Organic electroluminescent materials and devices

Abstract

To provide novel phosphorescent metal complexes comprising ligands having naphthalene or other fused heterocyclic moieties, such as benzofuran and benzothiophene, which are useful as emitters in OLEDs and improve device efficiency and FWHM of light emission.SOLUTION: The composition contains a compound containing a ligand LA represented by formula (1).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 403,424, filed October 3, 2016, the disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to compounds for use as phosphorescent emitters for organic electroluminescent devices, such as organic light-emitting devices (OLEDs). More particularly, the present disclosure relates to phosphorescent metal complexes that include ligands having naphthalene or other fused heterocyclic moieties, such as benzofuran and benzothiophene. [Background technology]

[0003] Optoelectronic devices utilizing organic materials are becoming increasingly desirable for several reasons. Because many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic light-emitting layer emits light can generally be easily tuned with appropriate dopants.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,623,999; 5,723,999; and 5,723,999, which are incorporated herein by reference in their entireties.

[0005] One application of phosphorescent emissive molecules is full-color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventionally, liquid crystal display emission from a white backlight is filtered with absorbing filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single EML devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art.

[0006] An example of a green emitting molecule has the following structure: [ka] The compound is tris(2-phenyl)iridium, denoted as Ir(ppy)3, having the formula:

[0007] In this figure and later figures herein, we depict the coordination bond from nitrogen to the metal (here Ir) as a straight line.

[0008] As used herein, the term "organic" includes polymeric and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. Small molecules can contain repeating units in some circumstances. For example, using a long-chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules can be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of the backbone. Small molecules can also serve as the core moiety of dendrimers, which consist of a series of chemical shells built on the core moiety. The core moiety of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

[0009] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there may be various organic layers in between.

[0010] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0011] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" if it is considered not to contribute to the photoactive properties of the emissive material, although the ancillary ligand may modify the properties of the photoactive ligand.

[0012] As used herein, and as would generally be understood by one of ordinary skill in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Because ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On 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. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0013] As used herein, and as will generally be understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

[0014] Further details on OLEDs and the above definitions can be found in US Pat. No. 6,223,999, which is incorporated herein by reference in its entirety. Summary of the Invention

[0015] According to an embodiment of the present disclosure, a ligand L represented by formula I: A Disclosed is a compound comprising: [ka] Formula I In the formula, ring B represents a 5- or 6-membered aromatic ring, and R 3 represents the maximum number of substitutions from no substitutions, X 1 , X 2 , X 3 , and X 4 are each independently CR or N, (1)X 1 , X 2 , X 3 , and X 4 at least two adjacent ones of are C—R and are fused to form a 5- or 6-membered aromatic ring; or (2)X 1 , X 2 , X 3 , and X 4 at least one of is nitrogen, or (3) Both (1) and (2) are true, (a)R 1 is CR 11 R 12 R 13 or R 2 to form a ring, or (b)R 2 is not hydrogen, or (c) Both (a) and (b); R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R 1 , R 2 , R 3 , R 11 , R12 , and R 13 Any two of the substituents may be bonded to form a ring, and L A is coordinated to the metal M, and L A may be linked to other ligands to comprise tridentate, tetradentate, pentadentate, or hexadentate ligands, and M may be coordinated to other ligands.

[0016] According to another aspect, the ligand L of formula I A Disclosed is a composition comprising a compound comprising:

[0017] According to another aspect, an emissive region in an OLED is disclosed, the emissive region comprising the ligand L of formula I: A The compound includes:

[0018] According to another aspect, a first device is disclosed that includes a first OLED, the first OLED including an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including the ligand L represented by Formula I: A The compound includes:

[0019] A consumer product is disclosed that includes a first OLED, the first OLED including an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including the ligand L represented by Formula I: A The compound includes: [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 shows an organic light-emitting device.

[0021] [Figure 2] FIG. 2 shows an inverted organic light-emitting device that does not have a separate electron transport layer. DETAILED DESCRIPTION OF THE INVENTION

[0022] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons migrate to the oppositely charged electrode, respectively. When an electron and hole localize on the same molecule, an "exciton," a localized electron-hole pair with an excited energy state, is formed. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may be localized on an excimer or exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0023] Early OLEDs used emissive molecules that emitted light from their singlet state ("fluorescence"), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0024] More recently, OLEDs have been demonstrated that have emissive materials that emit light from triplet states ("phosphorescence"). Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Vol. 395, No. 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entireties. Phosphorescence is described in further detail in U.S. Pat. No. 7,279,704, columns 5-6, which are incorporated by reference.

[0025] FIG. 1 shows an organic light-emitting device 100. The drawing is not necessarily to scale. Device 100 may include a substrate 110, an anode 115, a hole-injection layer 120, a hole-transport layer 125, an electron-blocking layer 130, an emissive 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. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in further detail in U.S. Pat. No. 7,279,704, cols. 6-10, which is incorporated by reference.

[0026] Further examples are available for each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole-transporting layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron-transporting layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes, including composite cathodes having a thin layer of metal, such as Mg:Ag, with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use 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, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0027] FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole-transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers described, in order. Because the most common OLED configuration has the cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 is sometimes referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers can be omitted from the structure of device 100.

[0028] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention can be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. A functional OLED may be achieved by combining the various layers described in various 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. While many of the examples provided herein describe various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally, mixtures, may be used. Layers may also have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole-transport layer 225 transports holes and injects holes into emissive layer 220 and may be described as a hole-transport layer or a hole-injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials, for example, as described with respect to Figures 1 and 2.

[0029] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) composed of polymeric materials, such as those disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as mesa structures as described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or recessed structures as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0030] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties; inkjet deposition; organic vapor phase deposition (OVPD), such as that described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety; and organic vapor jet printing (OVJP), such as that described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin-coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition via masks, such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, deposition via cold welding, and patterning associated with some deposition methods, such as inkjet and OVJP. Other methods may also be used. The material to be deposited may be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least three carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, because asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0031] Devices fabricated according to embodiments of the present invention may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited over, under, or adjacent to the substrate, the electrode, or any other portion of the device, including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials, as described in U.S. Pat. No. 7,968,146 and PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entireties. To be considered a "mixture," the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric to non-polymeric materials can be in the range of 95:5 to 5:95. The polymeric and non-polymeric materials can be made from the same precursor materials. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0032] Devices made according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electronic products or intermediate components. Such electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), and the like, which can be utilized by end-user product manufacturers. Such electronic component modules can optionally include drive electronics and / or power sources. Devices made according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Consumer products are disclosed that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more display devices of some kind. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made in accordance with the present invention. Many of the devices are intended for use within a temperature range comfortable to humans, such as 18°C ​​to 30°C, and more preferably room temperature (20-25°C), but can also be used outside this temperature range, e.g., between -40°C and +80°C.

[0033] 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.

[0034] As used herein, the terms "halo," "halogen," or "halide" include fluorine, chlorine, bromine, and iodine.

[0035] As used herein, the term "alkyl" refers to both straight-chain and branched-chain alkyl groups. Preferred alkyl groups contain 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Furthermore, the alkyl groups may be optionally substituted.

[0036] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group. Preferred cycloalkyl groups contain 3 to 10 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl. Furthermore, the cycloalkyl groups may be substituted.

[0037] As used herein, the term "alkenyl" refers to both straight-chain and branched-chain alkenyl groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl groups may be substituted.

[0038] As used herein, the term "alkynyl" refers to both straight-chain and branched-chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be substituted.

[0039] As used herein, the terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group having an aromatic group as a substituent. Additionally, the aralkyl group may be optionally substituted.

[0040] As used herein, the term "heterocyclic group" refers to aromatic and non-aromatic ring groups. Heteroaromatic ring groups also refer to heteroaryl. Preferred heteroaromatic ring groups contain 3 to 7 ring atoms and at least one heteroatom, and include cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers such as tetrahydrofuran and tetrahydropyran. Furthermore, the heterocyclic group may be substituted.

[0041] As used herein, the term "aryl" or "aromatic group" refers to monocyclic and polycyclic ring systems. A polycyclic ring can have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are "fused"), at least one of which is aromatic, e.g., the other rings are 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 carbon atoms, 10 carbon atoms, or 12 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl group may be substituted.

[0042] As used herein, the term "heteroaryl" refers to a monocyclic heteroaromatic group that can contain 1 to 5 heteroatoms. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), at least one of which is heteroaryl, and the other rings can be, for example, cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benziso ... Examples of heteroaryl groups include benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, and preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and their aza analogs. Furthermore, the heteroaryl group may be optionally substituted.

[0043] The alkyl, the cycloalkyl, the alkenyl, the alkynyl, the aralkyl, the heterocycle, the aryl, and the heteroaryl may be unsubstituted or substituted with one or more substituents selected from deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0044] As used herein, "substituted" indicates that a substituent other than H is attached to the relevant position, such as a carbon. Thus, for example, R 1 is monosubstituted, R 1 must be other than H. Similarly, R 1 is disubstituted, R 1 Two of the must be other than H. Similarly, R 1 is unsubstituted, R 1 is hydrogen at all substitution positions.

[0045] The term "aza" in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C—H groups in each fragment can be replaced with a nitrogen atom; for example, but not by way of limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those skilled in the art can easily imagine other nitrogen analogs of the above-described aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0046] It is understood that when a molecular fragment is described as a substituent or as being attached to another moiety, the name may be described as either the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (benzene, naphthalene, dibenzofuran). Different designations of substituents or attached fragments are considered equivalent herein.

[0047] This disclosure relates to novel ligands for metal complexes. These ligands contain naphthalene or other similar fused heterocycles. Furthermore, the fused units contain blocking side chains that are tert-butyl or tert-butyl derivatives. The combination of these elements within the ligands allows for the creation of a single isomer of the final cyclometallated complex. This also results in better efficiency, a red shift in emission color, and a narrower emission.

[0048] The present disclosure relates to phosphorescent metal complexes containing ligands bearing naphthalene or other fused heterocyclic moieties, such as benzofuran and benzothiophene. These moieties are substituted on the phenyl bonded to the iridium atom with aliphatic side chains that block the alignment and prevent attachment at undesired positions. The side chains are tert-butyl or tert-butyl derivatives. In addition to obtaining materials of much higher purity, the addition of the tert-butyl side chains allows for better EQE (external quantum efficiency) and FWHM (full width at half maximum) of the emission. The fused rings at the bottom of the ligands result in a red shift in the emission color, while the side chains on these rings result in a blue shift.

[0049] According to an embodiment of the present disclosure, a ligand L represented by formula I: A Disclosed is a compound comprising: [ka] Formula I In the formula, ring B represents a 5- or 6-membered aromatic ring, and R 3represents the maximum number of substitutions from no substitutions, X 1 , X 2 , X 3 , and X 4 are each independently CR or N, (1)X 1 , X 2 , X 3 , and X 4 at least two adjacent ones of are C—R and are fused to form a 5- or 6-membered aromatic ring; or (2)X 1 , X 2 , X 3 , and X 4 at least one of is nitrogen, or (3) Both (1) and (2) are true, (a)R 1 is CR 11 R 12 R 13 or R 2 to form a ring, or (b)R 2 is not hydrogen, or (c) Both (a) and (b); R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 any two of the substituents may be joined to form a ring; L A is coordinated to the metal M, L A may contain tridentate, tetradentate, pentadentate, or hexadentate ligands in combination with other ligands; M may be coordinated to other ligands.

[0050] In some embodiments of the compound, M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some embodiments, M is Ir or Pt.

[0051] In some embodiments of the compound, X 1 , X 2 , X 3 , and X 4 At least one of the groups is nitrogen.

[0052] In some embodiments of the compounds, R 1 is tert-butyl or substituted tert-butyl. In some embodiments of the compound, R 1 and R 2 form an aromatic ring, which may be further substituted.

[0053] In some embodiments of the above compounds, Ring B is phenyl.

[0054] In some embodiments of the compounds, the ligand L A is selected from the group consisting of: [ka] In the formula, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and any two substituents may be bonded to form a ring.

[0055] In some embodiments of the compounds, the ligand L A is a L based on the structure represented by Formula II below A1 ~L A260 , [ka] (In the formula, R 1 , R 2 , R 4 , and R 5 is defined as shown below) [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] L based on the structure represented by Formula III below A261 ~L A520 , [ka] (In the formula, R 1 , R 9 , R 10 , and Y are defined as shown below) [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] L based on the structure of Formula IV below A521 ~L A780 , [ka] (In the formula, R 1 , R 11 , R 12 , and X are defined as shown below) [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] L based on the structure of Formula IV below A781 ~L A1170 , [ka] (In the formula, R 1, R 2 , R 11 , and R 12 is defined as shown below) [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24] [Table 25] [Table 26] L based on the structure of Formula V below A1171 ~L A1266 , [ka] (In the formula, R 1 , R 2 , R 13 , and X are defined as shown below) [Table 27] [Table 28] [Table 29] L based on the structure of Formula VI below A1267 ~L A1298 , [ka] (In the formula, R 1 , R 2 , and R 14 is defined as shown below) [Table 30] [Table 31] R B1 ~R B23 has the following structure: [ka] R A1 ~R A51 has the following structure: [ka] [ka] is selected from the group consisting of:

[0056] In some embodiments of the compound, the compound has the formula (L A ) n Ir(L B ) 3-n wherein L B is a bidentate ligand and n is 1, 2, or 3.

[0057] In some embodiments of the compounds, L B is selected from the group consisting of: [ka] [ka]

[0058] L A L A1 ~LA1298 The formula Ir(L A )(L B In some embodiments of the compound having the formula Ir(L), the compound is selected from the group consisting of Compound 1 through Compound 22,066, wherein each compound x has the formula Ir(L Ak )2(L Bj ) and In the formula, x=1298j+k−1298, k is an integer from 1 to 1298, j is an integer from 1 to 17, and L B1 ~L B17 is defined as follows: [ka] [ka]

[0059] According to another embodiment, the ligand L of formula I A Disclosed is a composition comprising a compound comprising:

[0060] According to another aspect, a first device is disclosed that includes a first OLED comprising an anode, a cathode, and a ligand L represented by Formula I: A and an organic layer containing a compound comprising: [ka] Formula I In the formula, ring B represents a 5- or 6-membered aromatic ring, and R 3 represents the maximum number of substitutions from no substitutions, and X 1 , X 2 , X 3 , and X 4 are each independently CR or N, (1)X 1 , X 2 , X 3 , and X 4 at least two adjacent ones of are C—R and are fused to form a 5- or 6-membered aromatic ring; or (2)X1 , X 2 , X 3 , and X 4 at least one of is nitrogen, or (3) Both (1) and (2) are true, (a)R 1 is CR 11 R 12 R 13 or R 2 to form a ring, or (b)R 2 is not hydrogen, or (c) Both (a) and (b); R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 any two of the substituents may be joined to form a ring; L A is coordinated to the metal M, L A may contain tridentate, tetradentate, pentadentate, or hexadentate ligands in combination with other ligands; M may be coordinated to other ligands.

[0061] In some embodiments of the first device, the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0062] In some embodiments of the first device, the organic layer further comprises a host, wherein the host is selected from Host Group A defined above.

[0063] In some embodiments of the first device, the organic layer further comprises a host, and the host comprises a metal complex.

[0064] In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0065] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. 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 having 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 having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0066] According to another aspect, an emissive region in an OLED is disclosed, the emissive region comprising a ligand L represented by Formula I: A The compound includes: [ka] Formula I In the formula, ring B represents a 5- or 6-membered aromatic ring, and R 3 represents the maximum number of substitutions from no substitutions, and X 1 , X 2 , X 3 , and X 4 are each independently CR or N, (1)X 1 , X 2 , X 3 , and X 4 at least two adjacent ones of are C—R and are fused to form a 5- or 6-membered aromatic ring; or (2)X 1 , X 2 , X 3 , and X 4 at least one of is nitrogen, or (3) Both (1) and (2) are true, (a)R 1 is CR 11 R 12 R 13 or R 2 to form a ring, or (b)R 2 is not hydrogen, or (c) Both (a) and (b); R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R 1 , R 2 , R 3 , R 11 , R 12 , and R 13 any two of the substituents may be joined to form a ring; L A is coordinated to the metal M, L A may contain tridentate, tetradentate, pentadentate, or hexadentate ligands in combination with other ligands; M may be coordinated to other ligands.

[0067] In some embodiments of the emissive region, the compound is an emissive dopant or a non-emissive dopant.

[0068] In some embodiments of the light-emitting region, the light-emitting region further comprises a host, wherein the host comprises at least one selected from the group consisting of a metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0069] In some embodiments of the light-emitting region, the light-emitting region further comprises a host, wherein the host is selected from Host Group A consisting of: [ka] [ka]

[0070] According to another aspect, a consumer product is disclosed that includes an OLED that includes a compound of the present disclosure in an organic layer of the OLED.

[0071] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF) (also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0072] According to another aspect, compositions comprising the compounds described herein are also disclosed.

[0073] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, while in other embodiments, the compound can be a non-emissive dopant.

[0074] 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 that has little charge transport function. In some embodiments, the host may include a metal complex. The host may be a triphenylene, including a benzo-fused thiophene or a benzo-fused furan. Any substituent in the host may independently be C n H 2n+1 , O.C. 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 H2n+1 , Ar1, Ar1-Ar2, and C n H 2n The host can be unsubstituted or can be a non-fused substituent selected from the group consisting of -Ar1, -Ar2, and -Ar3. In the above substituents, n can range from 1 to 10, and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound, such as ZnS, containing inorganic materials.

[0075] The host may be a compound containing 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. The host may include a metal complex. The host may be a specific compound selected from the group consisting of, but not limited to, the following: [ka] [ka] Additional information about possible hosts is provided below.

[0076] In yet another aspect of the present disclosure, there is provided a composition comprising the novel compounds disclosed herein, which can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, and an electron transport layer material disclosed herein. Combination with other materials

[0077] The materials described herein as useful for a particular layer in an organic light-emitting device can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in conjunction 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 can readily consult the literature to identify other materials that may be useful in combination.

[0078] Conductive dopants: The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and thereby its conductivity. The conductivity can be increased by generating charge carriers in the matrix material or, depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and n-type conductive dopants are used in the electron transport layer.

[0079] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references that disclose these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO 06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US2012146012 [ka] HIL / HTL:

[0080] The hole injection / transport material used in the embodiments of the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of such materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives; MoO x p-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0081] Examples of aromatic amine derivatives used in the HIL or HTL include, but are not limited to, the following general structures: [ka]

[0082] Ar 1 From Ar 9are a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indole, and aromatic heterocyclic compounds such as oxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and 2 to 10 cyclic structural units of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are bonded to each other directly or via at least one 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. Each Ar can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0083] In one embodiment, Ar 1 From Ar9 teeth, [ka] are independently selected from the group consisting of: where k is an integer from 1 to 20; X 101 From X 108 is C (including CH) or N; Z 101 is NAr 1 , O, or S; Ar 1 has the same radical as defined above.

[0084] Examples of metal complexes used in the HIL or HTL include, but are not limited to, those of the following general formula: [ka] where Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 are independently selected from C, N, O, P, and S; L 101 is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k'' is the maximum number of ligands that can be attached to the metal.

[0085] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. 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 is + For the / Fc couple, it has a minimum oxidation potential of less than about 0.6 V in solution.

[0086] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these 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 [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0087] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Blocking layers can also be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below. host:

[0088] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may also contain a host material that uses the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is higher than that of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

[0089] Examples of metal complexes used as host materials preferably have the following general formula: [ka] where Met is a metal; 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k'' is the maximum number of ligands that can be attached to the metal.

[0090] In one embodiment, the metal complex is: [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0091] In another embodiment, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0092] Examples of other organic compounds used as the host material include aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, and benzimidazoline. and aromatic heterocyclic compounds such as benzofuropyridine, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be the same or different groups and which are bonded to each other directly or via at least one 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. Each option in each group can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0093] In one embodiment, the host compound contains at least one of the following groups in the molecule: [ka] In the formula, R 101 From R 107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20; and k''' is an integer from 0 to 20. X 101 From X 108 is selected from C (including CH) or N. Z 101 and Z 102 is NR 101 , O, or S.

[0094] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these materials. EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR201301 15564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090 167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US201 2075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US201402 25088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO20 09066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO201212 8298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472

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[0095] One or more additional emitter dopants can be used together with the compound of the present disclosure.The example of the additional emitter dopant is not particularly limited, and any compound can be used as long as the compound is typically used as an emitter material.Suitable emitter materials include, but are not limited to, compounds that can generate light emission through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0096] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these 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, US 2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US73 32232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586 , US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO200201 5645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842 , WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO20 11044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO201317 4471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450,

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[0097] A hole-blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape from the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a 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 a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0098] In one embodiment, the compound used in the HBL comprises the same molecule as that used as the host described above.

[0099] In another embodiment, the compound used in the HBL contains at least one of the following groups in the molecule: [ka] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0100] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound typically used to transport electrons may be used. In one embodiment, the compound used in the ETL contains at least one of the following groups in the molecule: [ka] In the formula, R 101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as that of Ar mentioned above. 1 From Ar 3 has the same definition as that of Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 is selected from C (including CH) or N.

[0101] In another embodiment, the metal complex used in the ETL comprises, but is not limited to, the following general formula: [ka] where (ON) or (NN) is a bidentate ligand with the metal coordinated to atoms O, N or N, N; 101 is another ligand; and k' is an integer value between 1 and the maximum number of ligands that can be attached to the metal.

[0102] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these materials. CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2 005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, U S20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US20 11210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO20 09148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO 2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535. [ka] [ka] [ka] Charge generation layer (CGL)

[0103] In tandem or stacked OLEDs, the CGL plays a key role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. Consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, until the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductivity dopants used in the transport layers.

[0104] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specifically mentioned substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., can be their undeuterated, partially deuterated, and fully deuterated versions. Similarly, substituent classes, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., can be their undeuterated, partially deuterated, and fully deuterated versions. synthesis

[0105] All material syntheses and reactions were carried out under a nitrogen atmosphere unless otherwise noted. All solvents for reactions were anhydrous and used as obtained from commercial sources.

[0106] Compound 3393 [Ir(L A17 )2(L B5 )] synthesis

[0107] Synthesis of 6-(tert-butyl)-4-chloro-2H-pyran-2-one [ka] A solution of 6-(tert-butyl)-4-hydroxy-2H-pyran-2-one (9.50 g, 56.50 mmol), POCl (31.9 mL, 198 mmol), and NEt (7.8 mL, 56.50 mmol) was heated to reflux overnight. The reaction flask was cooled to room temperature, and the reaction mixture was quenched with ice and extracted with EtOAc. The crude product was adsorbed onto Celite and purified by flash chromatography (CHCl / EtOAc / heptane, 1:4:45) to give 6-(tert-butyl)-4-chloro-2H-pyran-2-one (10.0 g, 95%) as a golden oil.

[0108] Synthesis of 1-(tert-butyl)-3-chloronaphthalene [ka] A solution of 6-(tert-butyl)-4-chloro-2H-pyran-2-one (8.90 g, 47.70 mmol) in 1,2-dimethoxyethane (100 mL) was heated to 100 °C. Then, isoamyl nitrite (9.63 mL, 71.50 mmol), predissolved in 1,2-dimethoxyethane (60 mL), and 2-aminobenzoic acid (9.81 g, 71.50 mmol), predissolved in 1,2-dimethoxyethane (60 mL), were simultaneously added dropwise to the reaction mixture using an addition funnel. The reaction mixture was stirred at 100 °C overnight. The reaction flask was cooled to room temperature, and the reaction mixture was concentrated in vacuo. The crude product was adsorbed onto Celite and purified by flash chromatography (CH2Cl2 / EtOAc / heptane, 1:2:47) to give 1-(tert-butyl)-3-chloronaphthalene (6.7 g, 64%) as a pale yellow oil.

[0109] Synthesis of 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ka] A solution of 1-(tert-butyl)-3-chloronaphthalene (6.20 g, 28.30 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (9.36 g, 36.90 mmol), Pd(dba) (0.52 g, 0.57 mmol), SPhos (0.93 g, 2.27 mmol), and KOAc (8.35 g, 85.00 mmol) in 1,4-dioxane (90 mL) was heated to 110 °C for 17 h. After this time, the reaction flask was cooled to room temperature, and the reaction mixture was filtered through a plug of Celite, eluting with EtOAc, and concentrated in vacuo. The crude product was adsorbed onto Celite and purified by flash chromatography (EtOAc / heptane, 1:49 to 1:9) to give 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.80 g, 93%) as an off-white solid.

[0110] Synthesis of 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dichloroquinoline [ka] 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.31 g, 13.90 mmol), 2,4,5-trichloroquinoline (3.20 g, 13.76 mmol), KCO (5.71 g, 41.30 mmol), THF (51 mL), and HO (17 mL) were combined in a flask. The reaction mixture was purged with N for 15 minutes, after which Pd(PPh) (0.80 g, 0.69 mmol) was added. The reaction mixture was then heated at 75 °C for 16 hours. After this time, the reaction flask was cooled to room temperature, and the reaction mixture was extracted with EtOAc. The crude product was adsorbed onto Celite and purified by flash chromatography (EtOAc / heptane, 1:49) to give 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dichloroquinoline (5.50 g, 99%) as a yellow solid.

[0111] Synthesis of 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dimethylquinoline [ka] A solution of 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dichloroquinoline (5.50 g, 14.46 mmol), Pd(dba) (0.53 g, 0.58 mmol), SPhos (0.95 g, 2.31 mmol), trimethylboroxine (4.85 mL, 34.70 mmol), and KPO (12.28 g, 57.80 mmol) in toluene (65.0 mL) and HO (6.50 mL) was purged with N for 15 minutes and heated at 100 °C for 19 hours. After this time, the reaction flask was cooled to room temperature, and the reaction mixture was extracted with EtOAc. The crude product was adsorbed onto Celite and purified by flash chromatography (EtOAc / heptane, 1:99 to 1:49) followed by reverse-phase chromatography (MeCN / HO, 90:10 to 92 / 8 to 95 / 5) to give 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dimethylquinoline (3.50 g, 71%) as a white solid.

[0112] Synthesis of iridium(III) dimers [ka] 2-(4-(tert-butyl)naphthalen-2-yl)-4,5-dimethylquinoline (3.52 g, 10.36 mmol) was dissolved in 2-ethoxyethanol (42.0 mL) and water (14.0 mL), and the mixture was degassed with N for 15 minutes. Iridium(III) chloride tetrahydrate (1.28 g, 3.45 mmol) was then added, and the reaction mixture was heated to 105 °C under N for 16 hours. After this time, the reaction flask was cooled to room temperature. The reaction mixture was diluted with MeOH and filtered to give a dark brown precipitate, which was dried using a vacuum oven (1.94 g, 62%).

[0113] Compound 3393 [Ir(L A17 )2(L B5 )] synthesis [ka] A solution of iridium(III) dimer (1.00 g, 0.55 mmol) and 3,7-diethylnonane-4,6-dione (1.30 mL, 5.53 mmol) in 2-ethoxyethanol (18 mL) was degassed with N for 15 minutes. KCO (0.76 g, 5.53 mmol) was then added, and the reaction mixture was stirred under N for 21 hours at room temperature. After this time, the reaction mixture was filtered through a plug of Celite, eluting first with MeOH and then with CHCl using another filter flask. The collected filtrate was then concentrated in vacuo. The crude product was adsorbed onto Celite and purified by flash chromatography using CHCl / heptane (1:99 to 1:49 to 1:9) (pretreated with heptane / triethylamine, 9:1) to give compound 3393 [Ir(L)] as a red solid. A17 )2(L B5 )] (0.35 g, 29%) was obtained.

[0114] Compound 3899 [Ir(L A523 )2(L B5 )] synthesis Synthesis of 4-(4-(tert-butyl)naphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine [ka] 4-Chloro-7-isopropylthieno[3,2-d]pyrimidine (2.10 g, 9.87 mmol), 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.22 g, 10.4 mmol), K2CO3 (3.41 g, 24.7 mmol), DME (53 mL), and HO (18 mL) were combined in a flask. The reaction mixture was purged with N2 for 15 minutes, after which Pd(PPh3)4 (0.57 g, 0.49 mmol) was added. The reaction mixture was then heated at 75 °C under N2 overnight. After completion of the reaction, the reaction flask was cooled to room temperature, and the reaction mixture was extracted with EtOAc. The crude product was purified by flash chromatography (heptane / EtOAc, 9:1 to 4:1) to give 4-(4-(tert-butyl)naphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine (3.26 g, 92% yield).

[0115] Synthesis of iridium(III) dimers [ka] 4-(4-(tert-butyl)naphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine (3.16 g, 8.77 mmol) was dissolved in 2-ethoxyethanol (37 mL) and water (12 mL), and the mixture was degassed with N for 15 minutes. Iridium(III) chloride tetrahydrate (1.00 g, 2.70 mmol) was then added, and the reaction mixture was heated to 105 °C under N overnight. After this time, the reaction flask was cooled to room temperature. The reaction mixture was diluted with MeOH and filtered to give a green precipitate, which was dried using a vacuum oven (quantitative).

[0116] Compound 3899 [Ir(L A523 )2(L B5 )] synthesis [ka] A solution of iridium(III) dimer (1.50 g, 0.79 mmol) and 3,7-diethylnonane-4,6-dione (1.26 g, 5.94 mmol) in 2-ethoxyethanol (26 mL) was degassed with N for 15 minutes. KCO (0.82 g, 5.94 mmol) was then added, and the reaction mixture was stirred overnight at room temperature under N. After this time, the reaction mixture was filtered through a plug of Celite, eluting first with MeOH and then with CHCl using another filter flask. The collected filtrate was then concentrated in vacuo. The crude product was purified by flash chromatography using CHCl / heptane (1:4) (pre-treated with heptane / triethylamine, 9:1) to give compound 3899 [Ir(L)] as a red solid. A523 )2(L B5 )] (0.70 g, 79%) was obtained.

[0117] Compound 5975 [Ir(L A783 )2(L B5 )] synthesis

[0118] Synthesis of 3-fluoronaphthalen-2-ol [ka] (Bromodifluoromethyl)trimethylsilane (35.3 ml, 227 mmol) was added to a solution of 1,3-dihydro-2H-inden-2-one (20 g, 151 mmol) and tetrabutylammonium bromide (4.88 g, 15.13 mmol) in toluene (500 ml). The reaction was heated to 100°C and stirred for 2.5 hours. (Bromodifluoromethyl)trimethylsilane (35.3 ml, 227 mmol) was added and the reaction was stirred at 100°C for an additional 3 hours. The reaction was allowed to cool to room temperature and tetra-n-butylammonium fluoride (1 M in THF) (30.3 ml, 30.3 mmol) was added. The reaction was allowed to stir for ∼18 hours at room temperature. The reaction was poured into 1N HCl (aq) and extracted with EtOAc. 1N NaOH (aq) was added to the organic phase and the layers were separated. The aqueous phase was acidified by the addition of 1N HCl and extracted again with EtOAc. The organic phase was washed with brine, dried (MgSO4), and concentrated under reduced pressure. The crude product was purified by flash chromatography (isohexane to 20% EtOAc in isohexane) to give 3-fluoronaphthalen-2-ol (8.9 g, 54.9 mmol, 36% yield).

[0119] Synthesis of 3-fluoronaphthalen-2-yl trifluoromethanesulfonate [ka] TfO (11.1 mL, 65.9 mmol) was added to a solution of 3-fluoronaphthalen-2-ol (8.90 g, 54.9 mmol) and EtN (9.2 mL, 65.9 mmol) in DCM (200 mL) at 0 °C. The reaction was stirred at this temperature for 1.5 h. The reaction was quenched by the addition of saturated aqueous NaHCO, and the mixture was extracted with DCM (×2). The combined organic extracts were dried (MgSO) and concentrated under reduced pressure. The crude product was purified by flash chromatography (isohexane to 10% EtOAc in isohexane) to give 3-fluoronaphthalen-2-yl trifluoromethanesulfonate (13.3 g, 82% yield) as a colorless oil.

[0120] Synthesis of 2-(3-fluoro-naphthalen-2-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane [ka] PdCl(dppf)-CHCl adduct (2.50 g, 3.06 mmol) was added to a degassed solution of 3-fluoronaphthalen-2-yltrifluoromethanesulfonate (18 g, 61.2 mmol), bis(pinacolato)diboron (46.6 g, 184 mmol), and potassium acetate (18 g, 184 mmol) in dioxane (200 mL). The reaction was heated to reflux for 2 hours and then allowed to cool to room temperature. The reaction was partitioned between EtOAc and water, and the layers were separated. The organic phase was dried (MgSO) and concentrated under reduced pressure to give the crude material. The crude material was filtered through a silica pad and washed with DCM. The filtrate was concentrated under reduced pressure to give a mixture of 2-(3-fluoro-naphthalen-2-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane and bis(pinacolato)diboron ( 1 H NMR evidence). Synthesis of (3-fluoronaphthalen-2-yl)boronic acid [ka] Concentrated HCl (153 mL, 1837 mmol) was added to a solution of crude 2-(3-fluoro-naphthalen-2-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane and bis(pinacolato)diboron mixture (50 g) in IPA (400 mL). The reaction flask was heated to reflux for ~18 hours. The reaction flask was allowed to cool to room temperature, and most of the IPA was removed under reduced pressure. The resulting precipitate was filtered. The precipitate was purified by flash chromatography (4 / 1 to 1 / 1 isohexane / EtOAc) and recrystallization from IPA / water. A total of three batches were obtained by recrystallization. The filtrate from the first recrystallization yielded additional material upon prolonged standing / slow evaporation. Similarly, a third batch was obtained from this second recrystallization. All batches were taken up in MeOH, combined, and concentrated under a stream of nitrogen. After drying in a vacuum oven for 3 days, 7.1 g of (3-fluoronaphthalen-2-yl)boronic acid / 2-(1-fluoronaphthalen-2-yl)-4,6-bis(3-fluoronaphthalen-2-yl)-1,3,5,2,4,6-trioxatriborinate was obtained in 50% yield over two steps.

[0121] Synthesis of 4-(3-fluoronaphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine [ka] A 250 mL RBF was charged with 4-chloro-7-isopropylthieno[3,2-d]pyrimidine (3.0 g, 14.1 mmol), (3-fluoronaphthalen-2-yl)boronic acid (2.95 g, 15.5 mmol), potassium carbonate (4.87 g, 35.3 mmol), Pd(PPh3)4 (0.49 g, 0.42 mmol), THF (53 mL), and water (18 mL), degassed with nitrogen, and heated to reflux at 70 °C overnight. The reaction mixture was cooled to room temperature and washed with brine. The organic layer was dried over sodium sulfate, filtered, and concentrated. The crude product was purified by flash chromatography (EtOAc / heptane, 1:19) to give 4-(3-fluoronaphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine (4.20 g, 92% yield) as a viscous oil that slowly crystallized on standing. Further purification was achieved by recrystallization from MeOH.

[0122] Synthesis of Ir(III) dimer [ka] 4-(3-Fluoronaphthalen-2-yl)-7-isopropylthieno[3,2-d]pyrimidine (2.35 g, 8.77 mmol) was dissolved in 2-ethoxyethanol (30 mL) and water (10 mL) in a flask. The reaction was purged with nitrogen for 15 minutes, and then iridium(III) chloride tetrahydrate (0.90 g, 2.43 mmol) was added. The reaction was heated overnight under nitrogen in a water bath set at 105 °C. The reaction was allowed to cool, diluted with MeOH, and the precipitate was filtered with MeOH and then dried in a vacuum oven for 2 hours to give 2.1 g of a dark red solid (98% yield), which was used directly in the next step.

[0123] Compound 5975 [Ir(L A783 )2(L B5 )] synthesis [ka] The dimer (1.00 g, 0.57 mmol), 3,7-diethylnonane-4,6-dione (0.92 g, 4.31 mmol), and 2-ethoxyethanol (19 mL) were combined in a flask. The reaction was purged with nitrogen for 15 minutes, and then potassium carbonate (0.60 g, 4.31 mmol) was added. The reaction was stirred overnight at room temperature under nitrogen. The reaction was diluted with MeOH, and the solid was filtered through Celite. The precipitate was collected using DCM. The solid was purified by flash chromatography (heptane / DCM, 4:1 to 3:1) to give compound 5975 [Ir(L)] as a red solid. A783 )2(L B5 )] (0.70 g, 58% yield).

[0124] Compound 6040 [Ir(L A848 )2(L B5 )] synthesis

[0125] Synthesis of 7-isopropyl-4-(3-methylnaphthalen-2-yl)thieno[3,2-d]pyrimidine [ka] 4-Chloro-7-isopropylthieno[3,2-d]pyrimidine (3.0 g, 14.1 mmol), (4,4,5,5-tetramethyl-2-(3-methylnaphthalen-2-yl)-1,3,2-dioxaborolane (3.86 g, 14.4 mmol), potassium carbonate (4.87 g, 35.3 mmol), DME (75 mL), and water (25 mL) were combined in a flask. The reaction was purged with nitrogen for 15 minutes, after which Pd(PPh) (0.489 g, 0.423 mmol) was added. was added. The reaction was heated to reflux in a water bath under nitrogen overnight. The reaction mixture was extracted with EtOAc. The organic phase was washed twice with brine, dried over sodium sulfate, filtered, and concentrated to a brown solid. The brown solid was purified using flash chromatography (heptane / EtOAc / DCM, 18:1:1 to 16:3:1) to give 7-isopropyl-4-(3-methylnaphthalen-2-yl)thieno[3,2-d]pyrimidine (3.50 g, 78% yield) as a white solid.

[0126] Synthesis of Ir(III) dimer [ka] 7-Isopropyl-4-(3-methylnaphthalen-2-yl)thieno[3,2-d]pyrimidine (2.93 g, 9.21 mmol), 2-ethoxyethanol (54 mL), and water (18 mL) were combined in a flask. After purging the reaction with nitrogen for 15 minutes, iridium(III) chloride tetrahydrate (1.05 g, 2.83 mmol) was added. The reaction was heated in a water bath at 105 °C under nitrogen overnight. The reaction was allowed to cool to room temperature, diluted with MeOH, and the precipitate was filtered with MeOH and then dried in a vacuum oven for 2 hours to give 2.2 g of a dark red solid (90% yield), which was used directly in the next step.

[0127] Compound 6040 [Ir(L A848 )2(L B5 )] synthesis [ka] The dimer (2.20 g, 1.28 mmol), 3,7-diethylnonane-4,6-dione (2.71 ml, 12.8 mmol), and 2-ethoxyethanol (30 ml) were combined in a flask. The reaction was purged with nitrogen for 15 minutes, after which potassium carbonate (1.76 g, 12.8 mmol) was added. The reaction was stirred at room temperature under nitrogen over the weekend. The reaction was diluted with MeOH, and the dark reddish-brown solid was filtered through Celite. The precipitate was collected using DCM to give a reddish-brown solid. This solid was purified by flash chromatography (75 / 15 / 10 heptane / DCM / EtN, followed by heptane / DCM (pretreated from 19:1 to 17:3) to give 1.10 g of a red solid. This solid was dissolved in DCM, MeOH was added, and the mixture was partially concentrated on a rotovap with a bath temperature of 30 °C. The precipitate was filtered and dried in a vacuum oven overnight to give compound 6040 [Ir(L)] as a red solid. A848 )2(L B5 )] (0.94 g, 36%) was obtained.

[0128] Synthesis of comparative compound 1

[0129] Synthesis of 4,5-dichloro-2-(3-methylnaphthalen-1-yl)quinoline [ka] 2,4,5-Trichloroquinoline (3.05 g, 13.1 mmol), 4,4,5,5-tetramethyl-2-(3-methylnaphthalen-1-yl)-1,3,2-dioxaborolane (3.87 g, 14.4 mmol), and potassium carbonate (5.44 g, 39.4 mmol) were placed in a flask. THF (98 mL) and water (33 mL) were then added, and the reaction mixture was degassed with nitrogen gas for 15 minutes. Pd(PPh3)4 (0.60 g, 0.53 mmol) was added, and the reaction was heated to reflux overnight. Upon completion, water was added, and the mixture was extracted with ethyl acetate. The crude material was purified by column chromatography using a mixture of heptane / ethyl acetate / DCM (90 / 5 / 5) as the solvent system. The product was then triturated with methanol followed by heptane to afford 3.30 g (74% yield) of the title compound.

[0130] Synthesis of 4,5-dimethyl-2-(3-methylnaphthalen-1-yl)quinoline [ka] 4,5-Dichloro-2-(3-methylnaphthalen-1-yl)quinoline (3.10 g, 9.17 mmol), Pd2(dba)3 (0.17 g, 0.18 mmol), SPhos (0.30 g, 0.73 mmol), and potassium phosphate (5.84 g, 27.5 mmol) were placed in a flask. Toluene (56 mL) and water (6 mL) were added, followed by the addition of 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinate (3.1 mL, 22.0 mmol) via syringe. The reaction mixture was degassed with nitrogen for 15 minutes and then heated to reflux overnight. Upon completion, water was added to the mixture, which was then extracted with ethyl acetate. The crude material was purified by column chromatography using heptane / ethyl acetate (90 / 10) as the solvent system. The product still contained 0.45% impurity and was again purified by column chromatography using heptane / ethyl acetate (95 / 5) as the solvent system to give the title compound as a white solid (2.35 g, 86% yield).

[0131] Synthesis of Ir(III) dimer TIFF2026004547000110.tif351704,5-Dimethyl-2-(3-methylnaphthalen-1-yl)quinoline (2.387 g, 8.03 mmol), 2-ethoxyethanol (39 mL), and water (13 mL) were combined in a flask. The mixture was purged with nitrogen for 15 minutes, then iridium(III) chloride tetrahydrate (0.85 g, 2.29 mmol) was added, and the reaction was heated at 105°C overnight under nitrogen. The mixture was cooled to room temperature, diluted with MeOH, and the precipitate was filtered to give 1.00 g (53% yield) of the dimer.

[0132] Synthesis of comparative compound 1 [ka] Ir(III) dimer (1.00 g, 0.61 mmol), 3,7-diethylnonane-4,6-dione (1.44 mL, 6.09 mmol), and 2-ethoxyethanol (20 mL) were combined in a flask. The reaction was purged with nitrogen for 15 minutes, after which potassium carbonate (0.84 g, 6.09 mmol) was added. The reaction was stirred at room temperature overnight. Methanol was added to the mixture, and the precipitate was filtered through a Celite pad. The solid on the Celite was then washed with DCM, and the product was collected in a filter flask. The collected product was solubilized in DCM and filtered through a silica pad. The product was then triturated with MeOH and recrystallized with DCM / EtOH to give 0.85 g (70% yield) of the desired product. experiment

[0133] Device Example

[0134] All example devices were fabricated by high-vacuum (<10-7 Torr) thermal evaporation. The anode electrode was 1150 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) and 1000 Å Al. All devices were immediately encapsulated with a glass lid sealed with epoxy resin in a nitrogen glove box (H2O and O2 <1 ppm) after fabrication, and a moisture getter was included in the package. The organic stack for the device example consisted of, from the ITO surface, a 100 Å HATCN hole-injection layer (HIL), a 450 Å HTM hole-transport layer (HTL), a 400 Å emissive layer (EML) containing Compound H as the host, 18% stabilizing dopant (SD), and either Comparative Compound 1 or Compounds 3393, 3899, 5975, or 6040 as the emitter (3%), and a 350 Å Liq (8-hydroxyquinoline lithium) doped with 40% ETM as the ETL. The emitters were selected to achieve the desired color, efficiency, and lifetime. SD was added to the electron-transporting host to facilitate positive charge transport in the emissive layer. A comparative device was fabricated in the same manner as the device example, except that Comparative Compound 1 was used as the emitter in the EML. Figure 1 shows a schematic device structure. Table 1 lists the device layer thicknesses and materials. The chemical structures of the device materials are shown below. [ka]

[0135] The device performance data are summarized in Table 2. Comparative Compound 1 exhibited a maximum emission wavelength (λmax) of 640 nm. The compounds of the present invention, i.e., compounds 3,393, 3,899, and 5,975, were designed to be blue-shifted relative to Comparative Compound 1 and exhibited better external quantum efficiency (EQE). Compound 6,040 was designed to be red-shifted. To obtain better device performance, different naphthalene positional isomers were used. We obtained peak wavelengths of 604 to 628 nm for the compounds of the present invention. Meanwhile, Compound 6,040 was red-shifted relative to Comparative Compound 1, which had a peak wavelength of 653 nm. The full width at half maximum (FWHM) was also significantly improved with the configuration of the present invention, with the compounds of the present invention exhibiting an FWHM of 0.76 to 0.74 compared to 1.00 for Comparative Compound 1. Compound 6,040 was slightly broader at 1.10. Furthermore, to fix the desired naphthalene orientation relative to the iridium in the final material, a bulky side chain (t-butyl, cycloalkyl, etc.) at the 4-position of the naphthyl moiety or optional substitution at the 3-position is required. The combination of naphthyl positional isomers combined with the side chain allows for the excellent performance of the compounds of the present invention. The EQEs are much higher for the compounds of the present invention, ranging from 1.20 to 1.51 in relative terms. [Table 32] [Table 33]

[0136] It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the present invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that various theories as to why the invention works are not intended to be limiting. [Prior art documents] [Patent documents]

[0137] [Patent Document 1] U.S. Patent No. 5,844,363 [Patent Document 2] U.S. Patent No. 6,303,238 [Patent Document 3] U.S. Patent No. 5,707,745 [Patent Document 4] U.S. Patent No. 7,279,704 [Explanation of symbols]

[0138] 100 Organic Light-Emitting Devices 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron Blocking Layer 135 Light-emitting layer 140 Hole Blocking Layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 cathode 162 First conductive layer 164 Second Conductive Layer 170 Barrier Layer 200 Inverted OLED, device 210 Substrate 215 cathode 220 Light-emitting layer 225 Hole transport layer 230 Anode

Claims

1. Ligand L represented by formula I: Ａ A composition comprising a compound comprising: 【Chemistry 1】 Formula I (Wherein, ring B represents a 5- or 6-membered aromatic ring, R ３ represents the maximum number of substitutions from no substitutions, X １ , X ２ , X ３ , and X ４ are each independently CR or N; (1) X ３ , and X ４ is CR and is fused to a 5- or 6-membered aromatic ring; or (2) X １ , X ２ , X ３ , and X ４ is nitrogen; or (3) Both (1) and (2), (a) R １ is CR １１ R １２ R １３ or R ２ to form a ring, or (b) R ２ is not hydrogen, or (c) both (a) and (b); R, R １ , R ２ , R ３ , R １１ , R １２ , and R １３ are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R １ , R ２ , R ３ , R １１ , R １２ , and R １３ any two of the substituents may be joined to form a ring; L Ａ is coordinated to the metal M, L Ａ may contain tridentate, tetradentate, pentadentate, or hexadentate ligands in combination with other ligands; M may be coordinated to another ligand, The compound is not Compound C8 below. 【Chemistry 2】

2. 2. The composition of claim 1, wherein M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu, or M is Ir or Pt.

3. 2. The composition of claim 1, wherein M is Ir or Pt.

4. X １ , X ２ , X ３ , and X ４ 2. The composition of claim 1, wherein at least one of is nitrogen.

5. R １ The composition of claim 1, wherein is tert-butyl or substituted tert-butyl.

6. R １ and R ２ The composition of claim 1 , wherein: forms an aromatic ring, said aromatic ring being optionally further substituted.

7. R ２ 10. The composition of claim 1, wherein is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, and combinations thereof.

8. The composition of claim 1, wherein ring B is phenyl.

9. The ligand L Ａ 2. The composition of claim 1, wherein is selected from the group consisting of: 【Transformation 3】 (In the formula, R １ , R ２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , and R １４ are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents may be joined to form a ring; X is S or O, and Y is C or N.

10. The ligand L Ａ 2. The composition of claim 1, wherein is selected from the group consisting of: L based on the structure of Formula III below Ａ２６１ ~L Ａ５２０ , 【Chemistry 4】 (In the formula, R １ , R ９ , R １０ , and Y are defined as shown below) Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 L based on the structure of Formula IV below Ａ５２１ ~L Ａ７８０ , 【Transformation 5】 (In the formula, R １ , R １１ , R １２ , and X are defined as shown below) Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 L based on the structure of Formula IV below Ａ７８１ ~L Ａ１１７０ , 【Transformation 6】 (In the formula, R １ , R ２ , R １１ , and R １２ is defined as shown below) Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 L based on the structure of Formula V below Ａ１１７１ ~L Ａ１２６６ , 【Transformation 7】 (In the formula, R １ , R ２ , R １３ , and X are defined as shown below) Table 22 Table 23 Table 24 L based on the structure of Formula VI below Ａ１２６７ ~L Ａ１２９８ , 【Transformation 8】 (In the formula, R １ , R ２ , and R １４ is defined as shown below) Table 25 Table 26 R Ｂ１ ~R Ｂ4 , R Ｂ６ ~R Ｂ８ , and R Ｂ１０ has the following structure: 【Chemistry 9】 R Ａ３ and R Ａ３４ has the following structure: 【Chemistry 10】

11. The compound has the formula (L Ａ ) ｎ Ir(L Ｂ ) ３－ｎ The composition of claim 1 having (In the formula, L Ｂ is a bidentate ligand, n is 1, 2, or 3.

12. L Ｂ 12. The composition of claim 11, wherein said compound is selected from the group consisting of: 【Chemistry 11】

13. The composition is selected from the group consisting of Compound 1 to Compound 22,066, wherein each compound x is of formula Ir(L Ａｋ ) ２ (L Ｂｊ ) In the formula, x=1298j+k−1298, k is an integer from 1 to 1298, j is an integer from 1 to 17, and L Ｂ１ ~L Ｂ１７ The composition of claim 10, wherein is defined as follows: 【Chemistry 12】 【Chemistry 13】

14. an anode; a cathode; an organic layer comprising the composition of claim 1 disposed between the anode and the cathode.

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