Organic light emitting diode material

Abstract

This application relates to organic light-emitting diode (OLED) materials. The present invention relates to organic light-emitting diode (OLED) materials. The materials may be compounds having Formula I. The compounds are suitable for use in organic light-emitting diodes. The compounds can also be used as charge transport and charge blocking layers, and as the main body in the light-emitting layer of an organic light-emitting device (OLED).

Description

[0001] This application is a divisional application of the invention patent application filed on July 11, 2014, with application number 201410331626.0 and entitled "Organic Light Emitting Diode Materials".

[0002] This application claims priority to U.S. Provisional Application No. 61 / 846,100, filed July 15, 2013, which is incorporated herein by reference in its entirety.

[0003] The claimed invention was made by one or more of the following parties who entered into a joint university-corporation research agreement, in the name of one or more of the following parties and / or in conjunction with one or more of the following parties: the University of Michigan Board of Trustees, Princeton University, the University of Southern California, and Universal Display Corporation. The agreement was effective on or before the date on which the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of the agreement. Technical Field

[0004] This invention relates to novel organic compounds comprising triphenylene and carbazole. These compounds can be used as host materials for organic light-emitting diodes (OLEDs). They can also be used as charge transport and charge blocking layers, and as host materials in the light-emitting layers of organic light-emitting devices (OLEDs). Background Technology

[0005] Optoelectronic devices utilizing organic materials are becoming increasingly popular for several reasons. Many of the materials used to manufacture such devices are relatively inexpensive, thus organic optoelectronic devices have the potential to achieve a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them well-suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices, organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials. For instance, the wavelength of light emitted by an organic emitting layer can often be easily tuned using appropriate dopants.

[0006] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly prominent technology for applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in U.S. Patents 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0007] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suitable for emitting specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Color can be measured using the CIE coordinate system, well-known in the art.

[0008] An example of a green emitting molecule is tris(2-phenylpyridine)iridium, denoted as Ir(ppy)3, which has the following structure:

[0009]

[0010] In this figure and in the figures later in this article, the valence bond from nitrogen to the metal (here, Ir) is depicted as a straight line.

[0011] As used herein, the term "organic" includes polymeric materials as well as small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist of a series of chemical shells built upon the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small-molecule emitter. Dendritic polymers can be "small molecules," and it is believed that all dendritic polymers currently used in the OLED field are small molecules.

[0012] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "on" the second layer, the first layer is positioned further from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "on" the anode.

[0013] As used herein, “solution-handleable” means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0014] When a ligand is believed to directly contribute to the photosensitivity of the emitting material, the ligand can be called "photosensitive." When a ligand is believed not to contribute to the photosensitivity of the emitting material, the ligand can be called "auxiliary," but auxiliary ligands can alter the properties of photosensitivity ligands.

[0015] As used herein, and as will be understood by those skilled in the art, if a first energy level is closer to the vacuum level, then the first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” (LUMO) level is “greater” or “higher” than the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to a smaller absolute value of IP (less negative IP). Similarly, a higher LUMO level corresponds to a smaller absolute value of electron affinity (EA) (less negative EA). On a conventional energy level diagram, the vacuum level is at the top, and the LUMO levels of a material are higher than the HOMO levels of the same material. A “higher” HOMO or LUMO level appears to be closer to the top of this diagram than a “lower” HOMO or LUMO level.

[0016] As used herein, and as will be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because work functions are typically measured as negative numbers relative to the vacuum level, thus implying that the “higher” work function is more negative. On a conventional energy level diagram, the vacuum level is at the top, and a “higher” work function is described as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow a different convention than those for work functions.

[0017] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety. Summary of the Invention

[0018] A new class of compounds containing triphenylene and carbazole was provided.

[0019] This invention provides a compound having Formula I:

[0020]

[0021] Where R 3a R 3b R 3c Or R 3d At least one of them has Equation II:

[0022]

[0023] Where R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has Equation III:

[0024] ---L 2 -G(III);

[0025] Where L 1 and L 2 The group is independently selected from the group consisting of: direct bonds, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof; wherein the aryl group and the heteroaryl group are optionally further substituted by one or more groups selected from the group consisting of: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof;

[0026] X is selected from the following groups: O, S, and Se;

[0027] Where G is carbazole, which can be optionally substituted;

[0028] Where R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof;

[0029] Where R is not Equation II 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and

[0030] R is not Equation III 4a R 4b R 4c R 5a R 5b R 5c and R 5dEach is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0031] In some embodiments, G is coupled with L at the nitrogen atom at the 9th position of carbazole. 2 connect.

[0032] In some embodiments, G is coupled with L at the carbon atom at position 1, 2, 3, or 4 of the carbazole. 2 connect.

[0033] In some embodiments, L 1 It is a direct key.

[0034] In some embodiments, R 4b R 5a Or R 5c One of them is L 2 -G.

[0035] In some embodiments, L 1 and L 2 Independently selected from the following groups: direct bond, phenyl, and biphenyl.

[0036] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl and combinations thereof, not R of formula II. 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, aryl, heteroaryl and combinations thereof, and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.

[0037] In some embodiments, R 1a R 1b R 1c R1d R 2a R 2b R 2c and R 2d Each of the following groups, independently selected: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazole, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof, not R of formula II. 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazole, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof, and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof.

[0038] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d It's hydrogen, not R in formula II. 3a R 3b R 3c and R 3d It is hydrogen, and not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d It is hydrogen.

[0039] In some embodiments, X is O.

[0040] In some embodiments, X is S.

[0041] In some embodiments, X is S, L 1 and L2 It is a direct key, and R 5a It is L 2 -G.

[0042] In some embodiments, X is S, L 1 It's a direct key, L 2 It is a phenyl group, and R 5a It is L 2 -G.

[0043] In some embodiments, G is substituted by one or more substituents selected from the group consisting of: deuterium, hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0044] In some embodiments, the compounds of the present invention have Formula IV:

[0045]

[0046] In some embodiments, the compounds of the present invention have formula V:

[0047]

[0048] In some embodiments, the compound is selected from the group consisting of:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] The present invention also provides an organic light-emitting device. The organic light-emitting device comprises:

[0056] anode;

[0057] cathode;

[0058] An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having formula I:

[0059]

[0060] Where R 3a R 3b R 3c Or R 3d At least one of them has Equation II:

[0061]

[0062] Where R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has Equation III:

[0063] ---L 2 -G(III);

[0064] Where L 1 and L 2 The group is independently selected from the group consisting of: direct bonds, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof; wherein the aryl group and the heteroaryl group are optionally further substituted by one or more groups selected from the group consisting of: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof;

[0065] X is selected from the following groups: O, S, and Se;

[0066] Wherein G is carbazole, which can be optionally substituted; and

[0067] Where R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof;

[0068] Where R is not Equation II 3a R 3b R 3c and R 3dEach is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and

[0069] R is not Equation III 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0070] The present invention also provides a formulation comprising a compound of formula I. Attached Figure Description

[0071] Embodiments of the invention are illustrated in the accompanying drawings, which are incorporated herein and form part of the specification, and together with the description serve to explain the principles of the invention and enable those skilled in the art to make and use the invention.

[0072] Figure 1 An organic light-emitting device was displayed.

[0073] Figure 2 An inverted organic light-emitting device without a separate electron transport layer was demonstrated.

[0074] Figure 3 Compound of formula IV was demonstrated. Detailed Implementation

[0075] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer at the cathode. The injected holes and electrons migrate toward the electrodes with opposite charges. When electrons and holes are confined to the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When excitons relax via photoemission mechanisms, light is emitted. In some cases, excitons may be confined to polarons or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0076] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs in timeframes of less than 10 nanoseconds.

[0077] Recently, OLEDs with emitting materials that emit light from the triplet state (“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), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5–6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0078] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. 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 cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as the example materials, are described in more detail in columns 6-10 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0079] There are numerous examples of each of these layers. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA 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 herein by reference in its entirety. Examples of emitter and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein 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 herein by reference in its entirety. Examples of cathodes, including composite cathodes having a thin metal layer such as Mg:Ag and an overlying transparent, conductive, sputtered-deposited ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. The principle 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 also incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0080] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing the layers described herein. Because the most common OLED configuration has a cathode disposed on the anode, and the device 200 has a cathode 215 disposed beneath the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 An example is provided of how some layers can be omitted from the structure of device 100.

[0081] Figure 1 and 2The simple layered structures described herein are provided as non-limiting examples, and it should be understood that embodiments of the invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. A functional OLED can be realized by combining the described layers in different ways based on design, performance, and cost factors, or several layers can be omitted entirely. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials (e.g., mixtures of host and dopant) or more generally, mixtures may be used. Furthermore, 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 emitter layer 220, and may be described as a hole transport layer or a hole injection layer. In some embodiments, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of different organic materials are described.

[0082] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. As another example, an OLED with a single organic layer can be used. OLEDs can be stacked, as described, for example, in No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure can be detached... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., all of which are incorporated herein by reference in their entirety.

[0083] Unless otherwise specified, any of the layers in the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (e.g., as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (e.g., as described in U.S. Patent No. 6,337,102 to Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (e.g., as described in U.S. Patent No. 7,431,968, which is incorporated herein 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 via a mask, cold soldering (e.g., as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet printing and OVJP. Other methods may also be used. The material to be deposited can be modified to be compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbons, can be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons can be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures can have better solution handling ability than materials with symmetric structures because asymmetric materials can have a lower tendency to recrystallize. Dendritic polymer substituents can be used to enhance the solution handling ability of small molecules.

[0084] Devices manufactured according to embodiments of the present invention may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited on, under, or adjacent to a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For the mixture to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric material to non-polymeric material can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0085] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent displays, flexible displays, laser printers, telephones, mobile phones, personal digital assistants (PDAs), laptop computers, digital cameras, video cameras, viewfinders, microdisplays, 3D displays, vehicles, large-area walls, theater or stadium screens, or signs. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to the present invention. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18 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 to +80 degrees Celsius).

[0086] 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.

[0087] As used herein, the term "halogen" or "halogen" includes fluorine, chlorine, bromine, and iodine.

[0088] As used herein, the term "alkyl" encompasses both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms and include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. Additionally, the alkyl group may optionally be substituted.

[0089] 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, etc. Additionally, cycloalkyl groups may optionally be substituted.

[0090] As used herein, the term "alkenyl" encompasses both straight-chain and branched alkenyl groups. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl groups may optionally be substituted.

[0091] As used herein, the term "alkynyl" encompasses both straight-chain and branched alkynyl groups. Preferred alkyl groups are alkyl groups containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0092] As used herein, the term "aralkyl" or "arylalkyl" covers an alkyl group having an aromatic group as a substituent. Additionally, aralkyl groups may optionally be substituted.

[0093] As used herein, the term "heterocyclic group" encompasses non-aromatic cyclic radicals. Preferred heterocyclic groups are those containing 3 or 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolidinyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Additionally, the heterocyclic group may optionally be substituted.

[0094] As used herein, the term "aryl" or "aromatic group" encompasses both monocyclic groups and polycyclic systems. A polycyclic system may have two or more rings in which two carbon atoms are shared by 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, heterocyclic, and / or heteroaryl. Additionally, the aryl group may optionally be substituted.

[0095] 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. The term "heteroaryl" also includes polycyclic heteroaromatic systems having two or more rings shared by two adjacent rings (the rings being "fused"), wherein at least one of the rings is a heteroaryl group; for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Additionally, the heteroaryl group may optionally be substituted.

[0096] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may optionally be substituted by one or more substituents selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0097] As used herein, the term "substituted" indicates that a substituent, not hydrogen, is bonded to the relevant carbon or nitrogen atom. Therefore, in R... 1 When replaced by a single unit, then an R 1 It must not be hydrogen. Similarly, in R... 1 When replaced by two, then the two Rs 1 It must not be hydrogen. Similarly, in R... 1 When "indicating no substitution", R 1 It is hydrogen for all available locations.

[0098] The term "aza" in the fragments described herein (i.e., aza-dibenzofuran, aza-dibenzothiophene, etc.) indicates that one or more CH groups in the individual fragment can be substituted with nitrogen atoms. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0099] It should be understood that when a molecular fragment is described as a substituent or additionally attached to another part, its name can be written as if it were a fragment (e.g., naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0100] Various carbazole-containing compounds have been developed as organic electroluminescent materials. Depending on the unique manner in which they are constructed with block linkages, these compounds exhibit different energy levels, molecular stacking, and charge transport properties, all of which significantly affect device performance. This invention discloses a novel class of compounds comprising triphenylene and carbazole. Unexpectedly, phosphorescent OLED devices using the compounds of this invention as host materials exhibit superior stability compared to compounds reported in the literature.

[0101] In some embodiments, a compound having formula I is provided:

[0102]

[0103] In compound I, R 3aR 3b R 3c Or R 3d At least one of them has Equation II:

[0104]

[0105] R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has Equation III:

[0106] ---L 2 -G(III);

[0107] L 1 and L 2 Independently selected from the group consisting of: direct bond, aryl group having 6-30 carbon atoms, heteroaryl group having 3-30 carbon atoms, and combinations thereof; wherein the aryl group and the heteroaryl group are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof; X is selected from the group consisting of: O, S, and Se; G is a carbazole that may be optionally substituted; R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; R not of formula II 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and is not R of formula III. 4a R 4b R 4c R 5a R 5b R5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0108] In some embodiments, G is coupled with L at the nitrogen atom at the 9th position of carbazole. 2 connect.

[0109] In some embodiments, G is coupled with L at the carbon atom at position 1, 2, 3, or 4 of the carbazole. 2 connect.

[0110] In some embodiments, L 1 It is a direct key.

[0111] In some embodiments, R 4b R 5a Or R 5c One of them is L 2 -G.

[0112] In some embodiments, L 1 and L 2 Independently selected from the following groups: direct bond, phenyl, and biphenyl.

[0113] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl and combinations thereof, not R of formula II. 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, aryl, heteroaryl and combinations thereof, and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.

[0114] In some embodiments, R 1a R 1bR 1c R 1d R 2a R 2b R 2c and R 2d Each of the following groups, independently selected: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazole, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof, not R of formula II. 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazole, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof, and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof.

[0115] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2d It's hydrogen, not R in formula II. 3a R 3b R 3c and R 3d It is hydrogen, and not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d It is hydrogen.

[0116] In some embodiments, X is O.

[0117] In some embodiments, X is S.

[0118] In some embodiments, X is S, L 1 and L 2 It is a direct key, and R 5a It is L 2 -G.

[0119] In some embodiments, X is S, L 1 It's a direct key, L 2 It is a phenyl group, and R 5a It is L 2 -G.

[0120] In some embodiments, G is substituted by one or more substituents selected from the group consisting of: deuterium, hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0121] In some embodiments, compounds having formula IV are provided:

[0122]

[0123] In compounds of formula IV, R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has the following formula:

[0124] ---L 2 -G(III);

[0125] L 1 and L 2 Independently selected from the group consisting of: direct bond, aryl group having 6-30 carbon atoms, heteroaryl group having 3-30 carbon atoms, and combinations thereof; wherein the aryl group and the heteroaryl group are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof; X is selected from the group consisting of: O, S, and Se; G is a carbazole that may be optionally substituted; R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b and R3d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0126] In some embodiments, G is coupled with L at the nitrogen atom at the 9th position of carbazole. 2 connect.

[0127] In some embodiments, G is coupled with L at the carbon atom at position 1, 2, 3, or 4 of the carbazole. 2 connect.

[0128] In some embodiments, L 1 It is a direct key.

[0129] In some embodiments, R 4b R 5a Or R 5c One of them is L 2 -G.

[0130] In some embodiments, L 1 and L 2 Independently selected from the following groups: direct bond, phenyl, and biphenyl.

[0131] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, aryl, heteroaryl and combinations thereof, and is not R of formula III. 4a R 4b R4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.

[0132] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazole, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof, and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof.

[0133] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b and R 3d It is hydrogen, and not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d It is hydrogen.

[0134] In some embodiments, X is O.

[0135] In some embodiments, X is S.

[0136] In some embodiments, X is S, L 1 and L 2 It is a direct key, and R 5a It is L 2 -G.

[0137] In some embodiments, X is S, L 1 It's a direct key, L 2 It is a phenyl group, and R 5a It is L 2 -G.

[0138] In some embodiments, G is substituted by one or more substituents selected from the group consisting of: deuterium, hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0139] In some embodiments, compounds having formula V are provided:

[0140]

[0141] In compound V, L 1 and L 2 Independently selected from the group consisting of: direct bonds, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof; wherein the aryl and heteroaryl groups are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, and combinations thereof; X is selected from the group consisting of: O, S, and Se; G is a carbazole that may be optionally substituted; R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b R 3d R 4a R 4b R 4c R 5b R 5c and R 5dEach is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0142] In some embodiments, G is coupled with L at the nitrogen atom at the 9th position of carbazole. 2 connect.

[0143] In some embodiments, G is coupled with L at the carbon atom at position 1, 2, 3, or 4 of the carbazole. 2 connect.

[0144] In some embodiments, L 1 It is a direct key.

[0145] In some embodiments, L 1 and L 2 Independently selected from the following groups: direct bond, phenyl, and biphenyl.

[0146] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b R 3d R 4a R 4b R 4c R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.

[0147] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b R 3d R 4a R 4b R 4c R 5b R 5c and R 5dEach is independently selected from the following groups: hydrogen, deuterium, phenyl, biphenyl, triphenyl, tetraphenyl, pentaphenyl, pyridyl, phenylpyridyl, pyridylphenyl, triphenylene, carbazolyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenyl and combinations thereof.

[0148] In some embodiments, R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b R 3d R 4a R 4b R 4c R 5b R 5c and R 5d It is hydrogen.

[0149] In some embodiments, X is O.

[0150] In some embodiments, X is S.

[0151] In some embodiments, X is S, and L 1 and L 2 It is a direct key.

[0152] In some embodiments, X is S, L 1 It is a direct key, and L 2 It is phenyl.

[0153] In some embodiments, G is substituted by one or more substituents selected from the group consisting of: deuterium, hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0154] In some embodiments, the compound is selected from the group consisting of:

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162] In some embodiments, an organic light-emitting device is provided. In some embodiments, the organic light-emitting device comprises:

[0163] anode;

[0164] cathode;

[0165] An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having formula I:

[0166]

[0167] Where R 3a R 3b R 3c Or R 3d At least one of them has Equation II:

[0168]

[0169] Where R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has Equation III:

[0170] ---L 2 -G(III);

[0171] Where L 1 and L 2 Independently selected from the group consisting of: direct bonds, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof; wherein the aryl and heteroaryl groups are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof; wherein X is selected from the group consisting of: O, S, and Se; wherein G is a carbazole that may be optionally substituted; wherein R 1a R 1b R 1c R 1d R 2a R 2b R 2c and R 2dEach is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; wherein R is not of formula II. 3a R 3b R 3c and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and R is not of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0172] In some embodiments, an organic light-emitting device is provided. In some embodiments, the organic light-emitting device comprises:

[0173] anode;

[0174] cathode;

[0175] An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having formula IV:

[0176]

[0177] Where R 4a R 4b R 4c R 5a R 5b R 5c Or R 5d At least one of them has Equation III:

[0178] ---L 2 -G(III);

[0179] L 1 and L 2Independently selected from the group consisting of: direct bonds, aryl groups having 6-30 carbon atoms, heteroaryl groups having 3-30 carbon atoms, and combinations thereof; wherein the aryl and heteroaryl groups are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, and combinations thereof; X is selected from the group consisting of: O, S, and Se; G is a carbazole that may be optionally substituted; R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b and R 3d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and is not R of formula III. 4a R 4b R 4c R 5a R 5b R 5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0180] In some embodiments, an organic light-emitting device is provided. In some embodiments, the organic light-emitting device comprises:

[0181] anode;

[0182] cathode;

[0183] An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having formula V:

[0184]

[0185] L 1 and L 2Independently selected from the group consisting of: direct bond, aryl group having 6-30 carbon atoms, heteroaryl group having 3-30 carbon atoms, and combinations thereof; wherein the aryl group and the heteroaryl group are optionally further substituted by one or more groups selected from: hydrogen, deuterium, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, nitrile, and combinations thereof; X is selected from the group consisting of: O, S, and Se; G is a carbazole that may be optionally substituted; R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a R 3b R 3d R 4a R 4b R 4c R 5b R 5c and R 5d Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

[0186] In some embodiments, the organic layer of the device is an emission layer, and the compound of formula I is the host. In some embodiments, the organic layer of the device is an emission layer, and the compound of formula IV is the host. In some embodiments, the organic layer of the device is an emission layer, and the compound of formula V is the host.

[0187] In some embodiments, the organic layer of the device further comprises a phosphorescent dopant. In some embodiments, the phosphorescent dopant is a transition metal complex having at least one ligand or (when the ligand is more than two-toothed) a portion of the ligand:

[0188]

[0189]

[0190] Where R a R b R c and R d It can represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group; and R can represent a monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted group. a R b R c and Rd Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof; and wherein R a R b R c and R d Two adjacent substituents may optionally be connected to form a fused ring or a polydentate ligand.

[0191] In some embodiments, the organic layer of the device is a barrier layer, and the compound is a barrier material in the organic layer.

[0192] In some embodiments, the device is a consumer product. In some embodiments, the device is an organic light-emitting device. In some embodiments, the device includes a lighting panel.

[0193] In some embodiments, the compounds described herein are provided in the formulation along with other materials present in the device. For example, the compounds of the present invention may be provided in the formulation in combination with various bodies, delivery layers, barrier layers, injection layers, electrodes, or other layers.

[0194] In some embodiments, a formulation comprising a compound of formula I is provided. In some embodiments, a formulation comprising a compound of formula IV is provided. In some embodiments, a formulation comprising a compound of formula V is provided.

[0195] Combination with other materials

[0196] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in said devices. For example, the emission dopants disclosed herein can be used in combination with a variety of host layers, transport layers, barrier layers, injection layers, electrodes, and other possible layers. 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 readily consult the literature to identify other materials that can be used in combination.

[0197] HIL / HTL:

[0198] The hole injection / delivery materials used in this invention are not particularly limited, and any compound can be used, provided that the compound is typically used as a hole injection / delivery material. Examples of such materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes, and crosslinkable compounds.

[0199] Examples of aromatic amine derivatives used in HILs or HTLs include (but are not limited to) the following general formula structures:

[0200]

[0201] Ar 1 To Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, olean, perylene, azulene; and the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indolodiazole Azides, benzoxazoles, benzoisoxazoles, benzothiazoles, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and a group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each Ar is further substituted with a substituent selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0202] In some embodiments, Ar1 To Ar 9 Choose independently from the following groups:

[0203]

[0204] k is an integer from 1 to 20; X 101 To X 108 It is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 Having the same functional groups as defined above.

[0205] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0206]

[0207] Met is a metal; (Y) 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0208] In some embodiments, (Y) 101 -Y 102 ) is a 2-phenylpyridine derivative.

[0209] In some embodiments, (Y) 101 -Y 102 ) is a carbaene ligand.

[0210] In some embodiments, Met is selected from Ir, Pt, Os, and Zn.

[0211] On the other hand, the metal complex has a voltage relative to Fc of less than about 0.6V. + The minimum oxidation potential in solution for / Fc pairs.

[0212] main body:

[0213] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as the light-emitting material, and may contain a host material using a metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used, as long as the triplet energy of the host is greater than that of the dopant. Although the table below categorizes host materials preferred for emitting various colors, any host material can be used with any dopant, provided the triplet criterion is satisfied.

[0214] Examples of metal complexes used as the host preferably have the following general formula:

[0215]

[0216] Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 Independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0217] In some embodiments, the metal complex is:

[0218]

[0219] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0220] In some embodiments, Met is selected from Ir and Pt.

[0221] On the other hand, (Y) 103 -Y 104 ) is a carbaene ligand.

[0222] Examples of organic compounds used as the host are selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, oleanyl, perylene, and azulene; and from the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, Indoxaazine, benzoxazole, benzoisoxaazole, benzothiazole, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and the group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each of these groups is further substituted with substituents selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0223] In some embodiments, the host compound contains at least one of the following groups in its molecule:

[0224]

[0225] R 101 To R 107 Independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, when it is aryl or heteroaryl, it has a similar definition to Ar as described above.

[0226] k is an integer from 1 to 20; k'" is an integer from 0 to 20.

[0227] X 101 To X 108 Selected from C (including CH) or N.

[0228] Z101 and Z 102 Selected from NR 101 、O or S.

[0229] HBL:

[0230] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to the desired area of ​​the OLED.

[0231] In some embodiments, the compound used in HBL contains the same molecule or the same functional group used as the above-described main body.

[0232] In some embodiments, the compound used in HBL contains at least one of the following groups in its molecule:

[0233]

[0234] k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0235] ETL:

[0236] An electron transport layer (ETL) can comprise a material capable of transporting electrons. The ETL can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used, as long as it is typically used for electron transport.

[0237] In some embodiments, the compound used in the ETL contains at least one of the following groups in its molecule:

[0238]

[0239] R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, which, when being aryl or heteroaryl, have a similar definition to Ar as described above.

[0240] Ar 1 To Ar 3 It has a similar definition to Ar mentioned above.

[0241] k is an integer from 1 to 20.

[0242] X 101 To X 108 Selected from C (including CH) or N.

[0243] In some embodiments, the metal complexes used in the ETL contain (but are not limited to) the following general formula:

[0244]

[0245] (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N or N, N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to a metal.

[0246] In any of the compounds described above used in each layer of an OLED device, hydrogen atoms may be partially or fully deuterated. Therefore, any specifically listed substituents (e.g., but not limited to, methyl, phenyl, pyridyl, etc.) encompass their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) also encompass their non-deuterated, partially deuterated, and fully deuterated forms.

[0247] In addition to and / or in combination with the materials disclosed herein, a variety of hole injection materials, hole transport materials, host materials, dopant materials, exciton / hole blocking layer materials, electron transport materials, and electron injection materials may 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 1 below. Table 1 lists the non-limiting categories of materials, non-limiting examples of compounds in each category, and references to the materials disclosed.

[0248] Table 1

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271] experiment

[0272] Throughout this document, the following chemical abbreviations are used: S-Phos is dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine, Pd2(dba)3 is tris(diphenylmethyleneacetone)dipalladium(0), THF is tetrahydrofuran, and DCM is dichloromethane.

[0273] Example 1

[0274] Synthetic compound 43-S

[0275]

[0276] A solution of n-butyllithium in hexane (2.5 M, 7.14 mL, 17.9 mmol) was slowly added to a solution of 9-(dibenzo[b,d]thiophene-2-yl)-9H-carbazole (4.8 g, 13.8 mmol) in THF (100 mL) at -78 °C. The solution was gradually heated to 5 °C and stirred between 0 and 10 °C for 6 hours. The solution was cooled to -78 °C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoboronane (4.3 mL, 20.6 mmol) was immediately added. The solution was slowly heated to room temperature and stirred overnight, followed by quenching with water. The reaction mixture was extracted with diethyl ether, washed with brine and water, dried over MgSO4, and the solvent was evaporated. The residue was purified by column chromatography on silica gel with heptane / DCM as eluent and wet milling with heptane to give 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)dibenzo[b,d]thiophen-2-yl)-9H-carbazole (3.8 g, 57%) as a white powder.

[0277]

[0278] A solution of 9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)dibenzo[b,d]thiophene-2-yl)-9H-carbazole (3.0 g, 6.3 mmol), 2-(3-bromophenyl)triphenylene (2.4 g, 6.31 mmol), Pd2(dba)3 (0.116 g, 0.126 mmol), S-Phos (0.104 g, 0.252 mmol), and K3PO4 (4.02 g, 18.93 mmol) in toluene (100 mL) and water (15 mL) was refluxed under nitrogen at 110 °C for 3 hours. After cooling to room temperature, the solution was diluted with water, and the solids were collected by filtration. The crude product was redissolved in boiling toluene (800 mL) and filtered through a short silica gel stopper topped with an anhydrous MgSO4 layer. The filtrate was concentrated, and the white solid was collected and wet-milled sequentially with boiling xylene and dichloromethane to give compound 43-S (3.5 g, 85%) as a white solid.

[0279] Example 2

[0280] Synthetic compound 17-S

[0281]

[0282] A mixture of 4,4,5,5-tetramethyl-2-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-1,3,2-dioxoboronpentane (2.7 g, 5.03 mmol), 9-(3'-bromo-[1,1'-biphenyl]-3-yl)-9H-carbazole (2.065 g, 5.18 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.138 g, 0.151 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.310 g, 0.755 mmol) was loaded into 250 mL of toluene. Potassium phosphate monohydrate (3.47 g, 15.10 mmol) was dissolved in 25 mL of water, and the solution was loaded into the reaction mixture. The reaction mixture was degassed with nitrogen and then heated under reflux overnight. The reaction mixture was cooled to room temperature. The toluene layer was separated and dried under vacuum. The crude residue stream was passed through a silica gel column using 35-99% toluene / hexane. The cleanest eluents were combined and concentrated under vacuum. The cleanest eluent was obtained by recrystallization from toluene. 9-(3'-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-[1,1'-biphenyl]-3-yl)-9H-carbazole (compound 17-S) (1.832 g, 2.52 mmol, 50% yield) was separated as a white solid.

[0283] Example 3

[0284] Synthetic compound 7-S

[0285]

[0286] 4-Bromo-6-(triphenyl-2-yl)dibenzo[b,d]thiophene (5 g, 10.22 mmol), 9H-carbazole (1.999 g, 11.95 mmol), sodium tert-butoxide (1.964 g, 20.43 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.280 g, 0.306 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.628 g, 1.532 mmol) were loaded into a three-necked flask containing 300 mL of m-xylene. The reaction mixture was degassed using nitrogen. The reaction mixture was then heated to reflux for 24 hours. The reaction mixture was cooled to room temperature and diluted with 100 mL of water. The mixture was passed through a diatomaceous earth pad. The organic layer was separated and dried over magnesium sulfate. The mixture was filtered and concentrated under vacuum. The crude residue was passed through a silica gel column using 35–50% toluene / hexane. The cleanest eluents were combined and concentrated under vacuum. The cleanest eluents were then wet-milled with hot ethanol to remove excess carbazole. The solid was then wet-milled with hot heptane / toluene. The white solid was collected by filtration and recrystallized from toluene. 9-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-9H-carbazole (compound 7-S) (3.04 g, 5.28 mmol, 51.7% yield) was isolated as a white solid.

[0287] Example 4

[0288] Synthetic compound 11-S

[0289]

[0290] 9H-3,9'-dicarbazole (1.88 g, 5.66 mmol), sodium tert-butoxide (1 g, 10.42 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.22 g, 0.240 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.5 g, 1.220 mmol) were loaded into a reaction flask containing 210 mL of o-xylene. The mixture was degassed with nitrogen and then heated to reflux for 2 1 / 2 days. The reaction mixture was cooled to room temperature. The solids were collected by filtration. The solids were dissolved in 1 L of hot toluene and then passed through a silica gel column. The column was washed with hot toluene. The toluene filtrate was concentrated under vacuum. The crude solids were wet-milled with 300 mL of hot ethanol and then filtered under vacuum. The collected solid was then recrystallized twice from hot toluene to give 9-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-9H-3,9'-dicarbazole (compound 11-S) (2.25 g, 3.04 mmol, 59.5% yield) as a white solid.

[0291] Example 5

[0292] Synthetic compound 4-O

[0293]

[0294] 4,4,5,5-Tetramethyl-2-(6-(triphenyl-2-yl)dibenzo[b,d]furan-4-yl)-1,3,2-dioxoboronylpentane (3 g, 5.76 mmol), 9-(3-bromophenyl)-9H-carbazole (2 g, 6.21 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.109 g, 0.119 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.195 g, 0.476 mmol) were loaded into a reaction flask containing 150 mL of toluene. Potassium phosphate (4.42 g, 20.85 mmol) was dissolved in 15 mL of water and then loaded into the reaction mixture. The reaction mixture was degassed with nitrogen and then heated under reflux overnight. The reaction mixture was cooled to room temperature. The solid was collected by filtration. This solid was wet-milled with 300 mL of warm methanol. The solid was filtered and dried under vacuum. The solid was then dissolved in 800 mL of refluxed toluene and passed through a silica gel pad. The filtrate was concentrated under vacuum and then recrystallized twice from toluene. 9-(3-(6-(triphenyl-2-yl)dibenzo[b,d]furan-4-yl)phenyl)-9H-carbazole (compound 4-O) (1.75 g, 2.75 mmol, 47.8% yield) was isolated as a white solid.

[0295] Example 6

[0296] Synthetic compound 4-S

[0297]

[0298] 4,4,5,5-Tetramethyl-2-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-1,3,2-dioxoboronpentane (2.88 g, 5.37 mmol), 9-(3-bromophenyl)-9H-carbazole (1.78 g, 5.53 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.098 g, 0.107 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.176 g, 0.429 mmol) were loaded into a reaction flask containing 150 mL of toluene. Potassium phosphate (3.99 g, 18.79 mmol) was dissolved in 15 mL of water and then loaded into the reaction mixture. The reaction mixture was degassed with nitrogen and then heated under reflux overnight. The reaction mixture was cooled to room temperature. The solids were collected by filtration and washed with methanol and ethyl acetate. The solid was then dissolved in approximately 500 mL of refluxed toluene and passed through a silica gel pad. The filtrate was concentrated under vacuum and then recrystallized from toluene. 9-(3-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)phenyl)-9H-carbazole (compound 4-S) (2.6 g, 74.3% yield) was isolated as a white solid.

[0299] Example 7

[0300] Synthetic compound 1-S

[0301]

[0302] 4,4,5,5-Tetramethyl-2-(6-(triphenyl-2-yl)dibenzo[b,d]thiophene-4-yl)-1,3,2-dioxoboronpentane (2.94 g, 5.49 mmol), 9-(4-bromophenyl)-9H-carbazole (1.75 g, 5.43 mmol), tris(diphenylmethyleneacetone)palladium(0) (0.099 g, 0.109 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.178 g, 0.435 mmol) were loaded into a reaction flask containing 120 mL of toluene. Potassium phosphate (4.04 g, 19.01 mmol) was dissolved in 10 mL of water and then loaded into the reaction mixture. The reaction mixture was degassed with nitrogen for 30 min and then heated under reflux overnight. The reaction mixture was cooled to room temperature. The solids were collected by filtration. The solid was wet-milled with 300 mL of warm methanol and washed with ethyl acetate. The solid was filtered and dried under vacuum. The solid was then dissolved in 1200 mL of refluxed toluene and passed through a silica gel pad. The filtrate was concentrated under vacuum and then recrystallized from toluene. Compound 1-S (1.1 g, 31.1% yield) was isolated as a white solid.

[0303] Example 8

[0304] Synthetic compound 20-S

[0305]

[0306] A solution of tris(diphenylmethyleneacetone)dipalladium(O) (0.142 g, 0.155 mmol), 4-bromo-6-(triphenyl-2-yl)dibenzo[b,d]thiophene (3.8 g, 7.76 mmol), 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxoboronan-2-yl)-9H-carbazole (3.01 g, 8.15 mmol), S-phos (0.255 g, 0.621 mmol), and K3PO4 (5.77 g, 27.2 mmol) in toluene (200 mL) and water (20 mL) was heated under reflux at N2 for 48 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane. After washing with water, the organic layer was concentrated. The remaining solids were wet-milled with methanol and then with ethyl acetate. The solid was dissolved in refluxed toluene and filtered while hot through a silica gel stopper topped with a layer of magnesium sulfate. The filtrate was concentrated, leaving a white solid, which was recrystallized from toluene to give compound 20-S (2.6 g, 43% yield) as a white solid.

[0307] Examples of comparator devices

[0308] Through high vacuum (<10) -7 Examples of comparative devices are fabricated using thermal evaporation. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... LiF followed by The composition is Al. Immediately after manufacturing, all devices are encapsulated in a nitrogen glove box (<1ppm H2O and O2) using an epoxy-sealed glass lid, and a desiccant is incorporated into the encapsulation.

[0309] The organic stack of the device instance consists of the following components sequentially from the ITO surface: Compound H is used as a hole injection layer (HIL); 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) was used as a hole transport layer (HTL); 15% of compound B1 was used as a dopant, and compounds H1 and H2 were used as emitter layers (EMLs). Alq (tri-8-hydroxyquinoline aluminum) is used as an electron transport layer (ETL).

[0310] As used herein, compounds H, NPD, Alq, B1, H1, and H2 have the following structures:

[0311]

[0312] Table 2 summarizes the performance of the device. Lifetime (LT) 80％ The time required for the device to decay to 80% of its initial brightness (L0) of 2000 nits is defined as this. Devices containing compounds H1 and H2 exhibit the same device lifetime, indicating that the carbazole substitution position on dibenzothiophene does not affect device performance. Therefore, the comparative device examples below using compound C as the host should provide a robust comparison of device results.

[0313] Table 2. Device Structure and Results

[0314]

[0315] Device Examples

[0316] Through high vacuum (<10) -7 An example of an apparatus for manufacturing by thermal evaporation. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... LiF followed by The composition is Al. Immediately after manufacturing, all devices are encapsulated in a nitrogen glove box (<1ppm H2O and O2) using an epoxy-sealed glass lid, and a desiccant is incorporated into the encapsulation.

[0317] The organic stack of the device instance consists of the following components sequentially from the ITO surface: Compound A is used as a hole injection layer (HIL); 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) was used as a hole transport layer (HTL); The compound of the present invention, doped with compound A, is used as a dopant, and 10% by weight of iridium phosphorescent compound is used as an emission layer (EML). The compound BL is used as a barrier layer (BL); Alq (tris-8-hydroxyquinoline aluminum) was used as the electron transport layer (ETL). The comparative examples with compound C were fabricated similarly to the device examples, but in device examples 1, 2 and 3, compounds 4-S, 7-S and 11-S were used as the host in the EML, respectively.

[0318] The device structures are provided in Table 3. As used herein, compounds A, C, NPD, BL, and Alq have the following structures:

[0319]

[0320] Table 3. Device Structure

[0321]

[0322] Table 4. Results of VTE device

[0323]

[0324] Table 4 provides the device's color coordinates and lifetime. For all instances, the color is recorded as green. The device lifetime LT is defined as a 20% degradation from its initial brightness. 80 At 40mA / cm 2 Measured under a constant current density. The LT values ​​in Table 4... 80 The data were normalized by comparing the lifetime of Example 1. As shown in Table 4, the LT80 of the device examples using compounds 7-S, 4-S, and 11-S of the present invention in the EML layer was 297%, 243%, and 47% longer, respectively, than that of the device examples using comparative compound C in the EML layer of the device.

[0325] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. A compound having formula I, (I)； Where R 3b Or R 3c Having Formula II: (II); Where R 5a Having Formula III: ---L 2 -G (III) Where L 1 It is a direct bond; where L 2 Choose from the following groups: direct bonds and aryl groups with 6-30 carbon atoms; X is selected from the following groups: O, S, and Se; Wherein G is carbazole; wherein G is optionally substituted by one or more substituents selected from the group consisting of: deuterium, hydrogen, C1-C 15 Alkyl groups, C3-C7 cycloalkyl groups, and combinations thereof; wherein G is attached at the nitrogen atom at the 9-position of the carbazole 2 connected; Where R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a and R 3d Each is independently selected from the following groups: hydrogen, deuterium, halogens, C1-C. 15 Alkyl groups, C3-C7 cycloalkyl groups, and combinations thereof; Where R is not Equation II 3b and R 3c Each is independently selected from the following groups: hydrogen, deuterium, halogens, C1-C. 15 Alkyl groups, C3-C7 cycloalkyl groups, and combinations thereof; and Where R 4a R 4b R 4c R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, halogens, C1-C. 15 Alkyl groups, C3-C7 cycloalkyl groups, and combinations thereof.

2. The compound according to claim 1, wherein the compound has formula V: (V)。 3. The compound of claim 1, wherein L 2 is selected from the group consisting of a direct bond, phenyl, and biphenyl.

4. The compound according to claim 1, wherein R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a and R 3d Each is independently selected from the following groups: hydrogen, deuterium, and combinations thereof, where R is not a member of formula II. 3b and R 3c Each is independently selected from the following groups: hydrogen, deuterium, and combinations thereof, where R 4a R 4b R 4c R 5b R 5c and R 5d Each is independently selected from the following groups: hydrogen, deuterium, and combinations thereof.

5. The compound according to claim 1, wherein R 1a R 1b R 1c R 1d R 2a R 2b R 2c R 2d R 3a and R 3d It is hydrogen, and R is not from formula II. 3b and R 3c It is hydrogen, and R is present in it. 4a R 4b R 4c R 5b R 5c and R 5d It is hydrogen.

6. The compound according to claim 1, wherein X is O.

7. The compound according to claim 1, wherein X is S.

8. The compound of claim 1, wherein X is S, and L 2 is a direct bond.

9. The compound of claim 1, wherein X is S, and L 2 is phenyl.

10. A first apparatus comprising an organic light-emitting device, the organic light-emitting device comprising: anode; cathode; An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound according to any one of claims 1-9.

11. The first device according to claim 10, further comprising a barrier layer, wherein the compound of formula I is a barrier material in the organic layer.

12. A formulation comprising the compound according to any one of claims 1-9.

Images