Organic electroluminescent materials and devices

Abstract

This application relates to organic electroluminescent materials and devices. A compound is provided having the structure of Formula I: in the structure of Formula I, A A ) n (L B ) 3‑n to A 1 to A 8 each is independently carbon or nitrogen; at least one of A 1 to A 8 is nitrogen; ring B is bonded to ring A via a C-C bond; iridium is bonded to ring A via an Ir-C bond; X is O, S, or Se; each of R 1 to R 5 is independently selected from a plurality of substituents, which can be linked to form a ring; n is an integer from 1 to 3; and at least one R 2 adjacent to ring C is not hydrogen. Formulations and devices, such as OLEDs, comprising the compound are also provided.

Description

[0001] This application is filed on September 29, 2017, with application number 201710905128.6 and invention title "Organic".

[0002] This is a divisional application of the invention patent application for "electroluminescent materials and devices". Technical Field

[0003] The present invention relates to compounds suitable for use as emitters; and devices including the same, such as organic light-emitting diodes. Background Technology

[0004] 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 diodes / devices (OLEDs), 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.

[0005] 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.

[0006] 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. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates, well known in the art.

[0007] An example of a green emitting molecule is tris(2-phenylpyridine)iridium, denoted as Ir(ppy)3, which has the following structure:

[0008]

[0009] 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.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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

[0017] According to one embodiment, a compound is provided having the formula Ir(L A ) n (L B ) 3-n It has the structure of Formula I: In the structure of Equation I:

[0018] A 1 A 2 A 3 A 4 A 5 A 6 A 7 and A 8 Each of them is either carbon or nitrogen;

[0019] A 1 A 2 A 3 A 4 A 5 A 6 A 7 and A8 At least one of them is nitrogen;

[0020] Ring B is bonded to ring A via a CC bond;

[0021] Iridium is bonded to ring A via Ir-C bonds;

[0022] X is O, S, or Se;

[0023] R 1 R 2 R 3 R 4 and R 5 Independently indicates monosubstituted to the highest possible substituent or no substituent;

[0024] R 1 R 2 R 3 R 4 and R 5 Any adjacent substituents may optionally be bonded together to form a ring;

[0025] R 1 R 2 R 3 R 4 and R 5 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;

[0026] n is an integer from 1 to 3; and

[0027] At least one R adjacent to ring C 2 It's not hydrogen.

[0028] According to another embodiment, an organic light-emitting diode / device (OLED) is also provided. The OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include the formula Ir(L... A ) n (L B ) 3-n The compound. According to another embodiment, the organic light-emitting device is incorporated into one or more devices selected from: consumer products, electronic component modules, and / or lighting panels.

[0029] According to yet another embodiment, a formulation is provided that contains the formula Ir(L A ) n (L B )3-n Compounds. Attached Figure Description

[0030] Figure 1 An organic light-emitting device was displayed.

[0031] Figure 2 An inverted organic light-emitting device without a separate electron transport layer was demonstrated. Detailed Implementation

[0032] 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.

[0033] Early OLEDs used emitting molecules that emitted light from singlet states (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.

[0034] 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.

[0035] Figure 1An 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 US 7,279,704, which is incorporated by reference.

[0036] 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.

[0037] Figure 2An 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.

[0038] Figure 1 and 2 The 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 one embodiment, 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.

[0039] 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, as described in, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure can deviate from... Figure 1 and 2The 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.

[0040] 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 OVJD. 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 handleability 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.

[0041] 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.

[0042] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. Such electronic component modules may optionally include driving electronics and / or power supplies. Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Such consumer products will include any kind of product containing one or more light sources and / or one or more of some type of visual display. Examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to the 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).

[0043] 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.

[0044] As used herein, the terms “halogen,” “halogen,” or “halogen” include fluorine, chlorine, bromine, and iodine.

[0045] 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, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl group may optionally be substituted.

[0046] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Preferred cycloalkyl groups are those containing 3 to 10 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may optionally be substituted.

[0047] 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.

[0048] As used herein, the term "alkynyl" encompasses both straight-chain and branched alkynyl groups. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0049] As used herein, the terms “aralkyl” or “arylalkyl” are used interchangeably and cover alkyl groups having aromatic groups as substituents. Additionally, aralkyl groups may optionally be substituted.

[0050] As used herein, the term "heterocyclic group" encompasses both aromatic and non-aromatic cyclic radicals. Heteroaromatic cyclic radicals also refer to heteroaryl groups. Preferred heterocyclic non-aromatic cyclic groups are heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Furthermore, the heterocyclic group may optionally be substituted.

[0051] 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 carbons 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. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, leucovorin, perylene, and azulene, with phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene being preferred. Additionally, the aryl group may optionally be substituted.

[0052] As used herein, the term "heteroaryl" encompasses a monocyclic heteroaryl aromatic group that may include one to five heteroatoms. The term "heteroaryl" also includes polycyclic heteroaryl aromatic 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, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zonal Phosphorus compounds, including quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselenene-phene-pyridine, and selenophene-dipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0053] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be unsubstituted or may be substituted by one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0054] As used in this article, "substituted" means that the substituent is not H bonded to the relevant position, such as carbon. Therefore, for example, in R... 1 When replaced by a single unit, then an R 1 It must not be H. Similarly, in R... 1 When replaced by two, then the two Rs 1 It must not be H. Similarly, in R... 1 When not replaced, R 1 It is hydrogen for all available locations.

[0055] The term "aza" in the fragments described herein (i.e., aza-dibenzofuran, aza-dibenzothiophene, etc.) indicates that one or more CH groups in the corresponding 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.

[0056] 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., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0057] According to one embodiment, a compound having the formula Ir(L) is described. A ) n (L B ) 3-n It has the structure of Formula I: In the structure of Equation I:

[0058] A 1 A 2 A 3 A 4 A 5 A 6 A 7 and A 8 Each of them is either carbon or nitrogen;

[0059] A 1 A 2 A 3 A 4 A 5 A 6 A 7 and A 8 At least one of them is nitrogen;

[0060] Ring B is bonded to ring A via a CC bond;

[0061] Iridium is bonded to ring A via Ir-C bonds;

[0062] X is O, S, or Se;

[0063] R 1 R 2 R 3 R 4 and R 5 Independently indicates monosubstituted to the highest possible substituent or no substituent;

[0064] R 1 R 2 R 3 R 4 and R 5 Any adjacent substituents may optionally be bonded together to form a ring;

[0065] R 1 R 2 R 3 R 4 and R 5 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;

[0066] n is an integer from 1 to 3; and

[0067] At least one R adjacent to ring C 2 It's not hydrogen.

[0068] In some embodiments, n is 1.

[0069] In some embodiments, the compound is selected from the group consisting of:

[0070] and

[0071]

[0072] In some embodiments, A 1 To A 8 Only one of them is nitrogen. In some embodiments, A 1 To A 4 It is carbon, and A 5 To A 8 Of these, only nitrogen is present.

[0073] In some embodiments, X is O.

[0074] In some embodiments, R 1 R 2 R 3 R 4 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, alkyl, cycloalkyl, partially fluorinated alkyl, partially fluorinated cycloalkyl, and combinations thereof. In some embodiments, R 1 R 2 R 3 R 4 and R5 Independently selected from the group consisting of: hydrogen, deuterium, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl.

[0075] In some embodiments, the compound is selected from the group consisting of: In some such embodiments, R immediately adjacent to N 1 The group selected is composed of: alkyl, cycloalkyl, partially or fully deuterated variants thereof, partially fluorinated variants thereof, and combinations thereof. In some such embodiments, R immediately adjacent to N... 1 The group consisting of the following is selected: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl and their partially or completely deuterated forms.

[0076] In some embodiments, LA is selected from the group consisting of: L Ap，1 To L Ap，634 and L Am，1 To L Am，634 L Ap，i and L Am，i It has the following structure: Where i is an integer from 1 to 634. In such embodiments, L Ap，1 To L Ap，634 and L Am，1 To L Am，634 , substituent R A1 R A2 R A3 and R A4 The definition is as follows:

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[0101] In some embodiments, L B Choose from the following groups: L B1 To L B856 L B，b It has the following structure: Where b is an integer from 1 to 856, and the substituent R B1 R B2 R B3 and R B4 The definition is as follows:

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[0134] In some embodiments, the compounds are selected from the group consisting of: compounds 1 to 1,085,408, wherein:

[0135] (I) For compounds 1 to 542,704, compound x has the formula Ir(L Ap,i (L) Bj )2; where x = 856i + j - 856; i is an integer from 1 to 634, and j is an integer from 1 to 856, and

[0136] (II) For compounds 542,705 to 1,085,408, compound x has the formula Ir(L Am,i (L) Bj )2; where x = 856i + j + 541, 848; i is an integer from 1 to 634, and j is an integer from 1 to 856.

[0137] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0138] In another embodiment, an organic light-emitting device (OLED) is described, comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode. As described herein, the organic layer may include an organic layer having the formula Ir(L A ) n (L B ) 3-n Compounds and their variants.

[0139] The OLEDs disclosed herein can be incorporated into one or more consumer products, electronic component modules, and lighting panels. The organic layer may be an emission layer, and the compound may be an emission dopant in some embodiments, while in other embodiments it may be a non-emission dopant.

[0140] The organic layer may further include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) bipolar, b) electron transport, c) hole transport, or d) wide bandgap material that plays a minimal role in charge transport. In some embodiments, the host may include a metal complex. The host may be triphenylene containing benzofused thiophene or benzofused furan. Any substituent in the host may be a non-fused substituent independently selected from the group consisting of: C n H 2n+1 OC n H 2n+1 ,OAr1,N(C n H 2n+1 2. N(Ar1)(Ar2), CH=CH-C n H 2n+1 C≡CC n H 2n+1 Ar1, Ar1-Ar2 and C n H 2n -Ar1, or the host cell may not have any substituents. In the aforementioned substituents, n can vary from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs. The host cell may be an inorganic compound. For example, a Zn-containing inorganic material, such as ZnS.

[0141] The host may be a compound comprising at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenene. The host may include a metal complex. The host may be (but is not limited to) specific compounds selected from the group consisting of:

[0142] And its combination.

[0143] The following provides additional information about possible subjects.

[0144] In another aspect of the invention, a formulation is described, comprising according to formula Ir(L A ) n (L B ) 3-n The compound may include one or more components selected from the group consisting of solvents, host materials, hole injection materials, hole transport materials, and electron transport layer materials disclosed herein.

[0145] Combination with other materials

[0146] 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.

[0147] Conductive dopants:

[0148] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by generating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0149] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein for OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0150]

[0151] HIL / HTL:

[0152] 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. xp-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes, and crosslinkable compounds.

[0153] Examples of aromatic amine derivatives used in HILs or HTLs include (but are not limited to) the following general formula structures:

[0154]

[0155] Ar 1 To Ar 9 Each of these is selected from the group consisting of aromatic cyclic hydrocarbons, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, olean, perylene, and azulene; and from 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 may be unsubstituted or may be substituted with a substituent selected from the group consisting of: 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.

[0156] In one respect, Ar 1 To Ar 9 Choose independently from the following groups:

[0157]

[0158] Where 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; Ar1 Having the same functional groups as defined above.

[0159] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0160]

[0161] Met is a metal that can have an atomic weight greater than 40; (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 an auxiliary 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.

[0162] In one respect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. On the other hand, (Y) 101 -Y 102 Met is a carbapenem ligand. On the other hand, Met is selected from Ir, Pt, Os, and Zn. On the other hand, the metal complex has a relative voltage of less than about 0.6 V with respect to Fc. + The minimum oxidation potential in solution for / Fc pairs.

[0163] Non-limiting examples of HIL and HTL materials for OLEDs that can be used in combination with the materials disclosed herein are illustrated below, along with references to those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP 2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077 473. TW201139402, US06517957, US20020158242, US20030162053, US20050 123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] EBL:

[0171] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0172] main body:

[0173] 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 the triplet energy of the dopant. Any host material can be used with any dopant, as long as the triplet criterion is satisfied.

[0174] Examples of metal complexes used as the host preferably have the following general formula:

[0175]

[0176] Where Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104Independently 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.

[0177] In one respect, metal complexes are:

[0178]

[0179] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0180] On the other hand, Met is selected from Ir and Pt. On the other hand, (Y 103 -Y 104 ) is a carbaene ligand.

[0181] Examples of other organic compounds used as the main body are selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, biphenylene, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, oleanyl, perylene, and azulene; and 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, indoloxazine, benzoxazole, benzoisoxazole, 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 choice within each group may be unsubstituted or may be substituted by substituents selected from the group consisting of: 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.

[0182] In one respect, the host compound contains at least one of the following groups in its molecule:

[0183]

[0184] Where R 101 To R 107 Each of these 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, and when it is aryl or heteroaryl, it has a definition similar 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 Selected from C (including CH) or N.

[0185] Z 101 and Z 102 Selected from NR 101 、O or S.

[0186] Non-limiting examples of bulk materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2 0090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US2010018 7984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US201401 83503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO200501455 1. WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO200900389 8. WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066 , WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644 , WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472.

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] Other projectiles:

[0193] One or more other emitter dopants may be used in conjunction with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used, provided that the compound is typically used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0194] Non-limiting examples of emitter materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR2012003 2054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US 20050123788, US20050244673, US2005123791, US2005260449, US20060008 670、US20060065890、US20060127696、US20060134459、US20060134462、US2 0060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20l10204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07l15981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] HBL:

[0201] 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 and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0202] In one respect, the compounds used in HBL contain the same molecules or the same functional groups used as the aforementioned main body.

[0203] On the other hand, the compounds used in HBL contain at least one of the following groups in their molecules:

[0204]

[0205] Where k is an integer from 1 to 20; L 101 It is another ligand, and k′ is an integer from 1 to 3.

[0206] ETL:

[0207] 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.

[0208] In one respect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0209]

[0210] Where R 101 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, when it is aryl or heteroaryl, has a similar definition to Ar as described above. 1 To Ar3 It has a similar definition to Ar above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0211] On the other hand, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0212]

[0213] Wherein (ON) or (NN) are bidentate ligands of a metal 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 connected to the metal.

[0214] Non-limiting examples of ETL materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US20 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535.

[0215]

[0216]

[0217]

[0218] Charge generation layer (CGL)

[0219] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0220] 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 substituent (e.g., but not limited to, methyl, phenyl, pyridyl, etc.) may be in its undeuterated, partially deuterated, or fully deuterated form. Similarly, substituent classes (e.g., but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their undeuterated, partially deuterated, or fully deuterated forms.

[0221] experiment

[0222] Synthetic compound 275205

[0223]

[0224] Step 1:

[0225]

[0226] 4-Iodo-1,2-dimethylbenzene (12.9 g, 55.6 mmol) was fed into a reaction flask containing dimethyl sulfoxide-d6 (D6-DMSO) (60 mL, 857 mmol), followed by sodium tert-butoxide (1.8 g, 18.75 mmol). The mixture was degassed with nitrogen and then stirred at 65 °C for 18 hours. The reaction mixture was cooled and quenched with 75 mL of D₂O. The mixture was stirred at room temperature (approximately 22 °C) for 45 minutes. The mixture was then diluted with 200 mL of water and extracted with 3 × 70 mL of dichloromethane (DCM). The extracts were dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude residue was subjected to silica gel column chromatography eluted with DCM / heptane 95 / 5 (v / v). The pure eluates were combined and concentrated under vacuum to give 4-iodo-1,2-bis(methyl-d3)benzene (12.1 g, 50.8 mmol, 91% yield).

[0227] Step 2

[0228]

[0229] 4-Iodo-1,2-bis(methyl-d3)benzene (16.9 g, 71.0 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis(1,3,2-dioxaborhecyclopentane) (19.83 g, 78 mmol), and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (2.030 g, 2.484 mmol) were fed into a reaction flask containing 200 mL of dioxane, followed by the addition of potassium acetate (14.61 g, 149 mmol). The mixture was degassed with nitrogen and then heated to reflux for 18 hours. The reaction mixture was cooled to room temperature (approximately 22 °C) and the dioxane was removed under vacuum. The crude product was diluted with 300 mL of water and extracted with 3 × 70 mL of DCM. The extracts were dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude residue was subjected to silica gel column chromatography with a gradient mixture of DCM / heptane 40 / 60 to 70 / 30 (v / v) to give 2-(3,4-bis(methyl-d3)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentane (11.5 g, 48.3 mmol, 68.0% yield) as a dark oil.

[0230] Step 3

[0231]

[0232] 8-(4-chloro-5-methylpyridin-2-yl)-2-methylbenzofurano[2,3-b]pyridine (6.2 g, 20.08 mmol), 2-(3,4-bis(methyl-d3)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentane (8.37 g, 35.1 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhos) (1.6 g, 3.90 mmol) and tris(diphenylmethyleneacetone)palladium(0)(Pd2(dba)3) (0.643 g, 0.703 mmol) were fed into a reaction flask containing 350 mL of 1,2-dimethoxyethane (DME). Tripotassium phosphate monohydrate (23.09 g, 100 mmol) was dissolved in 50 mL of water and fed into a reaction flask. The mixture was degassed and heated to reflux for 18 hours. The reaction mixture was cooled to room temperature and DME was removed under vacuum. The residue was partitioned between DCM and water. The DCM extracts were combined, dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude residue was subjected to silica gel column chromatography eluting with a gradient mixture of ethyl acetate / DCM 2 / 98 to 10 / 90 (v / v). The pure eluates were combined and concentrated under vacuum to give 8-v4-(3,4-bis(methyl-d3)phenyl)-5-methylpyridin-2-yl)-2-methylbenzofurano[2,3-b]pyridine (5 g, 13.00 mmol, 64.8% yield).

[0233] Step 4

[0234]

[0235] 8-(4-(3,4-bis(methyl-d3)phenyl)-5-methylpyridin-2-yl)-2-methylbenzofuran[2,3-b]pyridine (5 g, 13.00 mmol) was dissolved in 45 mL of tetrahydrofuran (THF). Dimethyl sulfoxide d6 (40 mL, 571 mmol) was added to the reaction mixture via syringe. Sodium tert-butoxide (0.63 g, 6.56 mmol) was added to the reaction mixture in a single dose. The mixture was degassed and heated at 65 °C for 17 h, then cooled to room temperature. The reaction mixture was quenched with 60 mL of D2O and stirred at room temperature for 45 min. The mixture was then diluted with 200 mL of water and extracted with 3 × 70 mL DCM. The extracts were combined, dried over magnesium sulfate, filtered, and concentrated under vacuum. The crude residue was subjected to column chromatography on a silica gel column eluted with 1–3 v / v THF / 97–99 v / v DCM. The eluates of the obtained product were combined and concentrated under vacuum to give 4 g of product. This substance was recrystallized several times from ethyl acetate to give 8-(4-(3,4-bis(methyl-d3)phenyl)-5-(methyl-d3)pyridin-2-yl)-2-(methyl-d3)benzofurano[2,3-b]pyridine (2.1 g, 5.38 mmol, 41.4% yield).

[0236] Step 5

[0237]

[0238] 8-(4-(3,4-bis(methyl-d3)phenyl)-5-(methyl-d3)pyridin-2-yl)-2-(methyl-d3)benzofurano[2,3-b]pyridine (2.1 g, 5.38 mmol) was dissolved in 65 mL of ethanol. The iridium salt shown above (2.23 g, 2.98 mmol) was fed into the reaction mixture containing 60 mL of methanol. This mixture was degassed with nitrogen and then heated in an oil bath at 73 °C for 6 days. Heating was interrupted. The reactants were diluted with 50 mL of methanol and then filtered under vacuum. The resulting substance was dried under vacuum and then dissolved in 400 mL of DCM, subsequently passed through an active basic alumina stopper. The DCM filtrate was concentrated under vacuum and then passed through a 7 × 120 g silica gel column, eluting first with 90-99 vol% toluene / 1-10 vol% heptane and second with 1-2 vol% ethyl acetate / 98-99 vol% toluene. The eluent was cleaned to obtain the desired iridium complex (0.4 g, 0.433 mmol, 8.05% yield).

[0239] Synthetic compound 812773

[0240]

[0241] Step 1

[0242]

[0243] 2,5-Dichloro-4-methylpyridine (7 g, 43.2 mmol), 2-methyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)benzofurano[2,3-b]pyridine (13.36 g, 43.2 mmol), and potassium carbonate (11.94 g, 86 mmol) were suspended in a mixture of DME (180 mL) and water (10 mL) at room temperature under nitrogen. Tetra(triphenylphosphine)palladium(0)(Pd(PPh3)4) (0.499 g, 0.432 mmol) was added in a fractional fraction, the reaction mixture was degassed, and heated at 100 °C for 14 hours under nitrogen. The reaction mixture was then cooled to room temperature, and the organic phase was separated and filtered. Ethanol (100 mL) was added in a fractional fraction, and the resulting mixture was stirred, followed by filtration of a white precipitate. The remaining solution was evaporated, and the residue was subjected to silica gel column chromatography with heptane / DCM 1 / 1 (v / v) followed by heptane / EtOAc 4 / 1 (v / v) to give a white solid, which was combined with the white precipitate. The combined solid was recrystallized from DCM / heptane to give 8-(5-chloro-4-methylpyridin-2-yl)-2-methylbenzofurano[2,3-b]pyridine (11 g, 83% yield).

[0244] Step 2

[0245]

[0246] 8-(5-chloro-4-methylpyridin-2-yl)-2-methylbenzofurano[2,3-b]pyridine (11 g, 35.6 mmol), p-tolylboronic acid (5.81 g, 42.8 mmol), and tripotassium hydrate (16.41 g, 71.3 mmol) were suspended in a mixture of DME (150 ml) and water (5 ml) to give a colorless suspension. Pd2(dba)3 (0.326 g, 0.356 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (Sphos, 0.293 g, 0.713 mmol) were added in a fractional fashion. The reaction mixture was degassed and heated at 100 °C for 14 hours under nitrogen. The reaction mixture was then cooled to room temperature. The organic phase was separated, filtered, and evaporated. The residue was then subjected to silica gel column chromatography with a gradient mixture of heptane / THF 9 / 1 (v / v) to give 2-methyl-8-(4-methyl-5-(p-tolyl)pyridin-2-yl)benzofurano[2,3-b]pyridine as a white solid (9.2 g, 71% yield).

[0247] Step 3

[0248]

[0249] 2-Methyl-8-(4-methyl-5-(p-tolyl)pyridin-2-yl)benzofurano[2,3-b]pyridine was dissolved in 55 g of DMSO-d6, and then 1.2 g of sodium tert-butoxide was added. The reaction mixture was degassed and stirred at 60 °C for 12 h under nitrogen. The reaction mixture was quenched with D2O, diluted with water, and extracted with ethyl acetate. The organic solution was dried over sodium sulfate, filtered, and evaporated. The residue was subjected to silica gel column chromatography eluting with heptane / THF 9 / 1 (v / v) to give 3.7 g of the deuterated product in 40% yield.

[0250] Step 4

[0251]

[0252] 2-(methyl-d3)_8-(4-(methyl-d3)-5-(4-(methyl-d3)phenyl)pyridin-2-yl)benzofurano[2,3-b]pyridine (3.67 g, 9.83 mmol, 2.45 equivalents) and the above iridium complex trifluoromethanesulfonate were suspended in 50 mL of a 1 / 1 (v / v) mixture of ethanol and methanol. The reaction mixture was degassed and heated to reflux under nitrogen for 96 hours. The reaction mixture was then cooled to room temperature and a yellow solid precipitate was filtered off. The target compound (1.1 g, 30% yield) was obtained by silica gel column chromatography eluting with toluene / heptane 9 / 1 (v / v), followed by crystallization from toluene / heptane and DCM / methanol to obtain the pure substance.

[0253] Device Examples

[0254] All example devices were subjected to high vacuum (<10) -7 Manufactured by thermal evaporation. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... Liq (lithium 8-hydroxyquinoline) followed by The device is composed of Al. Immediately after manufacturing, all devices are sealed in a nitrogen glove box (<1 ppm H₂O and O₂) with epoxy-sealed glass lids, incorporating a desiccant into the packaging. The organic stack of the device examples consists of the following components sequentially from the ITO surface: HAT-CN is used as a hole injection layer (HIL); The HTM serves as a hole transport layer (HTL); thickness The emitter layer (EML) contains a 6:4 weight ratio of H-body (H1):E-body (H2) and 12% by weight of green emitter. The device uses Liq (lithium 8-hydroxyquinoline) doped with 40% ETM as the ETL. The device structure is shown in Table 1.

[0255] Table 1: Schematic diagram of device structure

[0256]

[0257] Table 1 shows the schematic apparatus structure. The chemical structures of the materials used in the apparatus examples are shown below.

[0258]

[0259]

[0260] After manufacturing, the testing device was set to DC 80mA / cm. 2 The EL, JVL, and lifetime are calculated. An acceleration factor of 1.8 is assumed, based on 80 mA / cm². 2 Calculate LT at 1,000 nits 95 The device's performance is shown in Table 2.

[0261] Table 2: Device Performance

[0262]

[0263] Comparing compound 275205 with Comparative Example 1, compound 275205 exhibits significantly better stability in the device than Comparative Example 1. It is speculated that the extended conjugation of the pyridine ring contributes to electronic stability and extends device lifetime. Comparing compound 812773 with Comparative Example 2, compound 812773 unexpectedly demonstrates higher efficiency than Comparative Example 2 (27% eqe vs. 24% eqe at 1000 nits). In general, incorporating a partially twisted aryl ring on the pyridine ring improves lifetime and efficiency without causing a significant red shift in color.

[0264] 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 kind of Ir(L) A (L) B Compound 2 has the following structural formula: , Where X is O or S; Where R 1 R 3 R 4 and R 5 Independently indicates the substitution from monosubstituted to the highest possible substitution or no substitution; Where R 1 and R 5 Independently selected from the group consisting of: hydrogen, deuterium, straight-chain or branched alkyl groups containing 1 to 15 carbon atoms, cycloalkyl groups containing 3 to 10 cyclic carbon atoms, and combinations thereof; Where R 3 and R 4 Independently selected from the group consisting of: hydrogen, deuterium, halogens, straight-chain or branched alkyl groups containing 1 to 15 carbon atoms, cycloalkyl groups containing 3 to 10 cyclic carbon atoms, and combinations thereof; and Where R 2 Selected from: deuterium and combinations of the following groups: straight-chain or branched alkyl groups containing 1 to 15 carbon atoms.

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

3. The compound according to claim 1, wherein R 2 Selected from: a combination of deuterium and groups selected from the group consisting of: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl and 2,2-dimethylpropyl.

4. The compound according to claim 1, wherein R 1 R 3 R 4 and R 5 A combination of deuterium independently selected from the group consisting of: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropylalkyl, cyclopropyl, cyclopentyl, cyclohexyl, and adamantylalkyl.

5. The compound according to claim 1, wherein the R immediately adjacent to N... 1 Choose from the following groups: partially or fully deuterated straight-chain or branched alkyl groups containing 1 to 15 carbon atoms, and partially or fully deuterated cycloalkyl groups containing 3 to 10 cyclic carbon atoms.

6. The compound according to claim 1, wherein L A Selected from L Am, i L Am, i It has the following structure: , where i is an integer selected from the i defined in the table below, and the corresponding substituent R A1 R A2 R A3 and R A4 The definition is as follows: 。 7. The compound according to claim 1, wherein L B Choose from the following groups: those consisting of structure L B,b Defined L B1 To L B856 : , where b is an integer from 1 to 856, and the corresponding substituent R B1 R B2 R B3 and R B4 The definition is as follows: 。 8. A compound x The compound x Having the formula Ir(L Am,i (L) Bj )2; of which x = 856 i + j +541,848; i It is defined in Table 1 below. i an integer, and j It is an integer from 1 to 856; and Where L Am,i It has the following structure: , where R A1 R A2 R A3 and R A4 The definitions are as follows: Table 1 Table 1: Where L Bj Choose from the following structure L B,j Defined L B1 To L B856 : ,in j It is an integer from 1 to 856, and the corresponding substituent R B1 R B2 R B3 and R B4 The definition is as follows: 。 9. An organic light-emitting device (OLED) comprising: anode; cathode; and An organic layer disposed between the anode and the cathode comprises a compound according to any one of claims 1-8.

10. The organic light-emitting device OLED according to claim 9, wherein the organic layer is an emission layer, and the compound is an emission dopant or a non-emission dopant.

11. The organic light-emitting device OLED according to claim 9, wherein the organic layer further comprises a body, wherein the body comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azitene, azicarbazole, azi-dibenzothiophene, azi-dibenzofuran, and azi-dibenzoselenene.

12. The organic light-emitting device OLED according to claim 9, wherein the organic layer further comprises a host, wherein the host comprises a metal complex.

13. A consumer product comprising an organic light-emitting device (OLED), the OLED comprising: anode; cathode; and An organic layer disposed between the anode and the cathode comprises a compound according to any one of claims 1-8.

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