Organic electroluminescent materials and devices

Abstract

This application relates to organic electroluminescent materials and devices. The invention includes novel heterocyclic materials suitable for use as blue phosphorescent materials in OLED devices. The novel materials include two fused 5-membered aromatic or pseudoaromatic rings that combine with a 6-membered aromatic ring to act as chelating ligands for transition metals. The novel materials are computationally determined to have suitable triplet energies for use as blue emitters and have sufficient chemical stability for use in devices.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 62 / 501,134, filed May 4, 2017, the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials. For instance, the wavelength of light emitted by an organic emitting layer can often be easily tuned using appropriate dopants.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in U.S. Patents 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0006] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suited to emitting specific colors (called "saturated" colors). Specifically, these standards require pixels saturated with red, green, and blue light. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates, well-known in the field.

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

[0008]

[0009] In this figure and the figures below, we depict the coordinate bonds between nitrogen and the metal (Ir in this case) as straight lines.

[0010] As used herein, the term "organic" includes both polymeric materials and small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist of a series of chemical shells built on the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small-molecule emitter. Dendritic polymers can be "small molecules," and all dendritic polymers currently used in the OLED field are considered small molecules.

[0011] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "above" the second layer, the first layer is placed further away from the substrate. Unless specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "above" the anode.

[0012] As used herein, “solution-handleable” means capable of dissolving, dispersing or transporting in and / or depositing from a liquid medium in the form of a solution or suspension.

[0013] When a ligand is considered to directly contribute to the photosensitivity of the emissive material, the ligand may be referred to as "photosensitive." When a ligand is considered not to contribute to the photosensitivity of the emissive material, the ligand may be referred to as "auxiliary," but auxiliary ligands can alter the properties of photosensitizing ligands.

[0014] As used herein, and as will generally be understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) level is "greater than" or "higher than" the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, the LUMO levels of a material are higher than the HOMO levels of the same material. "Higher" HOMO or LUMO levels appear to be closer to the top of this diagram than "lower" HOMO or LUMO levels.

[0015] As used herein, and as will generally be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0016] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0017] There is a need in the art for novel heterocyclic materials suitable for use as blue phosphorescent materials in OLED devices. This invention addresses this need in the art. Summary of the Invention

[0018] According to one embodiment, a compound is provided having the structure of Formula I shown below:

[0019]

[0020] Where A is a fused ring system containing a six-membered ring, which is fused to a five-membered ring, and the five-membered ring is fused to a second five-membered ring;

[0021] Where B is a five- or six-membered carbon ring or a heterocyclic ring;

[0022] A and B are connected by a single key;

[0023] Where R A and R B Each can be used independently to represent a single substitution up to the maximum possible number of substitutions, or no substitution.

[0024] Where R A and R B Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof;

[0025] Where M is a metal with an atomic weight greater than 40;

[0026] A is coordinated to M via a non-carbabenine coordinate bond;

[0027] B is coordinated to M via polar covalent bonds;

[0028] M is bonded to one of the five-membered rings of A;

[0029] Where L is a substituted or unsubstituted cyclometalated ligand, and each L can be the same or different; and

[0030] Where m is at least 1, and m+n is the maximum number of ligands that can be attached to M.

[0031] According to another embodiment, an organic light-emitting diode / device (OLED) is also provided. The OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a compound of formula I. According to yet another embodiment, the organic light-emitting device is incorporated into one or more devices selected from: consumer products, electronic component modules, and / or lighting panels.

[0032] According to yet another embodiment, a formulation is provided that contains a compound of formula I. Attached Figure Description

[0033] Figure 1 An organic light-emitting device is shown.

[0034] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated. Detailed Implementation

[0035] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. When electrons and holes are localized on the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When excitons relax via photoemission mechanisms, light is emitted. In some cases, excitons may be localized on excimers or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0036] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs within timeframes of less than 10 nanoseconds.

[0037] Recently, OLEDs with emitting materials that emit light from the triplet state (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, Vol. 395, 151-154, 1998 (“Baldo-I”); and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Applied Physics Letters, Vol. 75, 3, 4-6 (1999) (“Baldo-II”), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0038] Figure 1An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0039] Further examples of each of these layers are available. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0040] Figure 2An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 Provide an example of how some layers can be omitted from the structure of device 100.

[0041] Figure 1 and 2 The simple layered structures illustrated herein are provided by way of non-limiting examples, and it should be understood that embodiments of the invention can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can 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 should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emitter layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of the different organic materials mentioned above.

[0042] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example, as described in, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can be deviated from... Figure 1 and 2The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0043] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition via a mask, cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and OVJD. Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handleability than those with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0044] Devices manufactured according to embodiments of the present invention may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in an environment including moisture, vapor, and / or gases. The barrier layer may be deposited on, under, or beside a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase 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 comprise a mixture of polymeric and non-polymeric materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For the process to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited and / or deposited simultaneously under the same reaction conditions. The weight ratio of polymeric to non-polymeric materials can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0045] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes the compounds of this disclosure in an organic layer. The consumer product should include any type of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (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 comprising multiple tiled displays, theater or stadium screens, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to the invention. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18 to 30 degrees Celsius, and more preferably at room temperature (20-25 degrees Celsius), but can be used outside this temperature range (e.g., -40 to +80 degrees Celsius).

[0046] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can utilize the materials and structures described herein. More generally, organic devices such as organic transistors can utilize the materials and structures described herein.

[0047] As used herein, the terms “halogen,” “halogen,” or “halogen group” include fluorine, chlorine, bromine, and iodine.

[0048] As used herein, the term "alkyl" encompasses both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl group may optionally be substituted.

[0049] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Preferred cycloalkyl groups are those containing 3 to 10 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may optionally be substituted.

[0050] As used herein, the term "alkenyl" encompasses both straight-chain and branched alkenyl groups. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl groups may optionally be substituted.

[0051] As used herein, the term "alkynyl" encompasses both straight-chain and branched alkynyl groups. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0052] As used herein, the terms “aralkyl” or “arylalkyl” are used interchangeably and cover alkyl groups having aromatic groups as substituents. Additionally, aralkyl groups may optionally be substituted.

[0053] As used herein, the term "heterocyclic group" encompasses both aromatic and non-aromatic cyclic groups. Aromatic heterocyclic groups also refer to heteroaryl groups. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 or 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolidinyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Furthermore, the heterocyclic group may optionally be substituted.

[0054] As used herein, the term "aryl" or "aromatic group" encompasses both monocyclic groups and polycyclic systems. A polycyclic system may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic; for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, etc. Perylene and azulene, preferably phenyl, biphenyl, biphenylene, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.

[0055] As used herein, the term "heteroaryl" encompasses a monocyclic heteroaromatic group that may include one to five heteroatoms. The term "heteroaryl" also includes polycyclic heteroaromatic systems having two or more rings shared by two adjacent rings (the rings being "fused"), wherein at least one of the rings is a heteroaryl, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole-carbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazole Phosphorus, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selelenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and its aza analogues. Additionally, the heteroaryl group may optionally be substituted.

[0056] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0057] As used in this article, "substituted" means that a substituent other than H is bonded to the relevant position, such as carbon. Therefore, for example, in R... 1 When replaced by a single unit, then an R 1 It must not be H. Similarly, in R... 1 When replaced by two, then the two Rs 1 It must not be H. Similarly, in R... 1 When not replaced, R 1 It is hydrogen for all available locations.

[0058] The term "aza" in the fragments described herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in each fragment can be substituted with nitrogen atoms. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0059] It should be understood that when a molecular fragment is described as a substituent or additionally linked to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linked fragments are considered equivalent.

[0060] The compounds of the present invention

[0061] This invention includes novel heterocyclic materials suitable for use as blue phosphorescent materials in OLED devices. The novel materials comprise two fused 5-membered aromatic or pseudoaromatic rings, which are bonded to a 6-membered aromatic ring to act as chelating ligands for a transition metal. The novel materials are computationally determined to have suitable triplet energies for use as blue light emitters and sufficient chemical stability for device applications.

[0062] In one aspect, the present invention comprises compounds of formula I:

[0063]

[0064] Where A is a fused ring system containing a six-membered ring, which is fused to a five-membered ring, and the five-membered ring is fused to a second five-membered ring;

[0065] Where B is a five- or six-membered carbon ring or a heterocyclic ring;

[0066] A and B are connected by a single key;

[0067] Where R A and R B Each can be used independently to represent a single substitution up to the maximum possible number of substitutions, or no substitution.

[0068] Where R A and R B Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof;

[0069] Where M is a metal with an atomic weight greater than 40;

[0070] A is coordinated to M via a non-carbabenine coordinate bond;

[0071] B is coordinated to M via polar covalent bonds;

[0072] M is bonded to one of the five-membered rings of A;

[0073] Where L is a substituted or unsubstituted cyclometalated ligand, and each L can be the same or different; and

[0074] Where m is at least 1, and m+n is the maximum number of ligands that can be attached to M.

[0075] In one embodiment, R A and R B Each is independently selected from the group consisting of: hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.

[0076] In one embodiment, B is a six-membered aromatic ring. In another embodiment, B is benzene.

[0077] In one embodiment, M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In another embodiment, M is either Ir or Pt.

[0078] In one embodiment, the compound is homogamic. In another embodiment, the compound is heterogamic.

[0079] In one embodiment, the M-fused ring system is selected from the group consisting of:

[0080]

[0081] Where C is a six-membered aromatic ring;

[0082] Where R 1 Indicates single substitution to the maximum possible number of substitutions, or no substitution;

[0083] Each X is independently selected from the following groups: O, S, Se, NR, CRR', SiRR', BR, and PR;

[0084] Where R 1R and R' are each independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof;

[0085] Where R 1 Any adjacent substituents in R and R' may optionally join or fuse to form a ring; and the dashed lines represent bonds to ring B.

[0086] In one embodiment, R 1 R and R' are each independently selected from the group consisting of: hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof.

[0087] In one embodiment, X is NR. In one embodiment, X is selected from the group consisting of O, S, and Se. In one embodiment, X is selected from the group consisting of CRR', SiRR', BR, and PR.

[0088] In one embodiment, the ring C contains at least five carbon atoms.

[0089] In one embodiment, the compound comprises a structure selected from the group consisting of:

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[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] In one embodiment, each L is independently selected from the following group:

[0214]

[0215]

[0216] Where Y 1 To Y 13 Each group is independently selected from the groups composed of carbon and nitrogen;

[0217] Y' is selected from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f RR, SiR e R f and GeR e R f ;

[0218] Where R e and R f Optional fusion or joining to form a ring;

[0219] Where R a R b R c and R d Each can independently represent a single substituent up to the maximum possible number of substitutions or no substitutions;

[0220] Where R a R b R c R d Re and R f Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and

[0221] Where R a R b R c and R d Any two adjacent substituents may optionally fuse or join to form a ring or a polydentate ligand.

[0222] In one embodiment, each L is independently selected from the following group:

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240] In one embodiment, each L is independently selected from the following group:

[0241]

[0242]

[0243] According to another aspect of this disclosure, an OLED is also provided. The OLED includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer may include a compound of formula I and its variants as described herein.

[0244] In some embodiments, the OLED has one or more features 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 including carbon nanotubes.

[0245] In some embodiments, the OLED further comprises a layer including a delayed phosphor emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. 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 at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0246] In some embodiments, the present invention relates to an emission region or emission layer. The emission region or emission layer may include the compounds of the present invention. In one embodiment, the compounds of the present invention are emission dopants or non-emission dopants.

[0247] In some embodiments of the emission region, the emission region further comprises a body, wherein the body comprises at least one selected from the group consisting of: metal complexes, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azir-triphenylene, azir-carbazole, azir-dibenzothiophene, azir-dibenzofuran, and azir-dibenzoselenene.

[0248] In some embodiments of the launch region, the launch region further includes a body, wherein the body is selected from the group consisting of:

[0249]

[0250]

[0251] And its combinations.

[0252] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may produce emission via phosphorescence, fluorescence, and thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0253] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0254] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels.

[0255] In one embodiment, the consumer product is selected from the group consisting of: flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and signs.

[0256] The organic layer may be an emission layer, and the compound may be an emission dopant in some embodiments, while in other embodiments it may be a non-emission dopant. In one embodiment, the organic layer further comprises a host, wherein the host comprises a metal complex.

[0257] The organic layer may further include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) bipolar, b) electron transport, c) hole transport, or d) wide bandgap material that plays a minimal role in charge transport. In some embodiments, the host may include a metal complex. The host may be triphenylene containing benzofused thiophene or benzofused furan. Any substituent in the host may be a non-fused substituent independently selected from the group consisting of: C n H 2n+1 OC n H 2n+1 ,OAr1,N(C n H 2n+1 2. N(Ar1)(Ar2), CH=CH-C n H 2n+1 C≡CC nH 2n+1 Ar1, Ar1-Ar2 and C n H 2n -Ar1, or the host is unsubstituted. In the aforementioned 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 their heteroaromatic analogs. The host can be an inorganic compound. For example, an inorganic material containing Zn, such as ZnS.

[0258] The host may be a compound containing at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenene. The host may include metal complexes. The host may be (but is not limited to) specific compounds selected from the group consisting of:

[0259]

[0260]

[0261] And its combination.

[0262] The following provides additional information about possible subjects.

[0263] In another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: solvents, carriers, hole injection materials, hole transport materials, and electron transport layer materials.

[0264] Combination with other materials

[0265] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a wide variety of other materials present in the device. For example, the emission dopants disclosed herein can be used in combination with a wide variety of possible host layers, transport layers, blocking layers, injection layers, electrodes, and other layers. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0266] Conductive dopants:

[0267] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by creating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0268] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein in OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0269]

[0270] HIL / HTL:

[0271] The hole injection / transport materials used in this invention are not particularly limited, and any compound can be used, as long as the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, such as MoO x p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0272] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures:

[0273]

[0274] Ar 1 To Ar 9 Each of these is selected from: groups composed of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, etc. Perylene and azurite; groups composed of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, cinnamon, quinazoline, quinoline Oxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenepyridine, and selelenophenedipyridine; and groups consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each Ar may be unsubstituted or may be substituted by substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof.

[0275] In one aspect, Ar 1 To Ar 9 Choose independently from the following groups:

[0276]

[0277] Where k is an integer from 1 to 20; X 101 To X 108 It is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 It has the same functional groups as defined above.

[0278] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0279]

[0280] Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P, and S; L 101It is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0281] In one aspect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. In another aspect, (Y) 101 -Y 102 Met is a carbapenem ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In yet another aspect, the metal complex possesses properties compared to Fc. + The minimum oxidation potential in solution with / Fc coupling is less than about 0.6V.

[0282] Non-limiting examples of HIL and HTL materials in OLEDs that can be used in combination with the materials disclosed herein are illustrated below, along with references to those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] EBL:

[0291] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0292] main body:

[0293] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as the light-emitting material, and may contain a host material using a metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used, as long as the triplet energy of the host is greater than that of the dopant. Any host material can be used with any dopant, as long as the triplet criterion is satisfied.

[0294] Examples of metal complexes used as the host preferably have the following general formula:

[0295]

[0296] Where Met is a metal; (Y) 103 -Y 104) is a bidentate ligand, Y 103 and Y 104 Independently selected from C, N, O, P, and S; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0297] In one respect, metal complexes are:

[0298]

[0299] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0300] In the other case, Met is selected from Ir and Pt. In the other case, (Y 103 -Y 104 ) is a carbaene ligand.

[0301] Examples of organic compounds used as the host are selected from groups composed of aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fenene, fluorene, pyrene, etc. Perylene and azurite; groups composed of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, cinnamon, quinazoline, quinoline Oxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenepyridine, and selelenophenedipyridine; and groups consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each choice in each group may be unsubstituted or may be substituted by substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof.

[0302] In one aspect, the host compound contains at least one of the following groups in its molecule:

[0303]

[0304] Where R 101 To R 107 Each of these groups is independently selected from the following groups: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to that of Ar mentioned above; k is an integer from 0 to 20 or from 1 to 20; k'" is an integer from 0 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0305] Z 101 and Z 102 Selected from NR 101 、O or S.

[0306] Non-limiting examples of material combinations disclosed herein used as host materials in OLEDs are illustrated below, along with references to those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280 965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966 , US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001 446. US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO20050 89025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO200 9066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO 2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,

[0307]

[0308]

[0309]

[0310]

[0311]

[0312] Other projectiles:

[0313] One or more other emitter dopants may be used in conjunction with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used, provided that the compound is commonly used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0314] Non-limiting examples of emitter materials in OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR201200 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,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。、

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321] HBL:

[0322] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0323] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as those used in the subject described above.

[0324] In another aspect, the compounds used in HBL contain at least one of the following groups in their molecules:

[0325]

[0326] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0327] ETL:

[0328] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, provided it is typically used for electron transport.

[0329] In one aspect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0330]

[0331]

[0332] Where R 101Ar is selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, which, when aryl or heteroaryl, have a similar definition to Ar as described above. 1 To Ar 3 It has a similar definition to Ar mentioned above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0333] In another aspect, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0334]

[0335] Wherein (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N, or N,N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to the metal.

[0336] Non-limiting examples of ETL materials that can be used in OLEDs with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US20 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0337]

[0338]

[0339]

[0340] Charge generation layer (CGL)

[0341] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0342] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms can be partially or fully deuterated. Therefore, any specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., can be in their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0343] experiment

[0344] Synthesis of L10 dimer

[0345]

[0346] Using a stir bar, 3-phenylbenzi[d]imidazole[5,1-b]thiazole (3.99 g, 15.94 mmol) and iridium(III) chloride tetrahydrate (2.56 g, 6.92 mmol) were added to a 250 mL flask. The reaction mixture was heated to reflux overnight. The mixture was then cooled to room temperature and MeOH was added. The solid was collected in glass frit to give a white solid (5.0 g, 99%). 1 H NMR (cd2cl2, 400MHz): d 8.68 (s, 1H), 7.59 (d, 1H), 7.24 (m, 1H), 7.12 (m, 1H), 6.95 (m, 2H), 6.82 (m, 1H), 6.48 (m, 1H), 6.08 (m, 1H).

[0347] Synthesis of L10 cations

[0348]

[0349] Iridium dimer (473 mg, 0.326 mmol) and side-oxygenated ((trifluoromethyl)sulfonyl)silver (167 mg, 0.651 mmol) were added to a 100 mL flask using a stir bar. DCM (3 mL) and NCCH3 (0.4 mL) were then added, and the solution was stirred at room temperature for several hours. After several hours, the solvent was removed under vacuum. The material was dissolved in DCM, and the solution was filtered through diatomaceous earth. The filtrate was pumped to give a white solid (540 mg, 90%). 1 H NMR (cd2cl2, 400MHz): d 9.18 (s, 1H), 8.19 (d, 1H), 7.85 (d, 1H), 7.68–7.48 (non-overlapping signal, 2H), 7.15 (m, 1H), 6.90 (t, 1H), 6.61 (t, 1H), 6.20 (d, 1H), 1.55 (br s, 6H).

[0350] Synthesis of L10 mixed complexes

[0351]

[0352] Reactant 1 (89.7 mg, 0.098 mmol) and 9-fluoro-3,3,4,4-tetramethyl-2-phenyl-3,4-dihydrodibenzo[b,ij]imidazole[2,1,5-de]quinazine (77 mg, 0.195 mmol) were added to a 25 mL Schlenk tube using a stir bar and circulated along the line via three vacuum / nitrogen backfill cycles. Ethoxyethanol (2 mL) was added, and the reactants were degassed for 10 min. The reactants were heated to 135 °C overnight. The reactants were cooled to room temperature, and saturated Na₂CO₃ / water and DCM were added. The aqueous layer was extracted three times with DCM. The organic layers were combined, dried over MgSO₄, and coated onto diatomaceous earth. Purification by normal-phase chromatography (solvent 1:1 heptane:dichloromethane) yielded a yellow solid (36 mg, 30%). LCMS: 1228.3 m / z 1 ¹H NMR (dmso-d6, 400MHz): d 8.44 (d, 1H), 8.42 (d, 1H), 7.96 (m, 1H), 7.87 (d, 1H), 7.73 (m, 1H), 7.71 (s, 1H), 7.70-7.54 (overlapping signal, 6H), 7.51-7.39 (m, 2H), 7.11 (t, 1H), 6.8 (br signal, 3H), 6.85 (dd, 1H), 6.75 (td, 1H), 6.58 (br m, 2H), 6.42 (td, 1H), 6.28 (dd, 1H), 6.21 (m, 2H), 6.14 (br m, 2H), 5.96 (tt, 1H), 1.35-0.68 (non-overlapping signal, 24H). 19 F NMR(cd2cl2,376.5MHz):d-111.3(m,1F),-111.9(m,1F). λ max (2-MeTHF,PMMA): 452nm.

[0353] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. A compound of formula I Equation I, The compound described herein comprises a structure selected from the group consisting of: Where L is ; Where Y 1 To Y 9 Each is carbon independently; Where R a R b and R c Each can independently represent a single substituent up to the maximum possible number of substitutions or no substitutions; Where R a Each is independently selected from the following groups: hydrogen, deuterium, halogen, C. 1-15 Alkyl, C 3-10 cycloalkyl, C 6-30 Aryl groups and their combinations; Where R b and R c Each is independently selected from the following groups: hydrogen, deuterium, halogen, C. 1-15 Alkyl, C 3-10 cycloalkyl groups and combinations thereof; Where R a and R b Two adjacent substituents fused or joined to form a ring; Where M is Ir; and Where m is at least 1, and m+n is the maximum number of ligands that can be attached to M.

2. The compound according to claim 1, wherein each L is independently selected from the group consisting of: 。 3. An organic light-emitting device (OLED), comprising: anode; cathode; and An organic layer disposed between the anode and the cathode, comprising the compound according to claim 1 or 2.

4. The OLED of claim 3, wherein the organic layer is an emission layer, and the compound is an emission dopant or a non-emission dopant.

5. The OLED of claim 3, wherein the organic layer further comprises a body, wherein the body comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azitene, azicarbazole, azitene-dibenzothiophene, azitene-dibenzofuran, and azitene-dibenzoselenene.

6. The OLED of claim 3, wherein the organic layer further comprises a body, wherein the body is selected from the group consisting of: , , , , , , , , , , , , , , , , , , , , , , and their combinations.

7. A consumer product including an organic light-emitting device (OLED), said organic light-emitting device comprising: anode; cathode; and An organic layer disposed between the anode and the cathode, comprising the compound according to claim 1 or 2.

8. The consumer product of claim 7, wherein the consumer product is selected from the group consisting of: flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and signs.

9. A formulation comprising the compound according to claim 1 or 2.

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