Organic electroluminescent materials and devices

Abstract

To provide a composition containing a first compound capable of functioning as a phosphorescent emitter in an OLED.SOLUTION: A first compound has at least one aromatic ring and at least one substituent R bonded directly to one of the at least one aromatic ring. Each substituent R is represented by the following formula: (a) G1 is selected from NR1, SiR1R2, GeR1R2, alkyl, cycloalkyl and combinations thereof; G2 is a non-aromatic polycyclic group; (b) G1 is a direct bond; G2 is a non-aromatic spiro polycyclic group; or (c) G1 is selected from a direct bond, NR1, SiR1R2, GeR1R2, alkyl, cycloalkyl and combinations thereof; G2 is a non-aromatic polycyclic group; R is bonded directly to phenyl, pyridine, or triazine. R1, R2 and R3 are various substituents. Compounds and devices such as OLED containing the first compound are also described.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 62 / 213,757 filed September 3, 2015; U.S. Provisional Patent Application No. 62 / 232,194 filed September 24, 2015; U.S. Provisional Patent Application No. 62 / 291,960 filed February 5, 2016; U.S. Provisional Patent Application No. 62 / 322,510 filed April 14, 2016; and U.S. Provisional Patent Application No. 62 / 330,412 filed May 2, 2016, which are incorporated by reference in their entirety.

[0002] Cross-reference of related applications The claimed invention was made in the interest of and / or in connection with one or more of the directors of the following parties to a university-company joint research agreement: the University of Michigan, Princeton University, the University of Southern California, and Universal Display Corporation. This agreement was in effect prior to the date on which the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of this agreement.

[0003] The present invention relates to compounds for use as light-emitting materials, and to devices such as organic light-emitting diodes containing such compounds. [Background technology]

[0004] Organic optoelectronic devices 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 to offer a cost advantage over inorganic devices. In addition, due to the inherent properties of organic materials, such as flexibility, they can be 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 photocells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials. For example, the wavelength of light emitted by the organic light-emitting layer can generally be easily adjusted with appropriate dopants.

[0005] OLEDs utilize a thin organic film that emits light when a voltage is applied to the entire device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in Patent Documents 1, 2, and 3, which are incorporated herein by reference in their entirety.

[0006] One application of phosphorescent molecules is in 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. Conventional liquid crystal displays emit light from a white backlight, which is filtered using absorption filters to produce red, green, and blue light. Similar techniques can be used with OLEDs. White OLEDs can be either a single EML device or a stacked structure. Color can be measured using CIE coordinates, which are well known in the art.

[0007] An example of a green light-emitting molecule is shown below: [ka] This is tris(2-phenyl)iridium, represented as Ir(ppy)3, which has the following properties:

[0008] In these drawings and subsequent drawings in this specification, the inventors depict the coordination bond from nitrogen to a metal (here, Ir) as a straight line.

[0009] As used herein, the term “organic” includes polymer materials 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 molecule” can actually be quite large. Small molecules can contain repeating units in some contexts. For example, using long-chain alkyl groups as substituents does not exclude molecules from the “small molecule” class. Small molecules may be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of said backbone. Small molecules can also serve as the core portion of a dendrimer, which consists of a series of chemical shells constructed on a core portion. The core portion of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be “small molecules,” and all dendrimers currently used in the field of OLEDs are considered to be small molecules.

[0010] In this specification, “top” means the part furthest from the substrate, while “bottom” means the part closest to the substrate. When the first layer is described as being “placed on top of” the second layer, the first layer is located 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 being “placed on top of” the anode, even if there are various organic layers in between.

[0011] As used herein, “solution processable” means that it can be dissolved, dispersed or transported in any liquid medium, either in solution or suspension form, and / or deposited from said medium.

[0012] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the light-emitting material. A ligand may be referred to as "auxiliary" if it is not considered to contribute to the photoactive properties of the light-emitting material, although auxiliary ligands can alter the properties of photoactive ligands.

[0013] As will be generally understood by those skilled in the art when used herein, the first “highest occupied molecular orbital” (HOMO) or “lowest empty molecular orbital” (LUMO) energy level is “greater” or “higher” than the second HOMO or LUMO energy level, if the first energy level is close to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. “Higher” HOMO or LUMO energy levels appear to be closer to the top of such a diagram than “lower” HOMO or LUMO energy levels.

[0014] As will be generally understood by those skilled in the art when used herein, if the first work function has a higher absolute value, then the first work function is "greater" or "higher" than the second work function. Since work functions are generally measured as negative numbers relative to the vacuum level, this means that a "higher" work function is even more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being far away from the vacuum level in the downward direction. Thus, the definitions of the HOMO and LUMO energy levels follow a different convention than that of the work function.

[0015] Further details about OLEDs and the definitions described above can be found in Patent Document 4, which is incorporated herein by reference in its entirety.

Summary of the Invention

[0016] According to one embodiment, a composition comprising a first compound is provided. In the composition, the first compound can function as a phosphorescent emitter in an organic light-emitting device at room temperature, the first compound has at least one aromatic ring and at least one substituent R, and each of the at least one substituent R is directly bonded to one of the at least one aromatic ring. Each of the at least one substituent R has the following formula:

Chemical Formula

[0017] According to other embodiments, organic light-emitting diodes / devices (OLEDs) are also provided. The OLED may include an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer may include the first compound described herein. 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.

[0018] Further embodiments provide a formulation comprising the first compound described herein. [Brief explanation of the drawing]

[0019] [Figure 1] Figure 1 shows an organic light-emitting device.

[0020] [Figure 2] Figure 2 shows an inverted organic light-emitting device that does not have another electron transport layer. [Modes for carrying out the invention]

[0021] Generally, an OLED includes at least one organic layer positioned between the anode and cathode and electrically connected to them. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons move to the oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. Light is emitted via a photoemission mechanism when the exciton relaxes. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may occur, but these are generally considered undesirable.

[0022] Early OLEDs used light-emitting molecules ("fluorescent") that emitted light from their singlet state, as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated in its entirety by reference. Fluorescence emission generally occurs within a timeframe of less than 10 nanoseconds.

[0023] More recently, OLEDs with light-emitting materials that emit light from a triplet state ("phosphorescence") have been demonstrated. See, in their entirety, Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Vol. 395, pp. 151-154, 1998 ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, pp. 4-6 (1999) ("Baldo-II"). Phosphorescence is described in further detail in U.S. Patent No. 7,279,704, paragraphs 5-6, which is incorporated by reference.

[0024] Figure 1 shows an organic light-emitting device 100. The figure is not necessarily to a constant 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, a light-emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as examples of materials, are described in further detail in US7,279,704, sections 6-10, which are incorporated by reference.

[0025] Further examples are available for each of these layers. For example, flexible and transparent substrate-anode combinations are disclosed in U.S. Patent No. 5,844,363, which is incorporated in its entirety by reference. 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 2003 / 0230980, which is incorporated in its entirety by reference. Examples of luminescent and host materials are disclosed in Thompson et al., U.S. Patent No. 6,303,238, which is incorporated in its entirety by reference. 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 2003 / 0230980, which is incorporated in its entirety by reference. U.S. Patents 5,703,436 and 5,707,745, which are incorporated in their entirety by reference, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with a transparent, conductive, sputtered-deposited ITO layer covering it. The theory and use of blocking layers are described in more detail in U.S. Patents 6,097,147 and U.S. Patent Application Publication 2003 / 0230980, which are incorporated in their entirety by reference. An example of an injection layer is provided in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference. A description of a protective layer can be found in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference.

[0026] Figure 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 described layers in order. The most common OLED configuration has a cathode positioned above the anode, and since device 200 has a cathode 215 positioned below the anode 230, device 200 is sometimes referred to as an "inverted" OLED. The same materials described for device 100 may be used in the corresponding layers of device 200. Figure 2 provides an example of how some layers may be omitted from the structure of device 100.

[0027] The simple layered structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention may be used in relation to a wide variety of other structures. The specific materials and structures described are substantially illustrative, and other materials and structures may be used. Functional OLEDs may be realized 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. Many of the examples provided herein describe various layers as containing a single material, but it is understood that combinations of materials, such as host and dopant mixtures, or more generally, mixtures, may be used. Furthermore, 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, the hole transport layer 225 transports holes and injects them into the light-emitting layer 220, and may be described as a hole transport layer or hole injection layer. In one embodiment, the OLED may be described as having an “organic layer” positioned between the cathode and the anode. The organic layer may consist of a single layer or may further consist of multiple layers of different organic materials, as described, for example, with respect to Figures 1 and 2.

[0028] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of polymer materials, as disclosed in U.S. Patent No. 5,247,190 by Friend et al., which is incorporated in whole by reference. Further examples include OLEDs having a single organic layer. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 by Forrest et al., which is incorporated in whole by reference. OLED structures may deviate from the simple layered structures illustrated in Figures 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 by Forrest et al., which is incorporated in whole by reference, and / or a recessed structure as described in U.S. Patent No. 5,834,893 by Bulovic et al.

[0029] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal deposition, such as those described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference; inkjet deposition; organic vapor deposition (OVPD), such as those described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated by reference; and organic vapor jet printing (OVJP), such as those described in U.S. Patent No. 7,431,968, which are incorporated by reference. Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal deposition. Preferred patterning methods include those described in U.S. Patents No. 6,294,398 and No. 6,468,819, which are incorporated in whole by reference, as well as patterning related to some deposition methods such as inkjet and OVJD. Other methods may be used. The material to be deposited may be modified to suit a particular deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbon atoms, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbon atoms may be used, with 3 to 20 carbon atoms 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.

[0030] 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 on, below, or next to the substrate, electrodes, or on any other part of the device, including edges. The barrier layer may consist of a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include single-phase and multi-phase compositions. 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 polymer and non-polymer materials as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For a material to be considered a "mixture," the polymer and non-polymer materials constituting the barrier layer must be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymer material to non-polymer material can be in the range of 95:5 to 5:95. The polymer and non-polymer materials can be made from the same precursor material. In one example, a mixture of polymer and non-polymer materials essentially consists of polymer silicon and inorganic silicon.

[0031] Devices fabricated 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 electrical products or intermediate components. Such electrical products or intermediate components include display screens and lighting devices (such as discrete light source devices or lighting panels) that can be used by end-user product manufacturers. Such electronic component modules may optionally include drive electronics and / or power supplies. Devices fabricated according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more incorporated electronic component modules (or units). Such consumer products include any type of product that includes one or more light sources and / or one or more types of display devices. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and / or lights for signal transmission, 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, 3-D displays, cars, large-area walls, theater or stadium screens, or billboards. Devices fabricated according to the present invention can be controlled using various control mechanisms, including passive matrices and active matrices. While most devices are intended for use within a human-comfortable temperature range, such as 18 to 30 degrees Celsius, more preferably room temperature (20 to 25 degrees Celsius), they can also be used outside this temperature range, for example, from -40 to +80 degrees Celsius.

[0032] 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 these materials and structures. More generally, organic devices such as organic transistors may use these materials and structures.

[0033] In the field of organic chemistry, polycyclic compounds are organic compounds characterized by closed rings of several atoms, mainly carbon. These ring substructures include cycloalkanes, aromatics, and other ring types. These compounds are three or more atoms in size and consist of combinations of linkages including tethering (e.g., biaryls), condensation (edge-to-edge in anthracenes and steroids), single-atom linkage (e.g., spiro compounds), and linkages involving bridging rings such as adamantane. While "poly" literally means "many," in this specification, polycyclic compounds also include those with fewer rings, such as bicyclic, tricyclic, and tetracyclic compounds.

[0034] In this specification, the terms "halo," "halogen," or "halide" include fluorine, chlorine, bromine, and iodine.

[0035] In this specification, the term "alkyl" means both linear and branched alkyl groups. Preferred alkyl groups include those containing 1 to 15 carbon atoms, such as 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 substituted.

[0036] In this specification, the term "cycloalkyl" means a cyclic alkyl group. Preferred cycloalkyl groups include those containing 3 to 10 ring carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl. Furthermore, the cycloalkyl groups may be substituted.

[0037] In this specification, the term "alkenyl" means both linear and branched alkenyl groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl groups may be substituted.

[0038] In this specification, the term "alkynyl" means both linear and branched alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be substituted.

[0039] In this specification, the terms "aralkyl" and "arylalkyl" are interchangeable and mean alkyl groups having aromatic groups as substituents. Furthermore, the aralkyl groups may be substituted.

[0040] In this specification, the term “heterocyclic group” means aromatic and non-aromatic ring groups. A heteroaromatic ring group also means a heteroaryl group. Preferred heterononaromatic ring groups are at least one heteroatom containing 3 to 7 ring atoms 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] In this specification, the terms “aryl” or “aromatic group” mean monocyclic and polycyclic systems. A polycyclic system may have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are “condensed”), at least one of which is aromatic, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6 carbon atoms, 10 carbon atoms, or 12 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthlene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl group may be substituted.

[0042] In this specification, the term “heteroaryl” means a monocyclic heteroaromatic group that may contain 1 to 5 heteroatoms. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are co-located by two adjacent rings (the rings are “condensed”), at least one of which is a heteroaryl, and for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups contain 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, oxathiaidine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, and Examples include nzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzoflopyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, with dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azavolin, 1,3-azavolin, 1,4-azavolin, borazine, and aza analogs thereof. Furthermore, the heteroaryl group may be substituted.

[0043] The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl atoms 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, phosphinol, and combinations thereof.

[0044] In this specification, "substituted" indicates that a substituent other than H is bonded to a related position such as carbon. Therefore, for example, R 1 If R is a one-substitution, 1 It must be something other than H. Similarly, R 1 If R is a disubstituted, 1 Two of them must be other than H. Similarly, R 1 If R is unsubstituted, 1 It is hydrogen at all substitution positions.

[0045] In this specification, the term "aza" in fragments such as aza-dibenzofuran and aza-dibenzothiophene means that one or more CH groups in each fragment can be replaced by nitrogen atoms. For example, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline, without limiting it. Those skilled in the art will readily conceive of other nitrogen analogs of the aza derivatives described above, and all such analogs are intended to be encompassed by the terms used herein.

[0046] When a molecular fragment is described as a substituent or as being attached to another part, it should be understood that its name may be written as either the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the whole molecule (benzene, naphthalene, dibenzofuran). In this specification, even if the substituent or attached fragment is described differently, these are considered equivalent.

[0047] According to one embodiment, a composition comprising a first compound is described. In the composition, the first compound can function as a phosphorescent emitter in an organic light-emitting device at room temperature, and the first compound has at least one aromatic ring and at least one substituent R, each of which substituent R is directly bonded to one of the at least one aromatic rings. Each of the at least one substituent R is given by the following formula: [ka] It is represented as, (a)G 1 , NR 1 , SiR 1 R 2 , GeR 1 R 2 Selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; G 2 is a non-aromatic polycyclic group, and has one or more R 3 It can be further replaced by; (b)G 1 It is a direct bond; G 2 is a non-aromatic spiropolycyclic group, and has one or more R 3 It can be further replaced by; or (c)G 1 Direct coupling, NR 1 , SiR 1 R 2 , GeR 1 R 2 Selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; G 2 is a non-aromatic polycyclic group, and has one or more R3 It can be further substituted; R is directly bonded to an aromatic ring selected from the group consisting of phenyl, pyridine, and triazine, and can be further condensed with other rings; R 1 , R 2 , and R 3 These are 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, phosphine, and combinations thereof; G 1 and G 2 Each of these may be independently, partially, or completely deuterated.

[0048] In some embodiments, G 1 is, SiR 1 R 2 In some embodiments, G 1 , NR 1 In some embodiments, G 1 is alkyl. In some such embodiments, G 1 The compound is selected from the group consisting of divalent methyl, ethyl, propyl, and butyl. In some embodiments, G 1 It is completely or partially deuterated.

[0049] In some embodiments, G 2 It is a polycyclic alkyl. In some embodiments, G 2 It is a carborane. In some embodiments, G 2 It contains at least one heteroatom. In some embodiments, G 2 It contains at least one heterocyclic group.

[0050] In some embodiments, the first compound can emit light from a triplet excited state to a ground singlet state at room temperature.

[0051] In some embodiments, the first compound is a metal-coordinate complex having a metal-carbon bond. In some such embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some such embodiments, the metal is Ir, and in other embodiments, the metal is Pt.

[0052] In some embodiments, the first compound is M(L 1 ) x (L 2 ) y (L 3 ) z It is expressed by the following formula: L 1 , L 2 , and L 3 They can be the same or different; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x+y+z represents the oxidation state of metal M; L 1 , L 2 , and L 3 Each of these is independently selected from the following group: [ka] [ka] [ka] X 1 ~X 17 Each is independently selected from the group consisting of carbon and nitrogen; X is selected from the group consisting of BR’, NR’, PR’, O, S, Se, C=O, S=O, SO2, CR’R’’, SiR’R’’, and GeR’R’’; R’ and R’’ may each independently condense or combine to form a ring; R a 、R b 、R c 、and R d each independently represents mono-substitution to the maximum number of possible substitutions or no substitution; R’, R’’, R a 、R b 、R c 、and R d are each 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; R a 、R b 、R c 、and R d Any two adjacent substituents of may condense or combine to form a ring or form a polydentate ligand; Said R a 、R b 、R c 、and R d At least one of includes said at least one substituent R.

[0053] In some embodiments where the first compound is represented by the structure M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments, the first compound is represented by the formula Ir(L 1 )2(L 2 ). In some such embodiments, L 1It is expressed as an expression selected from the group consisting of the following: [ka] L 2 The formula is as follows: [ka] It is represented as follows. In some such embodiments, L 2 It is expressed by the following formula: [ka] In the formula, R e , R f , R h , and R i These are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; R e , R f , R h , and R i At least one of them has at least two carbon atoms; R g This is 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.

[0054] The first compound is the Ir(L 1 )2(L 2 In some embodiments represented by the formula, ligand L 1 and L 2 These are different and are independently selected from the following groups. [ka] [ka]

[0055] The first compound is the Ir(L 1 )2(L 2 In some embodiments represented by the formula, ligand L 1 and L 2 Each of these is independently selected from the following group: [ka]

[0056] The first compound is M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments represented by the structure, the first compound is Pt(L 1 )2 or Pt(L 1 )(L 2 The formula is given by the first compound Pt(L 1 )2 or Pt(L 1 )(L 2 In some embodiments represented by the formula, one L 1 is, other L 1 It combines with, or L 2 It combines with it to form a tetradentate ligand.

[0057] The first compound is M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments represented by the structure, R a , R b , R c , and R d At least one of these comprises a partially or completely deuterated alkyl group or cycloalkyl group.

[0058] In some embodiments, G 2The following group is selected: [ka]

[0059] In some embodiments, the at least one substituent R is independently selected from the group consisting of the following: [ka] [ka] [ka]

[0060] The first compound is M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments represented by the structure, L 1 , L 2 , and L 3 At least one of these is selected from the group consisting of the following: [ka] [ka]

[0061] The first compound is the Ir(L 1 )2(L 2 In some embodiments represented by the formula, ligand L 1 and L 2 These are different and are independently selected from the following groups. [ka]

[0062] The first compound is M(L1 ) x (L 2 ) y (L 3 ) z In some embodiments represented by the formula, ligand L 1 The structure is as follows: [ka] L represented by A And, as shown below, L A1 ~L A2480 It is selected from the group consisting of the following. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0063] L1 is L A In some embodiments, the compound is compound x selected from the group consisting of compound 1 to compound 2,120,400, and compound x is of the formula Ir(L Ai )(L Bj ) is represented by 2, x = 2480j + i - 2480, i is an integer between 1 and 2,480. j is an integer between 1 and 855. L Bj The structure is as follows: [ka] Based on this, the results are shown in the table below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0064] In some embodiments, the first compound may be a luminescent dopant. In some embodiments, the compound may generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as type E delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0065] In other aspects of the present disclosure, an organic light-emitting device (OLED) is disclosed, comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode, comprising a first compound. The first compound can function as a phosphorescent emitter in the OLED at room temperature, and the first compound has at least one aromatic ring and at least one substituent R, each of which substituent R is directly bonded to one of the at least one aromatic rings. Each of the at least one substituent R is given by the following formula: [ka] It is represented as, (a)G 1 , NR 1 , SiR 1 R 2 , GeR 1 R 2Selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; G 2 is a non-aromatic polycyclic group, and has one or more R 3 It can be further replaced by; (b)G 1 It is a direct bond; G 2 is a non-aromatic spiropolycyclic group, and has one or more R 3 It can be further replaced by; or (c)G 1 Direct coupling, NR 1 , SiR 1 R 2 , GeR 1 R 2 Selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; G 2 is a non-aromatic polycyclic group, and has one or more R 3 It can be further substituted; R is directly bonded to an aromatic ring selected from the group consisting of phenyl, pyridine, and triazine, and can be further condensed with other rings; R 1 , R 2 , and R 3 These are 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, phosphine, and combinations thereof; G 1 and G 2 Each of these may be independently, partially, or completely deuterated.

[0066] The OLEDs disclosed herein can be incorporated into one or more consumer products, electronic component modules, and lighting panels. The organic layer may be an emissive layer, and in some embodiments, the compound may be an emissive dopant, and in other embodiments, the compound may be a non-emissive dopant.

[0067] The organic layer may also contain 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 bandgap material with little to no charge transport role. In some embodiments, the host may contain a metal complex. The host may be a triphenylene containing a benzo-condensed thiophene or a benzo-condensed furan. Any substituent in the host may independently be C n H 2n+1 , OC n H 2n+1 ,OAr1,N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, and C n H 2n -Ar1 can be a non-condensed substituent selected from the group consisting of Ar1, or the host can be unsubstituted. In the substituents described above, 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. Examples include Zn-containing inorganic materials such as ZnS.

[0068] The host may be a compound comprising 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, but is not limited to, a specific compound selected from the group consisting of the following. [ka] [ka] Additional information regarding possible hosts is provided below.

[0069] Other aspects of this disclosure describe formulations comprising the first compound. The formulation may include one or more components selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, and electron transport layer materials disclosed herein. Combination with other materials

[0070] Materials described herein as useful for specific layers in organic light-emitting devices may be used in combination with a wide variety of other materials present in the device. For example, the light-emitting dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other possible layers. 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 easily consult the literature to identify other materials that may be useful in combination. Conductive dopants:

[0071] Charge transport layers are doped with conductive dopants, significantly altering the density of charge carriers and thereby changing their conductivity. Conductivity is increased by generating charge carriers in the matrix material or, depending on the type of dopant, and changes in the Fermi level of the semiconductor can also be achieved. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0072] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO 06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US2012146012 [ka] HIL / HTL:

[0073] 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 materials include: phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; MoO x This includes, but is not limited to, metal oxide derivatives such as; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonnitrile; metal complexes; and crosslinkable compounds.

[0074] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the general structures shown below. [ka]

[0075] Ar 1 From Ar 9Each of these is 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, oxathiaidine, oxadiazine, indole, benzimidazole, indazole, and A group consisting of aromatic heterocyclic compounds such as xazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzophropyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenofenodipyridine; and a group consisting of 2 to 10 cyclic structural units that are the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and which are bonded to each other directly or via at least one of an oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit, and aliphatic cyclic group. Each Ar can be unsubstituted, or it can be 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, phosphinol, and combinations thereof.

[0076] In one aspect, Ar 1 From Ar9 teeth, [ka] They are independently selected from the group consisting of [the specified elements]. In the formula, 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 It has the same base as defined above.

[0077] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formulas. [ka] In the formula, Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 k' is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal; and k'+k'' is the maximum number of ligands that can adhere to the metal.

[0078] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os and Zn. In a further embodiment, the metal complex is Fc + For the / Fc couple, it has a minimum oxidation potential of less than approximately 0.6V in solution.

[0079] 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 the literature disclosing 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] EBL:

[0080] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons emitted from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the light-emitting element 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 embodiment, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below. host:

[0081] 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 greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

[0082] Examples of metal complexes used as host materials preferably have the following general formula. [ka] In the formula, Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 is independently selected from C, N, O, P and S; L 101 k' is another ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal; and k'+k'' is the maximum number of ligands that can adhere to the metal.

[0083] In one embodiment, the metal complex is the following complex. [ka] In the formula, (ON) is a bidentate ligand having a metal coordinated to atoms O and N.

[0084] In another embodiment, Met is selected from Ir and Pt. In a further embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0085] Other organic compounds used as hosts include the group of 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, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiaidine, oxadiazine, indole, benzimidazole The group consists of aromatic heterocyclic compounds such as indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzophropyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenofenodipyridine; and the group consists of 2 to 10 cyclic structural units that are the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and are bonded to each other directly or via at least one of an oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and aliphatic cyclic group. Each option in each group may be unsubstituted, or may be 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, phosphinol, and combinations thereof.

[0086] In one embodiment, the host compound contains at least one of the following groups in its molecule. [ka] In the formula, R 101 From R 107 Each 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, phosphinol, and combinations thereof, and if it is aryl or heteroaryl, it has the same definition as 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 From X 108 This is selected from C (including CH) or N. Z 101 and Z 102 is NR 101 Selected from O, or S.

[0087] Non-limiting examples of host materials that can be used in OLEDs in combination with the host compounds disclosed herein are exemplified below, along with the literature disclosing 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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[0088] One or more additional luminescent dopants may be used in conjunction with the compounds of this disclosure. The additional luminescent dopants are not particularly limited, and any compound commonly used as a luminescent material may be used. Suitable luminescent materials include, but are not limited to, compounds capable of generating light through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination thereof.

[0089] Non-limiting examples of light-emitting materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing 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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[0090] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons emitting from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the light-emitting material closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more hosts closest to the HBL interface.

[0091] In one embodiment, the compound used in the HBL contains the same molecule as the one used as the host described above.

[0092] In another embodiment, the compound used in the HBL contains at least one of the following groups in its molecule. [ka] In the formula, k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0093] An electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer 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, as long as it is typically used for electron transport.

[0094] In one embodiment, the compound used in the ETL contains at least one of the following groups in its molecule. [ka] TIFF0007872387000229.tif22152 formula, R 101 Ar 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, phosphinol, and combinations thereof, and if it is aryl or heteroaryl, it has the same definition as Ar mentioned above. 1 From Ar 3 It has the same definition as Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 This is selected from C (including CH) or N.

[0095] In another embodiment, the metal complex used in the ETL may include, but is not limited to, the following general formulas. [ka] In the formula, (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N, or N, N; L 101 ' is another ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal.

[0096] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing 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)

[0097] In tandem or stacked OLEDs, the transport layer (CGL) plays a crucial role in performance, consisting 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 electrodes. The consumed electrons and holes in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually stabilizes. Typical CGL materials include n-type and p-type conductive dopants used in the transport layer.

[0098] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms may be partially or completely deuterated. Therefore, any specifically mentioned substituents, such as but not limited to methyl, phenyl, and pyridyl, can be in non-deuterated, partially deuterated, and fully deuterated versions. Similarly, classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, and heteroaryl, can also be in non-deuterated, partially deuterated, and fully deuterated versions. [Examples]

[0099] Example of synthesis Synthesis Example 1 Synthesis of 8-(4-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzoflo[2,3-b]pyridine [ka] 8-(4-chloropyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (4.75 g, 16.12 mmol) and [1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene](3-chloropyridyl)palladium(II) dichloride (PEPPSI-IPr) (1.094 g, 1.612 mmol) were added to a reaction flask with 50 mL of tetrahydrofuran (THF). The mixture was degassed with nitrogen and then stirred at room temperature (approximately 22°C). Bicyclo[2.2.1]heptan-2-yl zinc(II) bromide (97 ml, 48.3 mmol) was then added to the reaction mixture via syringe. Stirring was continued at room temperature for 18 hours. The reaction mixture was quenched with aqueous ammonium chloride solution and then extracted with ethyl acetate. The extract was dried over magnesium sulfate, filtered, and then concentrated under vacuum to reduce its volume. The solid was filtered from the obtained concentrate. The filtrate was passed through a silica gel column and eluted with 2.5% to 5% THF / dichloromethane (DCM). The clearest fractions were combined and concentrated under vacuum to obtain 8-(4-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (4 g, 11.28 mmol, yield 70.0%) as a viscous, pale yellow oil.

[0100] Synthesis of 8-(4-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzoflo[2,3-b]pyridine [ka] 8-(4-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (4 g, 11.28 mmol) was dissolved in 40 mL of THF. Dimethyl sulfoxide-d6 (37.9 g, 451 mmol) was added to the reaction mixture by syringe, and sodium tert-butoxide (0.542 g, 5.64 mmol) was added. The resulting mixture was stirred and heated in a bath set to 65°C for 20 hours. The reaction mixture was quenched with 80 mL of D2O. The mixture was extracted twice with 400 mL of ethyl acetate. The extracts were combined, washed with aqueous LiCl solution, and then dried over magnesium sulfate. The extracts were then filtered and concentrated under vacuum. The residue was passed through a 3 × 120 g silica gel column using 2.5% to 3.5% THF / DCM. From the clarified product fraction, 8-(4-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzoflo[2,3-b]pyridine (2.7 g, 7.53 mmol, yield 66.7%) was obtained.

[0101] Compound 1064460[Ir(L A540 )(L B430 )2] Synthesis [ka] As shown in the synthesis scheme above, 8-(4-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzofl[2,3-b]pyridine (2.6 g, 7.25 mmol) and iridium salt (3.28 g, 4.19 mmol) were placed in a reaction flask with ethanol (32 mL) and methanol (32 mL). The reaction mixture was degassed with nitrogen and then heated in an oil bath set to 70°C for 3 days. The oil bath temperature was then increased to 80°C and the reaction mixture was stirred for a further 2 days. After this, the reaction flask was cooled to room temperature (approximately 20°C). The mixture was filtered to isolate a yellow solid, which was dried under vacuum without heating. This solid was dissolved in toluene and pre-adsorbed on silica gel. This material was passed through a 6 × 125 g silica gel cartridge and purified using silica gel chromatography. It was then eluted with 0.7% to 0.8% ethyl acetate / toluene to obtain a yellow solid, which was then pulverized twice with warm toluene. Subsequently, it was filtered to isolate compound 1064460 as a yellow solid (0.60 g, 0.646 mmol, yield 15.4%), and the mass of the desired product was confirmed by LC / MS. Synthesis Example 2

[0102] Synthesis of 8-(5-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzoflo[2,3-b]pyridine: TIFF0007872387000237.tif241518-(5-bromopyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (7 g, 20.64 mmol) and PEPPSI-IPr (1.051 g, 1.548 mmol) were added to a reaction flask with 150 mL of THF. Then, bicyclo[2.2.1]heptan-2-yl zinc(II) bromide (70.2 ml, 35.1 mmol) was added to the reaction flask by syringe, and the mixture was degassed with nitrogen. The mixture was stirred at room temperature (approximately 22°C) for 16 hours. Gas chromatography / mass spectroscopy analysis showed that the reaction was complete. The reaction mixture was quenched with aqueous ammonium chloride, and then most of the THF was removed under reduced pressure. Ethyl acetate was added to the aqueous solution of the mixture, and the mixture was heated in a 70°C bath for several hours. Subsequently, the organic layer was separated, and the aqueous phase was further extracted with ethyl acetate. The extracts were combined, washed with an aqueous solution of LiCl, and then dried over magnesium sulfate. The extracts were then filtered and concentrated under vacuum. The crude residue was passed through a 2 × 330 g silica gel column using 3%–6% THF / toluene. The clarified product fractions were combined and concentrated under vacuum to obtain 8-(5-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (6 g, 16.93 mmol, yield 82%) as a foamy solid.

[0103] Synthesis of 8-(5-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzoflo[2,3-b]pyridine [ka] 8-(5-(bicyclo[2.2.1]heptan-2-yl)pyridine-2-yl)-2-methylbenzofl[2,3-b]pyridine (7.34 g, 20.71 mmol) was placed in a reaction flask with 60 mL of THF and dimethyl sulfoxide-d6 (35 mL, 500 mmol). Then, sodium tert-butoxide (0.596 g, 6.21 mmol) was added all at once to the reaction mixture. The mixture was stirred and heated in an oil bath set to 65°C for 16 hours. The reaction mixture was cooled to room temperature (approximately 22°C) and then quenched with 80 mL of D2O. The mixture was extracted twice with 400 mL of ethyl acetate. The extracts were combined, washed with aqueous LiCl solution, and then dried over magnesium sulfate. The extracts were then filtered and concentrated under vacuum. The residue was passed through a 3 × 330 g silica gel column using 2.5% to 3.5% THF / toluene. From the clarified product fraction, 8-(5-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzoflo[2,3-b]pyridine (3.3 g, 9.21 mmol, yield 44.5%) was obtained.

[0104] Compound 1064122[Ir(L A202 )(L B430 )2] Synthesis [ka] As shown in the scheme above, 8-(5-(bicyclo[2.2.1]heptan-2-yl-2-d)pyridine-2-yl)-2-(methyl-d3)benzofl[2,3-b]pyridine (3.3 g, 9.21 mmol) and iridium salt (4.2 g, 5.37 mmol) were placed in a reaction flask with 40 mL of ethanol and 40 mL of methanol. The mixture was degassed with nitrogen and then heated in an oil bath set to 75°C for 5 days. The reaction mixture was cooled to room temperature (approximately 22°C). A yellow solid was filtered from the solution and then dried under vacuum. The yellow solid was dissolved in 400 mL of DCM and then passed through an activated plug of basic alumina. The filtrate of DCM was evaporated under vacuum. The crude residue was passed through a 7 × 120 g silica gel column and the column was eluted with 5% ethyl acetate / toluene. The main product initially eluted from the column was isolated as a yellow solid. This material was pulverized twice with toluene / heptane and then filtered for isolation. The desired iridium complex was isolated as a yellow solid (0.8 g, 0.86 mmol, yield 16.06%). The mass of the desired product was confirmed by liquid chromatography / mass spectroscopy (LC / MS) analysis. Device Examples

[0105] All of the example devices were under high vacuum (<10 -7The devices were fabricated by thermal deposition in Torr. The anode electrode was 750 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) and 1,000 Å Al. Immediately after fabrication, each device was sealed in a nitrogen glove box (H2O and O2 <1 ppm) with a glass lid sealed with epoxy resin, and a moisture getter was placed in the package. The laminate of the device example consisted of, in order from the ITO surface, a 100 Å HATCN as the hole injection layer (HIL); a 450 Å HTM as the hole transport layer (HTL); a 50 Å EBM as the electron blocking layer; a 400 Å EML containing two component host (H1:H2 3:2 ratio) and 12% light-emitting material (GD1 as inventive example 1 vs. GD2 as comparative example CE1); and a 350 Å Liq (8-hydroxyquinoline lithium) doped with 40% ETM as the ETL. The chemical structure of the device material is shown below. [ka]

[0106] Table 1 shows the thickness and material of the device layer. Table 1 Device structure for evaluation of green light emitters TIFF0007872387000241.tif42115

[0107] Using light-emitting example 1 (GD1) and comparative example CE1 (GD2), the efficiency superiority of devices containing the inventive compound versus the comparative compound was demonstrated. 10 mA / cm 2 The external quantum efficiency (EQE) and luminance efficiency (LE) of the device measured are shown in Table 2. Table 2 External quantum efficiency of the devices in the inventive and comparative examples. TIFF0007872387000242.tif20149

[0108] The observed LE and EQE of the inventive light-emitting device are considerably higher compared to the comparative light-emitting device.

[0109] The various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. The various theories of why the invention works are not intended to limit it. [Prior art documents] [Patent Documents]

[0110] [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]

[0111] 100 Organic Light-Emitting Devices 110 circuit boards 115 Anodes 120 Hole injection layer 125 Hole transport layer 130 electron blocking layer 135 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 OLEDs, devices 210 circuit boards 215 Cathode 220 Emitting layer 225 Hole transport layer 230 anodes

Claims

1. It is a compound, The compound can function as a phosphorescent material in an organic light-emitting device at room temperature; The aforementioned compound is represented by the formula Ir(L1)2(L2): The aforementioned L1 is represented as follows: 【Chemistry 1】 The aforementioned L2 is expressed as follows: 【Chemistry 2】 In the formula, X1 to X4 and X6 to X12 are carbon, and X5 is selected from the group consisting of carbon and nitrogen; X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO₂, CR'R'', SiR'R'', and GeR'R''; R' and R'' may each independently condense or bond to form a ring; R a, R b, and R c each independently represent the maximum number of substitutions possible from a mono-substitution, or no substitution at all; R', R'', R a, R b, and R c are each 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, phosphinol, and combinations thereof; Any two adjacent substituents of Ra, Rb, and Rc may condense or bond to form a ring or a polydentate ligand. At least one of Ra in L2 is a substituent R, The compound is characterized in that the substituent R is represented by the following formula. 【Transformation 3】 (In the formula, (b) G １ This is a direct bond; G ２ is a non-aromatic spiropolycyclic group, and has one or more R ３ It can be further replaced by; or (c) G １ This is a direct bond; G ２ is a non-aromatic polycyclic group, and has one or more R ３ It can be further replaced with; R3 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, phosphine, and combinations thereof; G2 may be partially or completely deuterated.

2. G ２ The compound according to claim 1, wherein is a polycyclic alkyl, a carborane, or a non-aromatic polycyclic group comprising at least one heteroatom.

3. The compound according to claim 1, which can emit light from a triplet excited state to a ground singlet state at room temperature.

4. The compound according to claim 1, wherein G2 is selected from the group consisting of the following. 【Chemistry 4】

5. The compound according to claim 1, wherein at least one substituent R is independently selected from the group consisting of the following. 【Transformation 5】

6. L2 has the following structure: 【Transformation 6】 The compound according to claim 1, wherein L Ai is represented by and selected from the group consisting of L A1 to L A1697 shown below (where i is limited to those described below). 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 【Chemistry 35】 【Transformation 36】 【Chemistry 37】 【Transformation 38】 【Chemistry 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】

7. The compound is compound x selected from the group consisting of compound 1 to compound 1,450,935, and compound x is represented by the formula Ir(L Ai)(L Bj)2, x = 1697j + i - 1697, where i is an integer from 1 to 1,697 and j is an integer from 1 to 855; L Ai is selected from L A1 to L A1697; L Bj has the following structure: 【Chemistry 43】 Based on this, the compound according to claim 6 shown in the table below. 【Chemistry 44】 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 [Transformation 50] 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】 【Chemistry 54】 【Transformation 55】 【Transformation 56】 【Chemistry 57】 【Transformation 58】 【Chemistry 59】 【Transformation 60】 【Chemistry 61】 【Transformation 62】 【Transformation 63】 【Chemistry 64】 【Transformation 65】 【Chemical Formula 66】

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