline and isoquinoline; Among them G 2 , G 3 and G 5 each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof; Among them G 2 , G 3 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof; Among them G 4 optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silane, and combinations thereof; where m is 0 or 1, Where n is 1, 2, 3 or 4.

4. The first compound according to claim 1, wherein the first compound has the following formula: Among them G 1 Selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene and fluorene; Where L 1 It is biphenyl; Where L 2 and L 3 Each is independently selected from the group consisting of a direct bond, a phenyl group, a biphenyl group, a terphenyl group, a pyridine group, a pyrimidine group, and combinations thereof; Among them G 4 Selected from the group consisting of biphenyl, naphthalene, phenanthrene, pyrazine, quinoline, isoquinoline and phenanthroline; Among them G 2 , G 3 and G 5 each independently selected from the group consisting of phenyl, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phenanthroline, aza-fluorene, and combinations thereof; Among them G 2 , G 3 and G 5 each optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silanyl, phenyl, biphenyl, terphenyl, pyridine, and combinations thereof; Among them G 4 optionally further substituted with one or more non-fused substituents selected from the group consisting of deuterium, alkyl, alkoxy, cycloalkyl, cycloalkoxy, halogen, nitro, nitrile, silane, and combinations thereof; where m is 1, Where n is an integer from 0 to 4; in, When m or n is greater than 1, each G 4 or G 5 may be the same or different; and Where, when n is 0, m is equal to 1, and each G 4 It's biphenyl.

5. The first compound according to any one of claims 1 to 3, G 4 Having a structure selected from the group consisting of:.

6. The first compound according to any one of claims 1 to 4, wherein G 1 Having a structure selected from the group consisting of: wherein X is selected from the group consisting of O, S and Se; Where R B1 and R B2 are independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, halogen, and combinations thereof; and Where R B1 and R B2 Optionally linked to form a ring.

7. The first compound according to any one of claims 1 to 4, wherein L 1 Select from the group consisting of:

8. The first compound according to any one of claims 1 to 4, wherein G 2 , G 3 and G 5 Independently selected from the group consisting of: Where R B1 and R B2 are independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, halogen, and combinations thereof; and Where R B1 and R B2 Optionally linked to form a ring.

9. The first compound according to any one of claims 1 to 4, wherein G 2 , G 3 , G 4 and G 5 At least one of them is substituted by at least one fluorine atom.

10. The first compound according to claim 1 or 4, wherein the first compound has the following formula: wherein X is selected from the group consisting of O, S and Se.

11. The first compound according to any one of claims 1, 2 or 4, wherein When n is 0 and m is 1, G 4 -G 1 Having a structure selected from the group consisting of:

12. A first compound, the first compound being selected from the group consisting of:

13. A material composition comprising the first compound according to any one of claims 1 to 12.

14. A first device, comprising a first organic light-emitting device, wherein the first organic light-emitting device comprises: anode; cathode; and An organic layer disposed between the anode and the cathode, the organic layer comprising the first compound according to any one of claims 1 to 12.

15. A metal complex having a general formula selected from the following: wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

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