Organic electroluminescent materials and devices

Abstract

A compound having a specific molecular shape that aligns the transition dipole moment (TDM) of the compound within the EML within the plane of the EML and produces a maximum light extraction effect is disclosed.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims priority to U.S. provisional application No. 62 / 799,975 filed February 1, 2019, under 35 USC § 119(e), the whole of which is incorporated herein by reference.

[0003] field

[0004] The present invention relates to a compound for use as an emitter and a device comprising the same, such as an organic light-emitting diode. Background Technology

[0005] Optoelectronic devices using organic materials are becoming increasingly important for various reasons. Since many of the materials used to manufacture such devices are relatively inexpensive, organic optoelectronic devices have potential in terms of cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, can make them highly suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic phototransistors, organic photocells, and organic photodetectors. In the case of OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can generally be easily controlled with a suitable dopant.

[0006] OLEDs use organic thin films that emit light when voltage is applied across the device. OLEDs are a technology that is becoming increasingly important for applications such as flat panel displays, lighting, and backlighting. Various OLED materials and compositions are described in U.S. Patents No. 5,844,363, 6,303,238, and 5,707,745, the full text of which is incorporated herein by reference.

[0007] One application of phosphorescent emitting molecules is full-color displays. Industrial standards for such displays require pixels tuned to emit specific colors referred to as "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, emissions from a white backlight are filtered using absorption filters to produce red, green, and blue emissions. The same technique can also be applied to OLEDs. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates known in the art.

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

[0009]

[0010] In the chemical formulas herein and below, the applicant illustrates the coordination bond from nitrogen to a metal (hereafter Ir) as a straight line.

[0011] As used herein, the term “organic” includes not only polymeric materials that can be used to fabricate organic optoelectronic devices, but also small molecule organic materials. “Small molecule” refers to any organic material that is not a polymer, and “small molecule” can actually be quite large. Small molecules may contain repeating units in some situations. For example, using a long-chain alkyl group as a substituent does not exclude the molecule from the “small molecule” type. Small molecules may also be incorporated into the polymer, for example, as pendant groups on the polymer main chain or as part of the main chain. Small molecules may also act as the core moiety of a dendrimer, which consists of a series of chemical shells formed on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and all dendrimers currently used in the OLED field are considered to be small molecules.

[0012] As used herein, "top part" means furthest from the substrate, and "bottom part" means closest to the substrate. If the first layer is described as being "placed on top of" the second layer, the first layer is placed far from the substrate. If the first layer is not specified as being "in contact" with the second layer, other layers may exist between the first layer and the second layer. For example, even if various organic layers exist between the cathode and the anode, the cathode may be described as being "placed on top of" the anode.

[0013] As used herein, "solution processability" means that it can be dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension, or can be deposited from a liquid medium.

[0014] If a ligand is considered to directly contribute to the photoactive properties of the emitting substance, the ligand may be referred to as "photoactive." If a ligand is considered not to contribute to the photoactive properties of the emitting substance, even though an auxiliary ligand may alter the properties of the photoactive ligand, the ligand may be referred to as "auxiliary."

[0015] As used herein, and as generally understood by those skilled in the art, where the first energy level is closer to the vacuum energy level, the first "highest occupied molecular orbital (HOMO)" or "lowest unoccupied molecular orbital (LUMO)" energy level is "greater" or "higher" than the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as negative energy with respect to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Likewise, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. "Higher" HOMO or LUMO energy levels appear closer to the top of the diagram than "lower" HOMO or LUMO energy levels.

[0016] As used herein, and as generally understood by those skilled in the art, if the absolute value of the first work function is greater, the first work function is "greater" or "higher" than the second work function. Since work functions are generally measured as negative numbers with respect to vacuum levels, this implies that the "higher" work function is more negative. In a typical energy level diagram with vacuum levels at the top, the "higher" work function is exemplified as being further down from the vacuum level. Therefore, the definition of HOMO and LUMO energy levels follows a different convention than that of work functions.

[0017] Further details regarding OLEDs and the foregoing definitions can be found in U.S. Patent No. 7,279,704, the full text of which is incorporated herein by reference.

[0018] A series of phosphorescent dopants having high efficiency is disclosed.

[0019] Formula [L A ] 3-n Ir[L B ] n A compound having is disclosed,

[0020] In the above formula,

[0021] n is 1, 2, or 3 and; L A is formula I is a ligand of; A is a fused ring structure containing three or more fused heterocyclic or carbocyclic rings; and Z 1 To Z 4 are each independently C or N; R 1 and R 2 ’ and ’ each independently represent a uniform substitution, the maximum allowable number of substitutions, or no substitution; 2 L’ A If a ligand is present, it may be the same or different; L B is Equation II It is a ligand of; R 3 and R 4Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently hydrogen, or a substituent selected from the group consisting of general substituents defined herein; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; 2 or 3 L B If a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to and does not form a loop.

[0022] An OLED comprising a compound of the present invention in an organic layer is also disclosed.

[0023] A consumer product including an OLED is also disclosed. Brief explanation of the drawing

[0024] Figure 1 illustrates an organic light-emitting device. Figure 2 illustrates an inverted organic light-emitting device that does not have a separate electron transport layer. FIGS. 3a to 3c are schematic diagrams of molecular forms (A), (B), and (C) that emit a dipole vector perpendicular to the C3 symmetry rotation axis in the molecule and, accordingly, parallel to the substrate according to the present invention. Specific details for implementing the invention

[0025] Generally, an OLED comprises one or more organic layers disposed between an anode and a cathode and electrically connected to them. When current is applied, the anode injects holes into the organic layer(s), and the cathode injects electrons. The injected holes and electrons move toward oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, "excitons" are generated, which are localized electron-hole pairs with excited energy states. Light is emitted when excitons relax through a photo-emission mechanism. In some cases, excitons may be localized on excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

[0026] Early OLEDs used emitting molecules that emit light ("fluorescence") from a singlet state, such as disclosed in, for example, U.S. Patent No. 4,769,292, the full text of which is incorporated by reference. Fluorescence emission generally occurs in a time frame of less than 10 nanoseconds.

[0027] More recently, OLEDs having an emitting material that emits light ("phosphorescence") from a triplet state have been presented. The literature [Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I")] and the literature [Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II") are incorporated by reference in their entirety. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, incorporated by reference.

[0028] FIG. 1 illustrates an organic light-emitting device (100). The drawing is not necessarily drawn to scale. The device (100) may include a substrate (110), an anode (115), a hole injection layer (120), a hole transport layer (125), an electron blocking layer (130), a light-emitting 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 compound cathode having a first conductive layer (162) and a second conductive layer (164). The device (100) may be fabricated by depositing layers in the order described. The properties and functions of the exemplary materials, as well as these various layers, are described in more detail in columns 6-10 of US Patent No. 7,279,704, which are incorporated by reference.

[0029] Further examples for each of these layers are also available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emission and host materials are disclosed in U.S. Patent No. 6,303,238 (Thompson et al.), which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Patents No. 5,703,436 and No. 5,707,745, the full text of which is incorporated by reference, including compound cathodes having thin layers of metals such as Mg:Ag having a stacked transparent, electrically conductive sputter-deposited ITO layer. The theory and applications of blocking layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, the full text of which is incorporated by reference. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated by reference. A description of a protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated by reference.

[0030] FIG. 2 illustrates an inverted structure OLED (200). The device comprises a substrate (210), a cathode (215), a light-emitting layer (220), a hole transport layer (225), and an anode (230). The device (200) can be fabricated by depositing layers in the order described. Since the most common OLED configuration has the cathode positioned above the anode and the device (200) has the cathode (215) positioned below the anode (230), the device (200) may be referred to as an "inverted structure" OLED. A material similar to that described for the device (100) may be used for the corresponding layers of the device (200). FIG. 2 provides an example of how some layers may be omitted from the structure of the device (100).

[0031] The simple stacked structure illustrated in FIGS. 1 and 2 is provided as a non-limiting example, and it is understood that embodiments of the present invention may be used in connection with various other structures. The specific materials and structures described are for illustrative purposes only, and other materials and structures may also be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of a host and a dopant, or more generally a mixture, may be used. Additionally, layers may have various underlying layers. The names given herein for the various layers are not intended to be strictly limited. For example, in the device (200), the hole transport layer (225) transports holes and injects holes into the light-emitting layer (220), and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between the cathode and the anode. This organic layer may comprise a single layer, or may further comprise a plurality of layers of different organic materials, for example, as described in relation to FIGS. 1 and 2.

[0032] OLEDs (PLEDs) comprising structures and materials not specifically described, such as polymer materials as disclosed in U.S. Patent No. 5,247,190 (Friend et al.), may also be used, the full text of which is incorporated herein by reference. As an additional example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 (Forrest et al.), the full text of which is incorporated herein by reference. OLED structures may deviate from the simple stacked structures shown in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 (Forrest et al.) and / or a pit structure as described in U.S. Patent No. 5,834,893 (Bulovic et al.), the full text of which is incorporated herein by reference.

[0033] Unless otherwise specified, any layer of any embodiment may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation as described in U.S. Patents No. 6,013,982 and 6,087,196 (the full text of which is incorporated herein by reference), ink-jet, organic vapor deposition (OVPD) as described in U.S. Patent No. 6,337,102 (Forrest et al.) (the full text of which is incorporated herein by reference), and organic vapor jet printing (OVJP) as described in U.S. Patent No. 7,431,968 (the full text of which is incorporated herein by reference). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred pattern-forming methods include pattern-forming associated with some deposition methods such as deposition through a mask, cold welding as described in U.S. Patents No. 6,294,398 and 6,468,819 (the full text of which is incorporated by reference), ink-jet, and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to be compatible with a specific deposition method. For example, branched or unbranched substituents, such as alkyl and aryl groups containing three or more carbons, may be used on small molecules to improve their solution-processability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Since asymmetric materials may have a lower tendency for recrystallization, materials with asymmetric structures may have better solution-processability than materials with symmetric structures. Dendrimer substituents may be used to improve the solution-processability of small molecules.

[0034] A device fabricated according to an embodiment of the present invention may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrode and organic layer from damage caused by exposure to harmful species in an environment containing moisture, vapor and / or gas. The barrier layer may be deposited on any other part of the device including the edge, on the electrode or, on the substrate, under the substrate, or on the side of the substrate. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may comprise a composition having multiple phases as well as a composition having a single phase. Any suitable material or combination of materials may be used in the barrier layer. The barrier layer may comprise an inorganic or organic compound or both. A preferred barrier layer comprises 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, the full text of which is incorporated herein by reference. To be considered a "mixture," the aforementioned polymer and non-polymer materials comprising a barrier layer must be deposited under the same reaction conditions and / or at the same time. The weight ratio of the polymer to the non-polymer material may be in the range of 95:5 to 5:95. The polymer and non-polymer materials may be produced from the same precursor material. In one example, the mixture of the polymer and non-polymer materials essentially consists of polymeric silicon and inorganic silicon.

[0035] A device manufactured according to an embodiment of the present invention may be contained within a wide variety of electronic component modules (or units) that may be included in various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light-emitting devices, such as individual light source devices, or lighting panels that may be used by end consumer product manufacturers. Such electronic component modules may optionally include driving electronic devices and / or power source(s). A device manufactured according to an embodiment of the present invention may be contained within a wide variety of consumer products that include one or more electronic component modules (or units). A consumer product comprising an OLED that includes a compound of the present disclosure in an organic layer within the OLED is disclosed. Such consumer products may include any type of product comprising one or more light source(s) and / or one or more of any type of image display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and / or signal lights, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal information terminals (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays tiled together, theater or stadium screens, phototherapy devices, and signage. Devices manufactured according to the present invention can be controlled using various control mechanisms, including passive matrices and active matrices.Many devices are intended to be used in a temperature range that provides comfort to people, such as 18°C ​​to 30°C, more preferably at room temperature (20°C to 25°C), but can also be used at temperatures outside the above temperature range, such as -40°C to +80°C.

[0036] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photodetectors, may use the materials and structures. More generally, organic devices, such as organic transistors, may use the materials and structures.

[0037] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0038] The term "acyl" refers to a substituted carbonyl radical (C(O)-R s It refers to ).

[0039] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s or -C(O)-OR s ) refers to radicals.

[0040] The term "ether" is -OR s It refers to radicals.

[0041] The terms "sulfanil" or "thio-ether" are used interchangeably, and -SR s It refers to radicals.

[0042] The term "sulfinyl" is -S(O)-R s It refers to radicals.

[0043] The term "sulfonyl" is -SO2-R s It refers to radicals.

[0044] The term "phosphino" is -P(R s Refers to )3 radicals, and each R s It may be the same or different.

[0045] The term "silyl" is -Si(R s Refers to )3 radicals, and each R s It may be the same or different.

[0046] The term "boril" is -B(R s )2 radical or its Lewis adduct -B(R s Refers to the )3 radical, where R s It may be the same or different.

[0047] In each of the above, R s may be hydrogen or a substituent, and said substituent is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0048] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyl radicals. A preferred alkyl group is one containing 1 to 15 carbon atoms and includes 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 is optionally substituted.

[0049] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 cyclic carbon atoms, including cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, cycloalkyl groups may be optionally substituted.

[0050] The terms "heteroalkyl" or "heterocycloalkyl" each refer to an alkyl or cycloalkyl radical having one or more carbon atoms substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl group is optionally substituted.

[0051] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene radicals. An alkenyl group is essentially an alkyl group comprising one or more carbon-carbon double bonds in an alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising one or more carbon-carbon double bonds within a cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl radical having one or more carbon atoms substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. A preferred alkenyl, cycloalkenyl, or heteroalkenyl group contains 2 to 15 carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.

[0052] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkene radicals. A preferred alkynyl group contains 2 to 15 carbon atoms. Additionally, the alkynyl group is optionally substituted.

[0053] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, the aralkyl group is optionally substituted.

[0054] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic radicals containing one or more heteroatoms. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteroaromatic cyclic radicals may also be used interchangeably with heteroaryls. Preferred heteronon-aromatic cyclic groups are those containing one or more heteroatoms and containing 3 to 7 ring atoms, including cyclic amines such as morpholino, piperidino, pyrrolidino, etc., and cyclic ethers / thio-ethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, heterocyclic groups may be optionally substituted.

[0055] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (these rings are "fused"), wherein one or more of the rings are aromatic hydrocarbyl groups, and, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6, 10, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl groups may be optionally substituted.

[0056] The term "heteroaryl" includes both monocyclic heteroaromatic groups and polycyclic aromatic ring systems comprising one or more heteroatoms. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N is a preferred heteroatom. A heteroaromatic monocyclic system is preferably a monocyclic ring having 5 or 6 ring atoms, and said ring may have 1 to 6 heteroatoms. A heteropolycyclic ring system may have two or more rings in which two carbons are common to two adjacent rings (these rings are "fused"), wherein one or more of the rings are heteroaryls, and, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryls. The heteropolycyclic aromatic ring system may have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. The preferred heteroaryl group contains 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.Suitable heteroaryl groups include dibenzothiophen, dibenzofuran, dibenzoselenopene, furan, thiophene, benzofuran, benzothiophene, benzoselenopene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, phenazine, Includes phenothiazine, phenoxazine, benzopuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenofyridine and selenofenodipyridine, preferably dibenzothiophen, dibenzofuran, dibenzoselenofen, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azabolin, 1,3-azabolin, 1,4-azabolin, borazine and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

[0057] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenopene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and each of these aza-analogs are of particular interest.

[0058] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more general substituents.

[0059] In many cases, the general substituent is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

[0060] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

[0061] In some cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0062] In other cases, the most desirable general substituent is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0063] The terms "substituted" and "substituted" refer to substituents other than H bonded to the relevant positions, such as carbon or nitrogen. For example, R 1 In the case where this represents a uniform substitution, one R 1 must be something other than H (i.e., substitution). Similarly, R 1 In the case where this represents a bisubstitution, R 1 Two of them must be something other than H. Similarly, R 1 In the case where this represents a non-substitution, R 1The available valence of the ring atom can be hydrogen, for example, the carbon atom of benzene and the nitrogen atom of pyrrole, or simply nothing for the ring atom with a fully charged valence, such as the nitrogen atom of pyridine. The maximum number of substitutions possible in a ring structure depends on the total number of available valences in the ring atom.

[0064] As used herein, “combinations thereof” indicates that one or more components of the applicable list are combined to form a known or chemically stable arrangement that a person skilled in the art can conceive from the applicable list. For example, alkyl and deuterium may be combined to form a partially or wholly deuteriden alkyl group; halogen and alkyl may be combined to form a halogenated alkyl substituent; and halogen, alkyl, and aryl may be combined to form a halogenated arylalkyl. In one case, the term substitution comprises a combination of two to four of the listed groups. In another case, the term substitution comprises a combination of two to three groups. In yet another case, the term substitution comprises a combination of two groups. A preferred combination of substituents is one containing up to 50 atoms that are not hydrogen or deuterium, or one containing up to 40 atoms that are not hydrogen or deuterium, or one containing up to 30 atoms that are not hydrogen or deuterium. In many cases, the preferred combination of substituents will include up to 20 atoms that are not hydrogen or deuterium.

[0065] In the fragments described herein, namely azadibenzofuran, azadibenzothiophene, etc., the notation "Aza" signifies that one or more of the CH groups in each aromatic ring can be substituted with nitrogen atoms, for example, azatriphenylene is dibenzo[ f,h ]Quinoxaline and Dibenzo[ f,h]Includes, but is not limited to, all quinoline. Those skilled in the art may readily consider other nitrogen analogs of the aforementioned aza derivatives, and all such analogs are intended to encompass the terms described herein.

[0066] As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US 2011 / 0037057, the entirety of which is incorporated herein by reference, describe the preparation of deuterium-substituted organometallic complexes. Additionally, the literature [Ming Yan, et al ., Tetrahedron 2015, 71, 1425-30] and literature[Atzrodt et al ., Angew. Chem. Int. Ed. (Reviews) See [2007, 46, 7744-65], the full text of which is incorporated herein by reference, which describes efficient routes for the deuteration of methylene hydrogens in benzylamine and the substitution of aromatic ring hydrogens with deuteration.

[0067] Where a molecular segment is described as a substituent or otherwise as being bonded to another moiety, it should be understood that its name may be described as the segment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as the whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different notations of such substituents or bonded segments are considered equivalent.

[0068] In some cases, pairs of adjacent substituents may be arbitrarily connected or fused to form a ring. Preferred rings are pentagonal, hexagonal, or heptagonal carbocyclic or heterocyclic rings, including cases where part of the ring formed by the pair of substituents is saturated and cases where part of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that two related substituents may exist on two adjacent rings having the two closest substituable positions, e.g., the 2, 2’ position of biphenyl or the 1, 8 position of naphthalene, or on the same ring adjacent to each other, as long as a stable fused ring system can be formed.

[0069] At the molecular scale, the emission pattern of each emitter molecule in the emissive layer (EML) of an OLED can be described as a vibrational dipole. Thus, emitter molecules emit most of the light in a direction perpendicular to the dipole. The emission intensity disappears along the dipole axis. Consequently, the average orientation of the emission dipole moments within the EML of the OLED significantly affects the ratio of light trapped in parasitic waveguide modes to the production emission in the forward direction. Therefore, an alternative method to increase light extraction efficiency is to align the transition dipole moments of the emitting molecules in the OLED horizontally, that is, within the plane of the device. In the novel compounds disclosed herein, the compounds have specific molecular shapes capable of aligning the transition dipole moments (TDM) of the compounds within the EML within the plane of the EML and generating a maximum light extraction effect. Molecular shapes (A), (B), and (C), respectively illustrated in FIGS. 3a, 3b, and 3c, illustrate the concept. For molecular forms (A), (B), and (C), the bulk rigid surface interacts more with the host molecule. Consequently, the emission dipole vector is perpendicular to the C3 symmetry rotation axis in the molecule, and the double degenerate TDM is parallel to the substrate. As a result of these molecular forms, higher optical output is observed.

[0070] Formula [L A ] 3-n Ir[L B ] n A compound having is disclosed,

[0071] In the above formula,

[0072] n is 1, 2, or 3 and; L A is formula I is a ligand of; A is a fused ring structure containing three or more fused heterocyclic or carbocyclic rings; and Z 1 To Z 4 are each independently C or N; R 1 and R 2 ’ and ’ each independently represent a uniform substitution, the maximum allowable number of substitutions, or no substitution; 2 L’ A If a ligand is present, it may be the same or different; L B is Equation II It is a ligand of; R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently hydrogen, or a substituent selected from the group consisting of the general substituents defined above; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R Xis selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; 2 or 3 L B If a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to and does not form a loop.

[0073] In some embodiments of the compound, each L present B In the ligand, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen.

[0074] In some embodiments of the compound, each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is a substituent selected from the group consisting of hydrogen, or the preferred general substituents defined above.

[0075] In some embodiments of the compound, A is a fused ring structure comprising a chemical group selected from the group consisting of dibenzofuran, dibenzothiofuran, carbazole, anthracene, phenanthrene, triphenylene, and aza derivatives thereof.

[0076] In some embodiments of the compound, Z 1 To Z4 are each C. In some embodiments, Z 1 To Z 4 One of them is N, and the rest are C.

[0077] In some embodiments of the compound, L 1 is a substituent of Formula III, and L 2 is a hydrogen or alkyl group. In some embodiments of the compound, L 2 is a substituent of Formula III, and L 1 is hydrogen or an alkyl group. In some embodiments of the compound, L 1 and L 2 Both are substituents of Formula III.

[0078] In some embodiments of the compound, each R 1 is a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof. In some embodiments of the compound, at least one R 1 is an alkyl or aryl group. In some embodiments, at least one R 3 is an alkyl group. In some embodiments, at least one R 4 is an alkyl group.

[0079] In some embodiments of the compound, R W , R X , and R Y is H. In some embodiments, R W and R Y is H. In some embodiments, at least one substituent of Formula III, R V , R X and R Z It contains a total of eight or more carbon atoms. In some embodiments, at least one substituent of Formula III, R V , R X and R Z It contains a total of 10 or more carbon atoms. In some embodiments, R V and R Zis each independently an alkyl or cycloalkyl group. In some embodiments, R V , R X , and R Z Each is independently an alkyl or cycloalkyl group.

[0080] In some embodiments of the compound, n is 3. In some embodiments, n is 2. In some embodiments, n is 1.

[0081] In some embodiments of the compound, each L B The ligands are identical. In some embodiments, each L B The ligands are not identical.

[0082] In some embodiments of the compound, A comprises four or more fused rings. In some embodiments, A comprises five or more fused rings. In some embodiments, A comprises six or more fused rings.

[0083] In some embodiments of the compound, each L A is selected from a group consisting of:

[0084]

[0085]

[0086] ;

[0087] In the above equation, R 4 and R 5 is R 1 It has the same definition as .

[0088] In some embodiments of the compound, each L A is selected from a group consisting of:

[0089]

[0090]

[0091] In some embodiments of the compound, each L A is L A1 to L A394Selected from a group consisting of;

[0092] Here,

[0093] L A1 to L A394 is Equation IV Based on the structure of;

[0094] G Y is G defined below Y1 to G Y32 Selected from a group consisting of:

[0095]

[0096]

[0097] ;

[0098] R P , R T , G Y and R 9 is defined as in the table below:

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] At this time,

[0109] am.

[0110] In some embodiments of the compound, each L B is selected from a group consisting of:

[0111] ;

[0112] R 6 and R 7 is R 3 and R 4 Having the same definition as;

[0113] Each R 1A , R 1B , R 2A , R 2B is a substituent independently selected from the group consisting of hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0114] In some embodiments of the compound, each L B is the L defined below B1 to L B115 Selected from a group consisting of:

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] Here, Equations 1, 2, and 3 are as defined below:

[0122] ;

[0123] R 1A , R 2A , R 1B , R 2B , R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B is selected from a group consisting of:

[0124] .

[0125] In some embodiments of the compound, the compound is of the formula Ir(L A i )(L B k Compound B having )2 y And; y = 115 i + k -115 and; i is an integer from 1 to 394, and k is an integer from 1 to 115; or the compound is of the formula Ir(L A i )2(L B k Compound C having ) z And; z = 115 i + k -115 and; i is an integer from 1 to 394, and k is an integer from 1 to 115.

[0126] In some embodiments of the compound, the compound is selected from the group consisting of the following:

[0127]

[0128]

[0129]

[0130] .

[0131] An organic light-emitting device (OLED) incorporating a compound of the present invention is also disclosed. The OLED comprises an anode; a cathode; and a portion disposed between the anode and the cathode, and the formula [L A ] 3-n Ir[L B ] n It comprises an organic layer comprising a compound having; wherein, in the above formula, n is 1, 2, or 3; and L A is formula I is a ligand of; A is a fused ring structure containing three or more fused heterocyclic or carbocyclic rings; and Z 1 To Z 4 are each independently C or N; R 1 and R 2 ’ and ’ each independently represent a uniform substitution, the maximum allowable number of substitutions, or no substitution; 2 L’ A If a ligand is present, it may be the same or different; L B is Equation II It is a ligand of; R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently hydrogen, or a substituent selected from the group consisting of the general substituents defined above; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; 2 or 3 L B If a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R ZAt least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to and does not form a loop.

[0132] In some embodiments of the OLED, the organic layer is a light-emitting layer, and the compound may be a light-emitting dopant or a non-light-emitting dopant. In some embodiments of the OLED, the organic layer further comprises a host, and the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0133] In some embodiments of the OLED, the host is

[0134]

[0135]

[0136]

[0137] and is selected from a group consisting of combinations thereof.

[0138] In some embodiments of the OLED, the organic layer further comprises a host, and the host comprises a metal complex.

[0139] In some embodiments of the OLED, the compound is a sensitizer and the OLED further comprises an acceptor; the acceptor is selected from the group consisting of a fluorescence emitter, a delayed fluorescence emitter, and combinations thereof.

[0140] In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and curved properties. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer containing carbon nanotubes.

[0141] In some embodiments, the OLED further comprises a layer containing a delay fluorescence emitter. In some embodiments, the OLED comprises an array of RGB pixels, or an array of white plus color filter pixels. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of 10 inches or more or an area of ​​50 square inches or more. In some embodiments, the OLED is a lighting panel.

[0142] In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound may produce luminescence through phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence); for example, U.S. Patent Application No. 15 / 700,352 published March 14, 2019, the full text of which is incorporated herein by reference), triplet-triplet extinction, or a combination of these processes. In some embodiments, the luminescent dopant may be a racemic mixture or may be rich in one enantiomer. In some embodiments, the compound may be homoligandic (each ligand is identical). In some embodiments, the compound may be heteroligandic (at least one ligand is different from the others).

[0143] Where one or more ligands are coordinated to the metal, the ligands may all be the same in some embodiments. In some other embodiments, at least one ligand is different from the remaining ligand(s). In some embodiments, all ligands may be different from each other. This is also true in embodiments where a ligand coordinated to the metal may be linked with other ligands coordinated to the metal to form a ternary, quaternary, quinary, or hexadentary ligand. Thus, where the coordination ligands are linked to each other, all ligands may be the same in some embodiments, and at least one of the linked ligands may be different from the other ligand(s) in some other embodiments.

[0144] In some embodiments, the compound may be used as a phosphorescent sensitizer in an OLED, wherein one or more layers within the OLED contain acceptors in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the compound may be used as one component of an exciplex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor, and the acceptor emits energy or further transfers energy to the final emitter. The acceptor concentration may be in the range of 0.001% to 100%. The acceptor may be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, emission may occur from some or all of the sensitizer, the acceptor, and the final emitter.

[0145] In some embodiments, the compound of the present invention is neutrally charged.

[0146] According to another embodiment, a formulation comprising the compound described herein is also disclosed.

[0147] The OLED disclosed herein may be included in one or more of consumer products, electronic component modules, and lighting panels. The organic layer may be a light-emitting layer, and the compound may be a light-emitting dopant in some embodiments, while the compound may be a non-light-emitting dopant in other embodiments.

[0148] The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) a bipolar material, b) an electron transport material, c) a hole transport material, or d) a wide band gap material having little role in charge transport. In some embodiments, the host may include a metal complex. The host may be a triphenylene-containing benzofused thiophene or a benzofused furan. Any substituent in the host is independently 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 The host may be a non-fusion substituent selected from the group consisting of -Ar1, or the host may not have a substituent. In the said substituent, n may be in the range of 1 to 10; Ar1 ​​and Ar2 may independently be selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host may be an inorganic compound, for example, a Zn-containing inorganic material, e.g., ZnS.

[0149] The host may be a compound comprising one or more chemical groups selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenopene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenopene. The host may comprise a metal complex. The host may be, but is not limited to, a specific compound selected from the group of hosts consisting of the following chemical formulas and combinations thereof:

[0150]

[0151]

[0152]

[0153] Additional information regarding available hosts is provided below.

[0154] A light-emitting region is initiated in an organic light-emitting device. The light-emitting region is denoted by the formula [L A ] 3-n Ir[L B ] n Compound comprising having, wherein, in the above formula, n is 1, 2, or 3; L A is formula I is a ligand of; A is a fused ring structure containing three or more fused heterocyclic or carbocyclic rings; and Z 1 To Z 4 are each independently C or N; R 1 and R 2 ’ and ’ each independently represent a uniform substitution, the maximum allowable number of substitutions, or no substitution; 2 L’ A If a ligand is present, it may be the same or different; L B is Equation II It is a ligand of; R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R1 , R 2 , R 3 , and R 4 is independently hydrogen, or a substituent selected from the group consisting of the general substituents defined above; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; 2 or 3 L B If a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to and does not form a loop.

[0155] In some embodiments of the light-emitting region, the compound may be a light-emitting dopant or a non-light-emitting dopant.

[0156] In some embodiments, the light-emitting region further comprises a host, and the host contains at least one group selected from the group consisting of a metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenopene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenopene.

[0157] In some embodiments of the light-emitting region, the light-emitting region further includes a host, and the host

[0158]

[0159]

[0160]

[0161] and is selected from a group consisting of combinations thereof.

[0162] In another aspect of the present disclosure, a formulation comprising a novel compound disclosed herein is described. The formulation may comprise one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport layer material disclosed herein.

[0163] The present invention comprises any chemical structure comprising the novel compound of the present invention, or a monovalent or polyvalent variant thereof. That is, the compound of the present invention, or a monovalent or polyvalent variant thereof, may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (or supermolecules). As used herein, a “monovalent variant of the compound” exhibits the same moiety as the compound except that one hydrogen is removed and replaced by a bond to the remainder of the chemical structure. As used herein, a “polyvalent variant of the compound” exhibits the same moiety as the compound except that one or more hydrogens are removed and replaced by bond(s) to the remainder of the chemical structure. In the case of supramolecules, the compound of the present invention may also be incorporated into a supramolecular complex without covalent bonding.

[0164] Combination with other substances

[0165] Materials described herein as useful for a specific layer in an organic light-emitting device may be used in combination with a wide variety of other materials present in the device. For example, the light-emitting dopant disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art may readily refer to the literature to identify other materials that may be useful in combination.

[0166] Conductive dopant:

[0167] The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which will consequently change its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the semiconductor's Fermi level can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer.

[0168] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references disclosing the materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0169]

[0170]

[0171] HIL / HTL:

[0172] The hole injection / transport material intended for use in the present invention is not specifically limited, and any compound may be used as long as it is conventionally used as a hole injection / transport material. Non-limiting examples of materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers comprising fluorohydrocarbons; polymers having conductive dopants; conductive polymers, e.g., PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, e.g., MoO₂ x; p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes and crosslinkable compounds may be examples.

[0173] Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the following structural formulas:

[0174]

[0175] Each Ar 1 or Ar 9is a group composed of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; Dibenzothiophen, Dibenzofuran, Dibenzoselenopene, Furan, Thiophene, Benzofuran, Benzothiophene, Benzoselenopene, Carbazole, Indolocarbazole, Pyridylindole, Pyrrolodipyridine, Pyrazol, Imidazole, Triazole, Oxazole, Thiazole, Oxadiazole, Oxatriazole, Dioxazole, Thiadiazole, Pyridine, Pyridazine, Pyrimidine, Pyrazine, Triazine, Oxazine, Oxathiazine, Oxadiazine, Indole, Benzimidazole, Indazole, Indoxazine, Benzoxazole, Benzisoxazole, Benzothiazole, Quinoline, Isoquinoline, Sinnoline, Quinazolin, Quinoxaline, Naphthiridine, Phthalasine, Pteridine, Xanthen, Acridine, Phenazine, Phenothiazine, Phenoxazine, A group consisting of aromatic heterocyclic compounds such as benzopyridine, propipyridine, benzothiopyridine, thienopiridine, benzoselenofenopiridine, and selenofenofyridine; and a group of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and selected from a group consisting of 2 to 10 cyclic structural units that are bonded through one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group or directly bonded to each other. Each Ar may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0176] In one mode, Ar 1 or Ar 9is independently selected from the group consisting of the following chemical formulas:

[0177]

[0178] Here, k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 eu NAr 1 , O or S and; Ar 1 It has the same mechanism as defined above.

[0179] Non-limiting examples of metal complexes used in HIL or HTL include the following chemical formulas:

[0180]

[0181] Here, Met is a metal and can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a 2-position ligand, and Y 101 and Y 102 is independently selected from C, N, O, P, and S; L 101 is an auxiliary ligand; k' is an integer value of the maximum number of ligands that can be bound to the metal, ranging from 1 to 1; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0182] In one mode, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex has a minimum oxidation potential versus Fc in solution of less than about 0.6 V. + / Fc has a couple.

[0183] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references disclosing such materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812,WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.,

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] EBL:

[0193] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can lead to significantly higher efficiency and / or longer lifetime compared to a similar device without a blocking layer. Additionally, the blocking layer can be used to confine light 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 than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in the EBL contains the same molecule or functional group as one of the hosts described below.

[0194] Host:

[0195] The light-emitting layer of the organic EL device of the present invention preferably comprises at least a metal complex as a light-emitting material and may comprise a host material using a metal complex as a dopant material. Examples of host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0196] An example of a metal complex used as a host preferably has the following chemical formula:

[0197]

[0198] Here, Met is a metal; (Y 103 -Y 104 ) is a 2-position ligand, and Y 103 and Y 104 is independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value of the maximum number of ligands that can be bound to the metal, from 1 to; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0199] In one embodiment, the metal complex , where (ON) is a 2-position ligand having a metal coordinately bonded to atoms O and N.

[0200] In another embodiment, Met is selected from Ir and Pt. In an additional embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0201] In one embodiment, the host compound is a group consisting of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; Aromatic heterocyclic compounds, e.g., dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, It contains at least one of the group consisting of phenazine, phenothiazine, phenoxazine, benzopuropyridine, purodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenofyridine and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units that are of the same or different type selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and are bonded through one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group, or are directly bonded to each other. Each option within each group may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0202] In one embodiment, the host compound contains one or more of the following groups in the molecule:

[0203]

[0204]

[0205] Here, R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and if it is aryl or heteroaryl, it has a definition similar to that of Ar described above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 is independently selected from C (including CH) or N. Z 101 and Z 102 is independently NR 101 , is selected from O or S.

[0206] Non-limiting examples of additional host materials that may be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references disclosing such materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0207]

[0208]

[0209]

[0210]

[0211]

[0212] additional Emitter:

[0213] One or more additional emitter dopants may be used in combination with the compounds of the present disclosure. Examples of additional emitter dopants are not particularly limited, and any compound that is typically used as an emitter material may be used. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing emission through phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet extinction, or a combination of these processes.

[0214] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references disclosing such materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663,US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, 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, WO07115981, 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.,

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221] HBL:

[0222] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can lead to significantly higher efficiency and / or longer lifetime compared to similar devices without a blocking layer. Additionally, the blocking layer can be used to confine light emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than one or more of the hosts closest to the HBL interface.

[0223] In one embodiment, the compound used in the HBL contains the same molecule or functional group as the aforementioned host.

[0224] In another embodiment, the compound used in HBL contains one or more of the following groups in the molecule:

[0225]

[0226] Here, k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0227] ETL:

[0228] The electron transport layer (ETL) may comprise a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as they are typically used to transport electrons.

[0229] In one embodiment, the compound used for ETL contains one or more of the following groups in the molecule:

[0230]

[0231] Here, R 101 Ar is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and if it is aryl or heteroaryl, it has a definition similar to that of Ar described above. 1 or Ar 3 has a definition similar to Ar described above. k is an integer from 1 to 20. X 101 To X 108 It is selected from C (including CH) or N.

[0232] In another embodiment, the metal complex used in the ETL includes, but is not limited to, the following chemical formula:

[0233]

[0234] Here, (ON) or (NN) is a dubate ligand having a metal coordinately bonded to atoms O, N or N, N; L 101is another ligand; k' is an integer value ranging from 1 to the maximum number of ligands to which a metal can be bound.

[0235] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references disclosing such materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0236]

[0237]

[0238]

[0239] Charge Generation Layer (CGL):

[0240] In tandem or stacked OLEDs, the CGL plays an essential role in terms of performance and consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and the electrodes. Electrons and holes consumed in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Conventional CGL materials include n and p conductive dopants used in the transport layer.

[0241] In any of the aforementioned compounds used in each layer of the OLED device, hydrogen atoms may be partially or completely deuterinated. Thus, any specifically listed substituents, e.g., methyl, phenyl, pyridyl, etc., may be in their non-deuterinated, partially deuterinated, and fully deuterinated forms. Likewise, substituent types, e.g., non-deuterinated, alkyl, aryl, cycloalkyl, heteroaryl, etc., may also be in their non-deuterinated, partially deuterinated, and fully deuterinated forms.

[0242] Experimental Example

[0243] Compound Ir[L of the present invention B93 ] 2 L A62 Synthesis of

[0244]

[0245] Step 1

[0246]

[0247] 10-chloronaphtho[1,2-b]benzofuran (4 g, 15.83 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-b(1,3,2-dioxaborolane) (5.23 g, 20.58 mmol), tris(dibenzylideneacetone)palladium (0) (0.435 g, 0.475 mmol), and S-Phos (1.2 g, 2.93 mmol) were added to a reaction flask containing 120 mL of dioxane. Subsequently, potassium acetate (3.34 g, 34.8 mmol) was added to the reaction flask. The mixture was degassed with nitrogen and heated under reflux for 18 hours. The reaction mixture was used in the next step without purification.

[0248] Step 2

[0249]

[0250] 4,4,5,5-tetramethyl-2-(naphtho[1,2-b]benzofuran-10-yl)-1,3,2-dioxaborolane (5.45 g, 15.83 mmol), 2-chloro-4-(4,4-dimethylcyclohexyl-1-d)-5-(methyl-d3)pyridine (4.98 g, 20.58 mmol), and tetrakis(triphenylphosphine)palladium (0) (0.548 g, 0.475 mmol) were added to the reaction mixture. Potassium phosphate tribasic monohydrate (10.92 g, 47.5 mmol) was dissolved in 30 mL of water and then added to the reaction mixture. The mixture was degassed with nitrogen and heated under reflux for 18 hours. After cooling the reaction mixture to room temperature, most of the dioxane was removed by vacuum. This mixture was treated with 200 mL of water. This mixture was extracted with 3 x 200 mL of DCM. The extract was dried over magnesium sulfate, filtered, and vacuum concentrated. The unrefined residue was passed through 2 x 330 g silica gel columns and eluted with 100% DCM followed by 1-5% ethyl acetate / DCM. The clear fractions were combined and vacuum concentrated to yield 4-(4,4-dimethylcyclohexyl-1-d)-5-(methyl-d3)-2-(naphtho[1,2-b]benzofuran-10-yl)pyridine (4.77 g, 11.26 mmol, 71.1% yield) as a white solid.

[0251] Step 3

[0252]

[0253] 4-(4,4-dimethylcyclohexyl-1-d)-5-(methyl-d3)-2-(naphtho[1,2-b]benzofuran-10-yl)pyridine (2.1 g, 4.96 mmol) and iridium salt (3.25 g, 2.74 mmol) were added to a reaction flask containing 40 mL of 2-ethoxyethanol and 40 mL of DMF. This mixture was stirred and heated in a bath set at 100°C for 14 days. Then, heating was stopped. The solvent was vacuumed off, and the crude product was passed through basic alumina to elute the column with 40% DCM / heptane. The solvent was vacuumed off. Subsequently, this crude material was passed through a 10 x 120 g silica gel column to elute the column with 40-80% toluene / heptane. The clean product fraction yielded an iridium complex (1.4 g, 1.003 mmol, 36.6% yield). The mass of the desired iridium complex was confirmed by LC / MS.

[0254] Synthesis of Comparative Example Compounds

[0255]

[0256] Step 1:

[0257]

[0258] di-μ-chloro-tetrakis[κ2(C2,N)-4,5-bis(methyl- d 3 )-2-(4-(methyl- d 3 )phenyl)-pyridine]diiridium(III) : Diglim (1.6 L) and DIUF water (340 mL) were added to a 5 L four-necked round-bottom flask, and nitrogen was supplied to the mixture for 15 minutes. Iridium(III) chloride hydrate (86 g, 272 mmol, 1.0 equivalent) and 4 , 5-bis(methyl- d 3)-2-(4-(methyl- d3) Phenyl)pyridine (129 g, 626 mmol, 2.3 equivalents) was added, and the reaction mixture was heated under reflux for 96 hours (103-105°C) [Note: The reaction proceeded with the post-treated fraction dissolved in high-temperature DMSO-d6 1 [Monitored by H NMR analysis]. Cool the reaction mixture, filter the solid, wash with methanol (3 x 300 mL), and then vacuum dry at 70°C for 2 hours to di-μ-chloro-tetrakis[κ2(C2,N)-4,5-bis(methyl- d 3)-2-(4-(methyl- d 3)-phenyl)pyridine]diiridium(III) (152 g, 88% yield) was obtained as a yellow solid.

[0259] Step 2:

[0260]

[0261] [Ir(4,5-bis(methyl- d 3 )-2-(4-(methyl- d 3 )phenyl)pyridine(-1H)) 2 (MeOH) 2 ](trifluoromethanesulfonate) : di-μ-chlorotetrakis[κ2(C2,N)-4,5-bis(methyl- d 3)-2-(4-(methyl- d A solution of [3)-phenyl)pyridine]diiridium(III) (152 g, 119 mmol, 1.0 equivalent) was prepared. To exclude light, the flask was wrapped in aluminum foil, and a solution of silver trifluoromethanesulfonate (67.3 g, 262 mmol, 2.2 equivalents) in methanol (500 mL) was added. The reaction mixture was stirred overnight at room temperature under nitrogen. The reaction mixture was filtered onto a short silica gel pad (220 g) topped with Celite (50 g), and the pad was washed with dichloromethane (3 x 500 mL). The filtrate was concentrated under reduced pressure, and the residue was dried in a vacuum oven to obtain [Ir(4,5-bis(methyl- d3)-2-(4-(methyl- d 3) Phenyl)pyridine(-1H))2-(MeOH)2](trifluoromethanesulfonate) (about 160 g, >100% yield) was obtained as a yellow solid with some residual solvent.

[0262] Step 3:

[0263]

[0264] bis[2-((4-(methyl- d 3 )phenyl-1-yl)-2'-yl)-4,5-bis(methyl- d 3 )pyridine-1-yl]-((4-(4,4-dimethylcyclohexyl-1- d )-5-(methyl- d 3 )-2-(naphtho[1,2-b]benzofuran-10-yl)-2'-yl)pyridine-1-yl) iridium(III) : In a 250 mL flask, [Ir(4,5-bis(methyl-) in tetrahydrofuran (45 mL) and ethanol (45 mL) d 3)-2-(4-(methyl- d 3)phenyl)pyridine(-1H))2-(MeOH)2](trifluoromethanesulfonate) (2.67 g, 3.27 mmol, 0.92 equivalents) and 4-(4,4-dimethyl-cyclohexyl-1- d )-5-(methyl- d 3)-2-(naphtho[1,2- bA mixture of benzofuran-10-yl)pyridine (1.5 g, 3.54 mmol, 1.0 equivalent) was treated with 2,6-rutidine (0.41 mL, 379 mg, 3.54 mmol, 1.0 equivalent). The reaction mixture was heated at 75°C. After 40 hours, <10% starting material was observed by LCMS analysis. The reaction mixture was cooled to room temperature and filtered. The solid residue (2 g) was placed in a dry loading cartridge and purified on a Buechi Reveleris automated system (a 120 g silica gel cartridge topped with basic alumina (40 g)) and eluted with 50% dichloromethane in heptane. A yellow residue that was not dissolved in 50% dichloromethane in heptane remained in the dry loading cartridge. The residue was purified on a Buechi Reveleris automated system (new 120 g silica gel cartridge topped with basic alumina (40 g)) and eluted with 70% dichloromethane in heptane. The combined product fraction was concentrated under reduced pressure. The solid (1.95 g, 98% LCMS purity) was redissolved in dichloromethane (100 mL), and methanol (100 mL) was added dropwise to precipitate the product. The solid was filtered and air-dried to obtain bis[2-((4-(methyl- d 3)phenyl-1-yl)-2'-yl)-4,5-bis(methyl- d 3)pyridine-1-yl]-((4-(4,4-dimethylcyclohexyl-1- d )-5-(methyl- d 3)-2-(naphtho[1,2-b]benzofuran-10-yl)-2'-yl)pyridine-1-yl)iridium(III) (1.63 g, 98.2% UPLC purity, 45% yield) was obtained as a yellow solid.

[0265] Device Example

[0266] All example devices, high vacuum (<10 -7It was fabricated by thermal evaporation (Torr). The anode electrode was 800 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) followed by 1000 Å Al. All devices were encapsulated with glass lids sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2) immediately after fabrication, and a moisture getter was introduced into the package. The organic stack of the device example consisted, from the ITO surface, 100 Å HAT-CN as a hole injection layer (HIL); 450 Å HTM as a hole transport layer (HTL); a 400 Å thick emissive layer (EML); and an emissive layer containing an H-host (H1):E-host (H2) in a 6:4 ratio and 12 wt% green emitter; As an ETL, it was sequentially composed of 350 Å Liq (8-hydroxyquinoline lithium) doped with 40% ETM. The device structure is presented in Table 1 below.

[0267] The chemical structure of the material used in the device is presented below.

[0268]

[0269]

[0270] EL and JVL of the two devices (DC 80 mA / cm²) 2 ) characteristics were measured. The results are presented in Table 2 below.

[0271]

[0272]

[0273] The data is normalized to the comparison example.

[0274] Example of the present invention Ir[L B93 ]2L A62 When comparing the device with the comparative example device, the luminance efficiency (LE), external quantum efficiency (EQE), and power efficiency (PE) of the device of the embodiment of the present invention are all higher than those of the comparative example device. The applicant [is Ir[L​B93 ]2L A62 It is believed that this is because the twisted aryl substitution of the auxiliary ligand aligns better with the transition dipole moment of the molecule. Furthermore, in the embodiment of the present invention Ir[L B93 ]2L A62 The device also has a lower voltage and a narrower FWHM, which are all desirable parameters for the display.

[0275] It should be understood that the various embodiments described herein are merely illustrative and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, as will be apparent to those skilled in the art, the claimed invention may include variations derived from the specific embodiments and preferred embodiments described herein. It should be understood that there is no intention to limit the various theories regarding why the invention is effective.

Claims

Claim 1 Formula [L A ] 3-n Ir[L B ] n Compound having: in the above formula, n is 1 or 2 and L A is formula I A is a ligand of; A is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings; A is a fused ring structure comprising a chemical group selected from the group consisting of dibenzofuran, dibenzothiophene, and aza derivatives thereof; A is coordinately bonded to Ir in one of the six-membered rings included in the chemical group; and Z 1 To Z 4 are each independently C or N and;R 1 and R 2 Each independently represents a uniform substitution, the maximum allowable number of substitutions, or a non-substitution; and 2 L A If a ligand is present, it may be the same or different;L B is Equation II It is a ligand of;R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently a substituent selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; and 2 L B Where a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to and does not form a loop, and also, however, When the six-membered ring coordinated with the above Ir has two or more substituents, the two substituents on the six-membered ring coordinated with the above Ir are not connected or fused together to form a ring. Claim 2 In paragraph 1, each existing L B In the ligand, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z A compound in which at least one of them is not hydrogen. Claim 3 In paragraph 1, each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 A compound in which the substituent is independently selected from the group consisting of hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof. Claim 4 delete Claim 5 In paragraph 1, Z 1 To Z 4 are compounds, each with C. Claim 6 In paragraph 1, Z 1 To Z 4 A compound in which one is N and the others are C. Claim 7 In paragraph 1, a compound corresponding to one of the following: (1) L 1 is a substituent of Formula III, and L 2 is a hydrogen or alkyl group; (2) L 2 is a substituent of Formula III, and L 1 is hydrogen or an alkyl group; (3) L 1 and L 2 Both are substituents of Formula III. Claim 8 In paragraph 1, n is a compound of 2. Claim 9 delete Claim 10 In paragraph 1, each L A Is Selected from a group consisting of; where R 4 and R 5 is R 1 A compound that has the same definition as . Claim 11 In paragraph 1, each L A is L A32 to L A212 Selected from a group consisting of; where L A32 to L A212 is Equation IV Based on the structure of;G Y is G defined below Y3 to G Y18 Selected from a group consisting of: R P , R T , G Y and R 9 is defined as in the table below: At this time, Phosphorus compound. Claim 12 In paragraph 1, each L B Is Selected from a group consisting of;R 6 and R 7 is R 3 and R 4 Having the same definition as; each R 1A , R 1B , R 2A , R 2B A compound in which the substituent is independently selected from the group consisting of hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof. Claim 13 In Paragraph 11, each L B is L B1 to L B115 Selected from a group consisting of; where L B1 to L B115 is defined as follows: Equations 1, 2, and 3 are defined as follows: ;R 1A , R 2A , R 1B , R 2B , R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B Is A compound selected from the group consisting of Claim 14 In Paragraph 13, the compound is of the formula Ir(L A i )(L B k Compound B having )2 y And; y = 115 i + k -115 and; i is an integer from 32 to 212, and k is an integer from 1 to 115; or the compound is of the formula Ir(L A i )2(L B k Compound C having ) z And; z = 115 i + k -115 and; i is an integer from 32 to 212, and k is a compound that is an integer from 1 to 115. Claim 15 Anode; cathode; and positioned between the anode and cathode, and equation [L A ] 3-n Ir[L B ] n An organic light-emitting device (OLED) comprising an organic layer containing a compound having: wherein, in the above formula, n is 1 or 2; and L A is formula I A is a ligand of; A is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings; A is a fused ring structure comprising a chemical group selected from the group consisting of dibenzofuran, dibenzothiophene, and aza derivatives thereof; A is coordinately bonded to Ir in one of the six-membered rings included in the chemical group; and Z 1 To Z 4 are each independently C or N and;R 1 and R 2 Each independently represents a uniform substitution, the maximum allowable number of substitutions, or a non-substitution; and 2 L A If a ligand is present, it may be the same or different;L B is Equation II It is a ligand of;R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently a substituent selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; and 2 L B If a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to form a ring, and additionally, if the six-membered ring coordinated with the Ir has two or more substituents, the two substituents on the six-membered ring coordinated with the Ir are not connected or fused together to form a ring. Claim 16 An OLED in which, in paragraph 15, the organic layer is a light-emitting layer and the compound may be a light-emitting dopant or a non-light-emitting dopant. Claim 17 An OLED according to claim 15, wherein the organic layer further comprises a host, and the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. Claim 18 In Paragraph 17, the host OLED selected from a group consisting of combinations thereof. Claim 19 Anode; cathode; and positioned between the anode and cathode, and equation [L A ] 3-n Ir[L B ] n A consumer product comprising an organic light-emitting device including an organic layer comprising a compound having: wherein, in the above formula, n is 1 or 2; and L A is formula I A is a ligand of; A is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings; A is a fused ring structure comprising a chemical group selected from the group consisting of dibenzofuran, dibenzothiophene, and aza derivatives thereof; A is coordinately bonded to Ir in one of the six-membered rings included in the chemical group; and Z 1 To Z 4 are each independently C or N and;R 1 and R 2 Each independently represents a uniform substitution, the maximum allowable number of substitutions, or a non-substitution; and 2 L A If a ligand is present, it may be the same or different;L B is Equation II It is a ligand of;R 3 and R 4 Each independently represents a uniform substitution or the maximum allowable number of substitutions, or no substitutions; and each L 1 , L 2 , R 1 , R 2 , R 3 , and R 4 is independently a substituent selected from the group consisting of hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; L 1 and L 2 At least one of them is Formula III It is a substituent of; and each R V , R W , R Y , and R Z is independently a substituent selected from the group consisting of hydrogen, or deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, and combinations thereof; R X is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof; and 2 L B Where a ligand is present, it may be the same or different; at least one ligand L B In, R V , R X and R Z It contains a total of 6 or more carbon atoms, and R V and R Z At least one of them is not hydrogen; any two substituents may be connected or fused together to form a ring, provided that L 1 is R 3 Connected to and not forming a loop, L 2 is R 4 It is connected to form a ring, and additionally, if the six-membered ring coordinated with the Ir has two or more substituents, the two substituents on the six-membered ring coordinated with the Ir are not connected or fused together to form a ring. Claim 20 In paragraph 1, the compound is a compound selected from the group consisting of the following:

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