Organic electroluminescent materials and devices

Abstract

A bis- or tris- heteroligand and a new organometallic complex having a large aspect ratio in one direction and its use to improve efficiency in OLEDs are disclosed.

Description

Technology Field

[0001] Cross-reference of related applications

[0002] The present application claims priority to U.S. provisional applications serial numbers 62 / 516,329 (filed June 7, 2017), 62 / 352,139 (filed June 20, 2016), 62 / 450,848 (filed January 26, 2017), 62 / 479,795 (filed March 31, 2017), and 62 / 480,746 (filed April 3, 2017) under 35 USC §119(e)(1), the full contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present disclosure relates to a compound for use as a phosphorescent emitter and a device comprising the same, such as an organic light-emitting diode. More specifically, the present disclosure relates to an organometallic complex having a large aspect ratio in one direction and its use in an OLED to improve efficiency. Background Technology

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

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

[0007] One application of phosphorescent emitting molecules is a full-color display. Industrial standards for such displays require pixels tuned to emit specific colors referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates known in the art.

[0008] An example of a green luminescent molecule is tris(2-phenylpyridine) iridium, represented as Ir(ppy)3 having the following chemical formula:

[0009]

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

[0011] In this document, the term "organic" includes not only polymeric materials that can be used to manufacture organic optoelectronic devices, but also small molecule organic materials. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small molecules may contain repeating units in some situations. For example, using a long-chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into the polymer, for example, as side chains on the polymer main chain or as part of the main chain. Small molecules may also act as the core moiety of a dendrimer, which consists of a series of chemical shells formed on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule," and it has been found that all dendrimers commonly used in the OLED field are small molecules.

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

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

[0014] If a ligand is found to directly contribute to the photoactive properties of a luminescent material, the ligand may be referred to as "photoactive." Even if an auxiliary ligand can alter the properties of the photoactive ligand, if the ligand is found not to contribute to the photoactive properties of the luminescent material, the ligand may be referred to as "auxiliary."

[0015] As used herein and as generally understood by those skilled in the art, when the first "highest occupied molecular orbital (HOMO)" or "lowest unoccupied molecular orbital (LUMO)" energy level approaches the vacuum energy level, the first energy level is "greater" or "higher" than the second HOMO or LUMO. Since the ionization potential (IP) is measured as negative energy with respect to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (the negative value of IP is smaller). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (the negative value of EA is smaller). In a typical 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. This indicates that "higher" HOMO or LUMO energy levels are closer to the upper part of the diagram than "lower" HOMO or LUMO energy levels.

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

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

[0018] According to aspects of the present disclosure, it includes a compound.

[0019] According to another aspect, an OLED is disclosed. The OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the chemical formula I.

[0020] According to another aspect, a consumer product comprising an OLED is disclosed, wherein the OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the chemical formula I.

[0021] A preparation comprising a compound having the chemical formula I is also disclosed. Brief explanation of the drawing

[0022] An organic light-emitting diode is shown in Fig. 1. Figure 2 shows an inverted organic light-emitting diode that does not have a separate electron transport layer. Specific details for implementing the invention

[0023] Generally, an OLED comprises one or more organic layers disposed between an anode and a cathode and electrically connected to them. When current is applied, the anode injects holes into the organic layer(s), and the cathode injects electrons. The injected holes and electrons move toward oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, "excitons" are formed, which are localized electron-hole pairs having an excited energy state. Light is emitted when excitons relax via a photoluminescence mechanism. In some cases, excitons may be localized on excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

[0024] Early OLEDs used light-emitting molecules that emit light ("fluorescence") from a single-claim state, such as disclosed in, for example, U.S. Patent No. 4,769,292, the full text of which is incorporated herein by reference. Fluorescence emission generally occurs over a time period of less than 10 nanoseconds.

[0025] More recently, OLEDs having a light-emitting material that emits light ("phosphorescence") from a triplet state have been exemplified. Reference [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,” Appl. Phys. Lett.See [ , vol. 75, No. 3, 4-6 (1999) ("Baldo-II")], the full text of which is incorporated herein by reference. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, incorporated by reference.

[0026] An organic light-emitting device (100) is illustrated in FIG. 1. The drawing is not necessarily drawn to scale. The device (100) may include a substrate (110), an anode (115), a hole injection layer (120), a hole transport layer (125), an electron blocking layer (130), a light-emitting layer (135), a hole blocking layer (140), an electron transport layer (145), an electron injection layer (150), a protective layer (155), a cathode (160), and a blocking layer (170). The cathode (160) is a compound cathode having a first conductive layer (162) and a second conductive layer (164). The device (100) may be manufactured by depositing layers in the order described. The properties and functions of the materials of example, as well as these various layers, are described more specifically in columns 6-10 of U.S. Patent No. 7,279,704, which are incorporated by reference.

[0027] Further examples for each of these layers are also available. For example, flexible and transparent substrate-anode combinations are disclosed in U.S. Patent No. 5,844,363, the full text of which is incorporated herein 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 No. 2003 / 0230980, the full text of which is incorporated herein by reference. An example of a luminescent and host material is disclosed in U.S. Patent No. 6,303,238 (Thompson et al.), the full text of which is incorporated herein 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 No. 2003 / 0230980, the full text of which is incorporated herein by reference. Examples of cathodes are disclosed in U.S. Patents No. 5,703,436 and No. 5,707,745, the full text of which is incorporated herein by reference, including compound cathodes having thin layers of metals such as Mg:Ag with stacked transparent, electrically conductive sputter-deposited ITO layers. The theory and applications of blocking layers are described more specifically in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, the full text of which is incorporated herein by reference. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated herein by reference. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, the full text of which is incorporated herein by reference.

[0028] FIG. 2 illustrates an inverted OLED (200). The device comprises a substrate (210), a cathode (215), a light-emitting layer (220), a hole transport layer (225), and an anode (230). The device (200) can be manufactured by stacking layers in the order described. Since the most common OLED structure has the cathode positioned above the anode and the device (200) has the cathode (215) positioned below the anode (230), the device (200) may be referred to as an "inverted" OLED. A material similar to that described for the device (100) may be used for the corresponding layer of the device (200). FIG. 2 provides an example of how some layers may be omitted from the structure of the device (100).

[0029] The simple stacked structure illustrated in FIGS. 1 and 2 is provided as a non-limiting example, and it should be understood that embodiments of the invention may be used in connection with various other structures. The specific materials and structures described are for illustrative purposes only, and other materials and structures may also be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be entirely omitted based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than these specifically described layers may be used. Although many examples provided herein describe various layers as comprising a single material, materials, such as a mixture of a host and a dopant, or more generally a mixture, may be used. Additionally, a layer may have a number of underlying layers. The names given herein for the various layers are not intended to be strictly limited. For example, in the device (200), the hole transport layer (225) transports holes and injects holes into the light-emitting layer (220), and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise a plurality of layers of different organic materials, for example, as described in relation to FIGS. 1 and FIGS. 2.

[0030] OLEDs comprising structures and materials not specifically described, such as polymer materials (PLEDs) as described in U.S. Patent No. 5,247,190 (Friend et al.), may be used, the full text of which is incorporated herein by reference. As an additional example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 (Forrest et al.), the full text of which is incorporated herein by reference. OLED structures may deviate from the simple stacked structures shown in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 (Forrest et al.) and / or a pit structure as described in U.S. Patent No. 5,834,893 (Bulovic et al.), the full text of which is incorporated herein by reference.

[0031] Unless otherwise specified, any layer of various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation as described in U.S. Patents No. 6,013,982 and 6,087,196 (the full text of which is incorporated herein by reference), ink-jet, organic vapor phase deposition (OVPD) as described in U.S. Patent No. 6,337,102 (Forrest et al.) (the full text of which is incorporated herein by reference), and organic vapor jet printing (OVJP) as described in U.S. Patent No. 7,431,968 (the full text of which is incorporated herein by reference). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred pattern-forming methods include deposition through a mask, cold welding as described in U.S. Patents No. 6,294,398 and 6,468,819 (the full text of which is incorporated herein by reference), and pattern-forming associated with some deposition methods such as ink-jet and OVJD. The material to be deposited may be modified to be compatible with a specific deposition method. For example, substituents such as branched or unbranched alkyl and aryl groups, preferably containing three or more carbons, may be used on the small molecule to improve its solution processing capability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials having an asymmetric structure may have better solution processing capabilities than those having a symmetric structure, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to improve the solution processing capability of the small molecule.

[0032] Devices manufactured according to embodiments of the present invention may additionally optionally include a blocking layer. One purpose of the blocking layer is to prevent the electrode and organic layer from being damaged by exposure to harmful species in an environment containing moisture, vapor and / or gas. The blocking layer may be deposited on the substrate, under the substrate, or on the side of the substrate, or on any other part of the device including the electrode or edge. The blocking layer may comprise a single layer or multiple layers. The blocking layer may be formed by various known chemical vapor deposition techniques and may comprise a composition having multiple phases as well as a composition having a single phase. Any suitable material or combination of materials may be used in the blocking layer. The blocking layer may incorporate inorganic or organic compounds, or both. A preferred blocking layer comprises a mixture of polymeric and non-polymeric materials as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, the full text of which is incorporated herein by reference. Considering the "mixture," the aforementioned polymer and non-polymer materials, including the blocking layer, must be deposited under the same reaction conditions and / or at the same time. The weight ratio of the polymer to the non-polymer material may be in the range of 95:5 to 5:95. The polymer and non-polymer materials may be produced from the same precursor material. In one example, the mixture of the polymer and non-polymer materials essentially consists of polymeric silicon and inorganic silicon.

[0033] A device manufactured according to an embodiment of the present invention may be incorporated into a wide range of electronic component modules (or units) that can be incorporated into various electronic products or intermediate components. Examples of said electronic products or intermediate components include display screens, individual light source elements, or lighting elements such as lighting panels that can be utilized by end-user product manufacturers. The electronic component modules may, in some cases, include driving electronics and / or power source(s). A device manufactured according to an embodiment of the present invention may be incorporated into a wide range of consumer goods having one or more electronic component modules (or units) incorporated therein. The consumer goods include any type of product comprising one or more light source(s) and / or one or more of some types of image displays. Some examples of the above consumer goods include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal information terminals (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, automobiles, video walls including multiple displays tiled together, theater or stadium screens or signage. The elements according to the present invention may be controlled using various control mechanisms, including passive matrices and active matrices. Many elements are intended to be used in a temperature range that is comfortable for humans, e.g., 18°C ​​to 30°C, more preferably at room temperature (20°C to 25°C), but may also be used at temperatures outside of said temperature range, e.g., -40°C to +80°C.

[0034] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photodetectors, may use the materials and structures. More generally, organic devices, such as organic transistors, may use the materials and structures.

[0035] As used herein, "halo," "halogen," or "halide" includes fluorine, chlorine, bromine, and iodine.

[0036] As used herein, "alkyl" refers to both straight-chain and branched-chain alkyl radicals. Preferred alkyl groups are those containing 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl groups may be optionally substituted.

[0037] As used herein, "cycloalkyl" means a cyclic alkyl radical. A preferred cycloalkyl group is one containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, etc. Additionally, the cycloalkyl group may be optionally substituted.

[0038] As used herein, "alkenyl" refers to both straight-chain and branched-chain alkene radicals. A preferred alkenyl group contains 2 to 15 carbon atoms. Additionally, the alkenyl group may be optionally substituted.

[0039] As used herein, "alkynyl" refers to both straight-chain and branched-chain alkyne radicals. A preferred alkynyl group contains 2 to 15 carbon atoms. Additionally, the alkynyl group may be optionally substituted.

[0040] As used herein, "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group having an aromatic group as a substituent. Additionally, an alkylaryl group may be optionally substituted.

[0041] As used herein, "heterocyclic group" refers to aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also refer to heteroaryls. Preferred hetero-non-aromatic cyclic groups are those containing one or more heteroatoms and containing three or seven ring atoms, including cyclic amines such as morpholino, piperdino, pyrrolidino, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Additionally, heterocyclic groups may be optionally substituted.

[0042] As used herein, "aryl" or "aromatic group" refers to monocyclic groups and polycyclic ring systems. Polycyclic rings may have two or more rings ("condensed" rings) in which two carbons are common to two adjacent rings, and one or more of the rings may be, for example, aromatic, and the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6, 10, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl groups may be optionally substituted.

[0043] As used herein, the term "heteroaryl" comprises a single-ring hetero-aromatic group that may contain 1 to 5 heteroatoms. The term heteroaryl also comprises a polycyclic heteroaromatic system having two or more rings ("condensed" rings) in which two atoms are common to two adjacent rings, wherein one or more of the rings are, for example, heteroaryl, and the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophen, dibenzofuran, dibenzoselenopen, furan, thiophene, benzofuran, benzothiophen, benzoselenopen, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, phenazine, Includes phenothiazine, phenoxazine, benzopuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenofyridine, and selenofenodipyridine, preferably dibenzothiophen, dibenzofuran, dibenzoselenofen, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azabolin, 1,3-azabolin, 1,4-azabolin, borazine and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

[0044] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0045] As used herein, "substituted" indicates that a substituent other than H is bonded to a relevant position, e.g., a carbon. Thus, for example, R 1 In the case of this single substitution, one R 1 must be something other than H. Similarly, R 1 In this case of substitution, R 1 Two of them must be something other than H. Similarly, R 1 In this unsubstituted case, R 1 is hydrogen for all possible positions.

[0046] In the segments described herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., the designation "aza" implies that one or more of the CH groups in each segment may be substituted with nitrogen atoms; for example (but not limited thereto), azatriphenylene includes both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those skilled in the art may readily consider other nitrogen analogs of the aza derivatives described above, and all such analogs are deemed to encompass the terms described herein.

[0047] Those skilled in the art will understand that when a molecular segment is described as a substituent or, if not, is attached to another moiety, its name may be described as if it were a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as the whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different notations of such substituents or attached segments are considered to be the same.

[0048] In the present disclosure, organometallic complexes based on Ir, Os, Rh, Ru, Re, Pt, or Pd are provided, comprising bis- or tris- heteroligands and having a large aspect ratio in one direction. The inventors have discovered that incorporating these compounds into OLEDs improves device efficiency. The ligands are arranged such that the molecular length in one direction is longer than in any other direction, thereby inducing a large aspect ratio. When applied as emitters in PhOLED devices, compounds with a large aspect ratio exhibit enhanced external quantum efficiency (EQE) because they are preferentially oriented horizontally to the plane of the substrate (i.e., parallel to the substrate), thereby maximizing light extraction from the emitter compound. Horizontal orientation maximizes the surface area of ​​the photoluminescent molecule facing the photoluminescent facade of the device. Some examples of the organometallic compounds disclosed herein have three different bidentate cyclometalated ligands coordinated to an iridium metal center. Some other examples of the above organometallic compounds have two different bidentate cyclometalated ligands coordinated to a platinum metal center.

[0049] According to an aspect of the present disclosure, a compound having a chemical formula selected from the group consisting of the following is disclosed:

[0050]

[0051]

[0052] In the above formula,

[0053] Rings A, B, C, D, E, and F are pentary or hexacyclic or heterocyclic rings;

[0054] In Chemical Formula I: AB, CD, and EF are metal M 1 It contains three bidentate ligands that coordinate to; AB, CD, and EF are distinct from each other; in the octahedral coordination arrangement, ring A is transpositioned with respect to ring D, ring B is transpositioned with respect to ring E, and ring C is transpositioned with respect to ring F;

[0055] In Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with each other; AB, and CD are distinct from each other; in an octahedral coordination arrangement, ring A is trans positioned with respect to ring D, ring B is trans positioned with respect to the oxygen atom, and ring C is trans positioned with respect to the oxygen atom;

[0056] In chemical formula III: L 1 and L 3 are each independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; and if n1 or n2 is 1, L 2 or L 4 ga is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; and if n1 or n2 is 0, L 2 or L 4 is not present; Q 1 , Q 2 , Q 3 and Q 4 Each is independently selected from the group consisting of directly bonded and oxygen; and any Z1 , Z 2 , Z 3 and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 and Q 4 is a direct combination;

[0057] In a square planar coordination array, ring A is in a trans position with respect to ring D, and ring B is in a trans position with respect to ring C;

[0058] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution or the maximum possible number of substitutions, or a non-substitution;

[0059] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Each is independently selected from the group consisting of carbon and nitrogen;

[0060] M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd;

[0061] The first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between atoms of;

[0062] The second distance is M 1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between atoms of;

[0063] The third distance is M 1The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between atoms of;

[0064] The fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between atoms of;

[0065] The 5th distance is M 2 The furthest R from 2 R in the atom 3 M of M 2 The furthest R from 3 It is the distance between atoms of;

[0066] The first distance is at least 1.5 Å longer than the second and third distances, respectively;

[0067] The fourth distance is at least 1.5 Å longer than the fifth distance;

[0068] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof;

[0069] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7Among them, any two substituents are arbitrarily connected or condensed to form a ring. The aforementioned 1.5 Å is the distance of the CC bond (i.e., methyl group addition) from the calculation.

[0070] In other words, the above description defines the relationship between the long axes of the molecule defined by different substituent pairs in each complex represented by Chemical Formulas I, II, and III. Each of the identified substituent pairs is a coordinating metal M 1 or M 2 These are substituents located on substantially opposite sides of each other. The two terminal points of the long axis of each defined molecule are the atoms of the respective paired substituents furthest from the corresponding coordination metal.

[0071] In some embodiments of the compound, each substituent R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two substituents within it, if they are identical or more, can be arbitrarily connected or condensed to form a ring.

[0072] In some specific examples of the compound, M 1 is Ir, and M 2 is Pt.

[0073] In some embodiments of the compound, rings A, B, C, D, E, and F are each independently selected from the group consisting of phenyl, pyridine, and imidazole. In some embodiments of the compound, rings A, C, and E in formulas I and III, and rings A and D in formula II are phenyl.

[0074] In some embodiments of the compound, rings B, D, and F in formulas I and III, and rings B and C in formula II are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazol.

[0075] In some embodiments of the compound, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof.

[0076] In some embodiments of the compound, the first distance is at least 4.3 Å longer than the second distance and the third distance, respectively, and the fourth distance is at least 4.3 Å longer than the fifth distance. The value of 4.3 Å represents the diameter of the phenyl ring. Thus, in the compound, the first distance is at least 4.3 Å longer than the second distance and the third distance, and the fourth distance is at least 4.3 Å longer than the fifth distance.

[0077] In some embodiments of the compound, the first distance is at least 5.9 Å longer than the second and third distances, respectively, and the fourth distance is at least 5.9 Å longer than the fifth distance. The value of 5.9 Å represents the distance encompassing the para-tolyl group.

[0078] In some embodiments of the compound, one or more of rings A, B, C, D, E, and F are condensed by another pentagonal or hexagonal ring. The other pentagonal or hexagonal ring may be an aromatic ring or a non-aromatic ring. The aromatic ring may be a phenyl ring.

[0079] In some embodiments where the compound is formula I, one or more of (i), (ii), and (iii) apply, and (i) 1 R 1 1 R 2 Connected to, and (ii) 1 R 3 1 R 4 Connected to, and (iii) 1 R 5 is 1 R 6It is connected to. In some embodiments where the compound is formula II, one or more of (i) and (ii) apply, and (i) 1 R 1 This 1 R 2 Connected to, and (ii) 1 R 3 1 R 4 It connects to.

[0080] In some embodiments, the first distance is at least 3.0 Å longer than the second distance and the third distance, respectively, and the fourth distance is at least 3.0 Å longer than the fifth distance. The value of 3.0 Å represents a distance encompassing two methyl groups.

[0081] Table 1 below lists the maximum linear lengths for various substituents defined along the long axis. These maximum linear lengths are defined as the distance between the two farthest atoms along the long axis of a specific substituent. The listed values ​​can be used to evaluate the difference in length between the long axes of the two molecules defined above, in relation to the structures of Formulas I, II, and III, depending on the substituents that differ between the long axes of the two molecules to be compared. For example, if the difference in length between the long axes of the two molecules is the result of one molecule's long axis being longer than the other due to an additional phenyl substituent, the fourth entry in Table 1 below indicates that the difference in length between the long axes of the two molecules is 4.3 Å or more (requiring an additional CC bond to form the link). Any two or more of the fragments below can be linked together, and their distance can be calculated simply by summing this number and the total length of the distance of the single CC bonds used to link them.

[0082]

[0083] In some embodiments of the compound, the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of:

[0084]

[0085]

[0086] In the above equation, each X 1 To X 13 It is independently selected from the group consisting of carbon and nitrogen;

[0087] 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";

[0088] R' and R" are arbitrarily condensed or connected to form a ring;

[0089] R a , R b , R c , and R d Each represents a uniform substitution or the maximum possible number of substitutions, or a non-substitution;

[0090] R', R", R a , R b , R c , and R d 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, phosphino, and combinations thereof;

[0091] R a , R b , R c , and R d Any two of the substituents are optionally condensed or linked to form a ring. In some embodiments of the compound, the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of the following:

[0092]

[0093]

[0094]

[0095] In some embodiments of the compound, n1 is 1 and n2 is 0. In some embodiments, n1 is 1 and n2 is 1. In some embodiments, n1 is 0 and n2 is 0.

[0096] In some embodiments of the compound, each Q 1 , Q 2 , Q 3 , and Q 4 is a direct bond. In some embodiments, Q 1 , Q 2 , Q 3 , and Q 4 One of them is oxygen, and Q 1 , Q 2 , Q 3 , and Q 4 The remaining three are direct bonds. In some embodiments, Q 1 , Q 2 , Q 3 , and Q 4 Two of them are oxygen, and Q 1 , Q 2 , Q 3 , and Q 4 The remaining two of them combine directly.

[0097] In some embodiments of the compound, Z 1 , Z 2 , Z 3 , Z 4 Two of them are carbon atoms, and Z 1 , Z 2 , Z 3 , Z 4 The remaining two of them are nitrogen atoms. In some embodiments, Z 1 , Z 2 , Z 3 , Z 4 Three of them are carbon atoms, and Z 1 , Z 2 , Z 3 , Z 4 The remaining one of them is a nitrogen atom. In some embodiments, each Z 1 , Z2 , Z 3 , Z 4 is a carbon atom.

[0098] Each Q 1 , Q 2 , Q 3 , and Q 4 In some embodiments where the bond is a direct bond, the compound is in a cis configuration. In some embodiments, the compound has one or more Pt-carbene or Ir-carbene bonds.

[0099] In some embodiments of the compound, the compound of formula III is selected from the group consisting of the following:

[0100]

[0101]

[0102] In some embodiments of the compound, the compound is selected from the group consisting of the following:

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] In the above formula, X is selected from the group consisting of O, Se, and Se;

[0109] X' is carbon or nitrogen;

[0110] R 1' , R 2' , R 3' , and R 4' Each represents a uniform substitution or the maximum possible number of substitutions, or a non-substitution;

[0111] Each R 1' , R 2' , R 3' , and R 4'is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0112] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are optionally connected or condensed to form a ring. In some embodiments of the compound, one or more R 1 is in the para position for N coordinating to Ir, and one or more R 4 is in the para position relative to the carbon coordinately bonded to Ir. In some other embodiments of the compound, R 1 and R 1' One or more of and one or more R 4 and R 4' is selected from a group consisting of:

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] In some embodiments of the compound, the compound is selected from the group consisting of the following:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167] According to another aspect of the present disclosure, an organic light-emitting diode (OLED) is disclosed, wherein the OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having a chemical formula selected from the group consisting of the following:

[0168]

[0169] In the above formula, rings A, B, C, D, E, and F are each pentagonal or hexagonal carbocyclic or heterocyclic rings;

[0170] In Chemical Formula I: AB, CD, and EF are metal M 1 Forms three bidentate ligands that coordinate with each other; AB, CD, and EF are distinct from each other; in the octahedral coordination arrangement, ring A is transpositioned with respect to ring D, ring B is transpositioned with respect to ring E, and ring C is transpositioned with respect to ring F;

[0171] In Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with each other; AB, and CD are distinct from each other; in an octahedral coordination arrangement, ring A is trans positioned with respect to ring D, ring B is trans positioned with respect to the oxygen atom, and ring C is trans positioned with respect to the oxygen atom;

[0172] In chemical formula III: L 1 and L 3 are each independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; and if n1 or n2 is 1, L 2 or L 4 ga is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; and if n1 or n2 is 0, L 2 or L 4 does not exist; Q 1 , Q 2 , Q 3 , and Q 4Each is independently selected from the group consisting of directly bonded and oxygen; and any Z 1 , Z 2 , Z 3 , and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 , and Q 4 is a direct combination;

[0173] In a square planar coordination array, ring A is in a trans position with respect to ring D, and ring B is in a trans position with respect to ring C;

[0174] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution or the maximum possible number of substitutions, or a non-substitution;

[0175] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 Each is independently selected from the group consisting of carbon and nitrogen;

[0176] M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd;

[0177] The first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between atoms of;

[0178] The second distance is M 1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between atoms of;

[0179] The third distance is M 1 The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between atoms of;

[0180] The fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between atoms of;

[0181] The 5th distance is M 2 The furthest R from 2 M in the atom of 2 The furthest R from 3 It is the distance between atoms of;

[0182] The first distance is at least 1.5 Å longer than the second and third distances, respectively;

[0183] The fourth distance is at least 1.5 Å longer than the fifth distance;

[0184] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof;

[0185] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7Any two of the substituents are arbitrarily connected or condensed to form a ring.

[0186] In some embodiments of an OLED in which a compound in the organic layer is formula I, one or more of (i), (ii), and (iii) are applied, wherein (i) 1 R 1 This 1 R 2 Connected to, and (ii) 1 R 3 This 1 R 4 Connected to, and (iii) 1 R 5 ga 1 R 6 It is connected to. In some embodiments where the compound is formula II, one or more of (i) and (ii) apply, and (i) 1 R 1 This 1 R 2 Connected to, and (ii) 1 R 3 This 1 R 4 It connects to.

[0187] In some embodiments of the OLED, the organic layer is a light-emitting layer and the compound is a light-emitting dopant or a non-light-emitting dopant.

[0188] In some embodiments of the OLED, the organic layer further comprises a host, and the host comprises triphenylene containing benzo-condensed thiophene or benzo-condensed furan;

[0189] Any substituent in the host is 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 - It is an independently selected non-condensed substituent from the group consisting of -Ar1, or the host has no substituent;

[0190] n is 1 to 10 and;

[0191] Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0192] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host comprises one or more chemical groups selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0193] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host is

[0194]

[0195]

[0196] and is selected from a group consisting of combinations thereof.

[0197] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host comprises a metal complex.

[0198] According to another aspect, a consumer product comprising the OLED described above is disclosed. In some embodiments of the consumer product, the consumer product is selected from the group consisting of flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal information terminals (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, virtual reality or augmented reality displays, automobiles, video walls including multiple displays tiled together, theater or stadium screens, and signage.

[0199] According to another aspect, a preparation comprising a compound having a chemical formula selected from the group consisting of the following is disclosed:

[0200]

[0201] In the above formula, rings A, B, C, D, E, and F are each pentagonal or hexagonal carbocyclic or heterocyclic rings;

[0202] In the above chemical formula I: AB, CD, and EF are metal M 1 It contains three bidentate ligands that coordinate to; AB, CD, and EF are distinct from each other; in the octahedral coordination arrangement, ring A is transpositioned with respect to ring D, ring B is transpositioned with respect to ring E, and ring C is transpositioned with respect to ring F;

[0203] In Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with each other; AB, and CD are distinct from each other; in an octahedral coordination arrangement, ring A is trans positioned with respect to ring D, ring B is trans positioned with respect to the oxygen atom, and ring C is trans positioned with respect to the oxygen atom;

[0204] In chemical formula III: L 1 and L 3 are each independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; and if n1 or n2 is 1, L 2 or L 4 ga is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; and if n1 or n2 is 0, L 2 or L4 does not exist; Q 1 , Q 2 , Q 3 , and Q 4 Each is independently selected from the group consisting of direct bonding and oxygen; and any Z 1 , Z 2 , Z 3 , and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 , and Q 4 is a direct combination;

[0205] In a square planar coordination array, ring A is in a trans position with respect to ring D, and ring B is in a trans position with respect to ring C;

[0206] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution or the maximum possible number of substitutions, or a non-substitution;

[0207] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 Each is independently selected from the group consisting of carbon and nitrogen;

[0208] M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd;

[0209] The first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between atoms of;

[0210] The second distance is M1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between atoms of;

[0211] The third distance is M 1 The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between atoms of;

[0212] The fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between atoms of;

[0213] The 5th distance is M 2 The furthest R from 2 M in the atom of 2 The furthest R from 3 It is the distance between atoms of;

[0214] The first distance is at least 1.5 Å longer than the second and third distances, respectively;

[0215] The fourth distance is at least 1.5 Å longer than the fifth distance;

[0216] R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof;

[0217] R, R', R 1 , R 2 , R3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are arbitrarily connected or condensed to form a ring.

[0218] In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compound may produce phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also called E-type delayed fluorescence), triplet-triplet extinction, or a combination of these processes.

[0219] The OLED disclosed herein may be integrated into one or more of consumer goods, electronic component modules, and lighting panels. The organic layer may be a light-emitting layer, and the compound may be a light-emitting dopant in some embodiments, but the compound may be a non-light-emitting dopant in other embodiments.

[0220] The formulation may comprise 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.

[0221] experiment

[0222] Synthesis of Compound 437

[0223] Step 1

[0224]

[0225] CC-2 (2.3 g, 2.71 mmol) was dissolved in dry dichloromethane (400 ml). The mixture was degassed with N2 and cooled to 0°C. 1-bromopyrrolidine-2,5-dione (0.81 g, 2.71 mmol) was dissolved in DCM (300 mL) and added dropwise. After addition, the temperature was gradually raised to room temperature and stirred for 12 hours. A saturated NaHCO3 (20 mL) solution was added. The organic phase was separated and collected. The solvent was removed, the residue was coated onto Celite, and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v) to produce the product CC-2-Br (0.6 g, 24%).

[0226] Step 2

[0227]

[0228] CC-2-Br (0.72 g, 0.775 mmol) was dissolved in a mixture of toluene (40 ml) and water (4 ml). The mixture was purged with N2 for 10 minutes. K3PO4 (0.411 g, 1.937 mmol), SPhos (0.095 g, 0.232 mmol), Pd2dba3 (0.043 g, 0.046 mmol), and phenylboronic acid (0.189 g, 1.55 mmol) were added. The mixture was heated at 110°C under N2 for 12 hours. Then, the reaction mixture was cooled to room temperature, and the product was extracted with DCM. The organic phase was separated and collected. The solvent was removed, the residue was coated onto Celite, and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v). The product was purified by crystallization from toluene / MeOH to form compound 437 (0.7 g).

[0229] Synthesis of Compound 438.

[0230]

[0231] CC-2-Br-2 (0.6 g, 0.646 mmol) was dissolved in a mixture of toluene (100 ml) and water (10 ml). The mixture was purged with N2 for 10 minutes. K3PO4 (0.343 g, 1.61 mmol), SPhos (0.080 g, 0.19 mmol), Pd2dba3 (0.035 g, 0.039 mmol), and [1,1-biphenyl]4-ylboronic acid (0.256 g, 1.29 mmol) were added. The mixture was heated at 110°C under N2 for 12 hours. Then, the reaction mixture was cooled to room temperature, the product was extracted with DCM, and the organic phase was separated. The solvent was removed, the residue was coated onto Celite, and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v). The product was purified by crystallization from toluene / MeOH to form compound 438 (0.64 g).

[0232] Synthesis of Compound 161

[0233] Step 1

[0234]

[0235] CC-1 (2.04 g, 2.500 mmol) was dissolved in dry dichloromethane (400 ml). The mixture was degassed with N2 and cooled to 0°C. 1-bromopyrrolidine-2,5-dione (0.445 g, 2.500 mmol) was dissolved in DCM (200 mL) and added dropwise. After addition, the temperature was gradually raised to room temperature and stirred for 16 hours. A saturated NaHCO3 (20 mL) solution was added. The organic phase was separated and collected. The solvent was removed, the residue was coated onto Celite, and purified on a silica gel column eluted with 70 / 30 toluene / heptane to form the product CC-1-Br (0.6 g).

[0236] Step 2

[0237]

[0238] CC-1-Br (1.16 g, 1.296 mmol) was dissolved in a mixture of toluene (120 ml) and water (12.00 ml). The mixture was purged with N2 for 10 minutes. K3PO4 (0.688 g, 3.24 mmol), Sphos (0.160 g, 0.389 mmol), Pd2dba3 (0.071 g, 0.078 mmol), and phenylboronic acid (0.316 g, 2.59 mmol) were added. The mixture was heated at 110°C under N2 for 16 hours. After the reaction was complete, it was cooled to room temperature, and the product was extracted with DCM. The organic phase was separated and collected. The solvent was removed, the residue was coated onto Celite, and purified on a silica gel column eluted with 70 / 30 toluene / heptane. The product was purified by recrystallization in toluene / MeOH to form compound 161 (1.0 g).

[0239] Synthesis of Compound 401

[0240] Step 1

[0241]

[0242] 2-chloro-5-methylpyridine (10.03 g, 79 mmol), (3-chloro-4-methylphenyl)boronic acid (13.4 g, 79 mmol), and potassium carbonate (21.74 g, 157 mmol) were dissolved under nitrogen in a mixture of DME (150 ml) and water (20 ml) to form a colorless suspension. After adding Pd(PPh3)4 (0.909 g, 0.786 mmol) to the reaction mixture, the mixture was degassed and heated at 95°C for 12 hours. It was then cooled to room temperature, the organic phase was separated, and evaporated. The residue was subjected to column chromatography on a silica gel column, eluted with heptane / THF 9 / 1 (v / v), and provided as white solid heptane 10 g (58% yield) after crystallization.

[0243] Step 2

[0244]

[0245] 2-(3-chloro-4-methylphenyl)-5-methylpyridine (10 g, 45.9 mmol), ((methyl-d3)sulfonyl)methane-d3 (92 g, 919 mmol), and sodium 2-methylpropane-2-oleate (2.65 g, 27.6 mmol) were dissolved together under nitrogen to form a dark solution. The reaction mixture was heated at 80°C under nitrogen for 12 hours, cooled, diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered, and evaporated. It was purified by column chromatography on silica gel, eluted with heptane / THF 9 / 1 (v / v) to form a white solid, and then crystallized from heptane to provide a colorless crystalline material (9.1 g, 81% yield).

[0246] Step 3

[0247]

[0248] 2-(3-chloro-4-(methyl-d3)phenyl)-5-(methyl-d3)pyridine (7.45 g, 33.3 mmol), phenylboronic acid (6.09 g, 49.9 mmol), potassium phosphate (15.34 g, 66.6 mmol), Pd2(dba)3 (0.305 g, 0.333 mmol), and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (Sphos, 0.273 g, 0.666 mmol) were dissolved under nitrogen in a mixture of DME (150 ml) and water (25 ml) to form a red suspension. The reaction mixture was then degassed and heated under reflux. After heating overnight, a conversion rate of approximately 80% was achieved. Adding more pH boronic acid did not improve the conversion. The organic phase was separated, the residue was evaporated and purified by column chromatography on silica gel, eluted with heptane / THF 9 / 1, and crystallized from heptane. White solid (6.2 g, 70% yield).

[0249] Step 4

[0250]

[0251] Under a nitrogen atmosphere, 4,5-bis(methyl-d3)-2-henylpyridine (1.427 g, 7.54 mmol), 5-(methyl-d3)-2-(6-(methyl-d3)-[1,1'-biphenyl]-3-yl)pyridine (2 g, 7.54 mmol), and [IrCl(COD)]2 (2.53 g, 3.77 mmol) were dissolved in ethoxyethanol (50 ml) under nitrogen to form a red solution. The reaction mixture was heated under a cold current for 1 hour to form a precipitate. More than 30 mL of ethoxyethanol was added, and reflux was continued for 48 hours, after which the reaction mixture was cooled to room temperature. The unpurified material was used in the next step without further purification.

[0252] Step 5

[0253]

[0254] The iridium dimer suspended in ethoxyethanol (derived from step 4) was mixed with pentane-2,4-dione (2.59 g, 25.9 mmol) and sodium carbonate (3.43 g, 32.3 mmol) in 50 ml of methanol under a nitrogen atmosphere, stirred at 55°C under nitrogen for 24 hours, and evaporated. The yellow residue was column-chromatographed on a silica gel column and eluted with a gradient mixture of heptane / toluene to yield 5 g (36% yield) of the target acac complex.

[0255] Step 6

[0256]

[0257] After dissolving the acac complex (5 g, 6.72 mmol) in DCM (20 mL), HCl was added all at once in ether (16.80 ml, 33.6 mmol), stirred for 10 minutes, and evaporated. The residue was ground in methanol. The solid was filtered and washed with methanol and heptane to obtain a yellow solid (4.55 g, 100% yield).

[0258] Step 7

[0259]

[0260] Ir dimer (4.55 g, 3.34 mmol) and (((trifluoromethyl)sulfonyl)oxy) (2.062 g, 8.03 mmol) were suspended in 50 ml of DCM / methanol 1 / 1 (v / v) mixture and stirred at room temperature for 72 hours, filtered through Celite, and evaporated to yield a yellow solid (4.75 g, 83% yield).

[0261] Step 8

[0262]

[0263] A mixture of triflic salt (3 g, 3.5 mmol) and 2-(l3-methyl-d2)-8-(4-(2,2-dimethylpropyl-1,1-d2)pyridine-2-yl)benzofuro[2,3-b]pyridine (2.56 g, 7.7 mmol) in 30 mL of methanol was stirred under nitrogen at 65°C for 5 days. The mixture was then cooled and the methanol evaporated. The residue was subjected to column chromatography on silica gel and eluted with 2% ethyl acetate in toluene, yielding two product isomers (a complex with high Rf of 1.7 g and a complex with low Rf of 0.7 g). The complex with low Rf is target compound 401.

[0264] Sojaye

[0265] All example devices are in high vacuum (<10 -7It was fabricated by thermal evaporation (Torr). The anode electrode was 750 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) followed by 1,000 Å Al. All devices were encapsulated with glass lids sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2) immediately after fabrication, and a moisture getter was introduced into the package. The organic stack of the device example was constructed sequentially as follows: from the ITO surface, 100 Å HAT-CN as the hole injection layer (HIL); 450 Å HTM as the hole transport layer (HTL); and a 400 Å thick emissive layer (EML). The emissive layer contained H-host (H1):E-host (H2) in a 6:4 ratio and 12 wt% green emitter. 350 Å Liq(8-hydroxyquinoline lithium) was doped with 40% ETM as the ETL. The device structure is shown in Table 1 below. Table 1 below shows the schematic device structure. The chemical structure of the device material is shown below.

[0266]

[0267]

[0268] When fabricating, set the device to DC 80 mA / cm 2 EL, JVL, and lifetime were evaluated for the tested values. Device performance is shown in Table 3 below, and voltage, LE, EQE, PE, and LT 97% All were normalized for the comparison compounds.

[0269]

[0270]

[0271] When Compounds 437 and 438 were compared to the Comparative Example, the efficiency of the two Compounds 437 and 438 was higher than that of the Comparative Example. Presumably, Compounds 437 and 438 possess a higher horizontal emission dipole orientation than the Comparative Example. Elongated and planar substituents with high electrostatic potential amplify surface region interactions between the Ir complex and the host molecule, causing the Ir complex to stack parallel to the film surface and increasing the outcoupling efficiency. In addition, the 80 mA / cm² of the two Compounds 437 and 438 2 LT in 97% It is much larger than that of the comparative example, which indicates that the slender substituent not only increases efficiency but also increases the stability of the complex within the device.

[0272] Table 4 below provides a summary of device data recorded at 9000 nit for the device example. The EQE values ​​were normalized to device C-2.

[0273]

[0274] The data in Table 4 above indicates that a device using the compound of the present invention as an emitter has the same color as the comparative example but achieves higher efficiency. It is noted that the only difference between the compound of the present invention and the comparative compound (CC-1) is that the compound of the present invention has a phenyl moiety that substitutes one of the protons in the comparative compound, thereby increasing the distance between terminal atoms in one direction across the Ir metal center. The device results appear to be important in that a larger aspect ratio of the emitter molecule leads to higher device efficiency.

[0275] Combination with other substances

[0276] Materials described herein as useful for a specific layer in an organic light-emitting device may be used in combination with various other materials present in the device. For example, the light-emitting dopant disclosed herein may be used in association with various hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art may readily refer to literature identifying other materials that may be useful in combination.

[0277] Conductivity dopant :

[0278] The charge transport layer can be doped with a conductive dopant to substantially alter the charge carrier density, which will change its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, changes in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer.

[0279] Non-limiting examples of conductive dopants that can be used in OLEDs with the materials disclosed herein are exemplified below in conjunction with the references disclosing these materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0280]

[0281] HIL / HTL:

[0282] The hole injection / transport material intended for use in the present invention is not particularly limited, and any compound typically used as a hole injection / transport material may be used. Non-limiting examples of materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers comprising fluorohydrocarbons; polymers having conductive dopants; conductive polymers, e.g., PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, e.g., MoO₂ x ; p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes and crosslinkable compounds may be examples.

[0283] Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the following chemical formulas:

[0284]

[0285] Ar 1 or Ar 9Each 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; Dibenzothiophen, Dibenzofuran, Dibenzoselenopene, Furan, Thiophene, Benzofuran, Benzothiophene, Benzoselenopene, Carbazole, Indolocarbazole, Pyridylindole, Pyrrolodipyridine, Pyrazol, Imidazole, Triazole, Oxazole, Thiazole, Oxadiazole, Oxatriazole, Dioxazole, Thiadiazole, Pyridine, Pyridazine, Pyrimidine, Pyrazine, Triazine, Oxazine, Oxathiazine, Oxadiazine, Indole, Benzimidazole, Indazole, Indoxazine, Benzoxazole, Benzoisoxazole, Benzothiazole, Quinoline, Isoquinoline, Sinnoline, Quinazolin, Quinoxaline, Naphthiridine, Phthalasine, Pteridine, Xanthen, Acridine, Phenazine, Phenothiazine, A group consisting of aromatic heterocyclic compounds such as phenoxazine, benzopuropyridine, propipyridine, benzothienopyridine, thienodipyridine, benzoselenofenopyridine, and selenofenopyridine; and a group consisting of 2 to 10 cyclic structural units selected from the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are directly bonded to each other or bonded through one or more of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units, and aliphatic cyclic groups. Each Ar may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0286] In one aspect, Ar 1 or Ar 9 is independently selected from a group consisting of:

[0287]

[0288] Here, k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 eu NAr 1 , O or S and; Ar 1 It has the same structure as defined above.

[0289] Non-limiting examples of metal complexes used in HIL or HTL include the following:

[0290]

[0291] Here, Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 is independently selected from C, N, O, P, and S; L 101 is an auxiliary ligand; k' is an integer value of the maximum number of ligands that can be bound to the metal, from 1 to; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0292] In terms of work, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In addition, the metal complex has a minimum oxidation potential versus Fc in solution of less than about 0.6 V. + / Fc have a couple.

[0293] Non-limiting examples of HIL and HTL materials that can be used in OLEDs together with the materials disclosed herein are exemplified below together with the references 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.,

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301] .

[0302] EBL:

[0303] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can lead to substantially higher efficiency and / or longer lifetime compared to a similar device without a blocking layer. Additionally, the blocking layer can be used to confine light emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used for the EBL contains the same molecule or the same functional group used as one of the hosts described below.

[0304] Host:

[0305] The light-emitting layer of the organic EL device of the present invention preferably comprises at least a metal complex as a light-emitting dopant material and may comprise one or more host materials using a metal complex as a dopant material. Examples of host materials are not particularly limited, but 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 satisfied.

[0306] An example of a metal complex used as a host preferably has the following chemical formula:

[0307]

[0308] Here, Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 is independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value of the maximum number of ligands that can be attached to the metal, ranging from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0309] In one aspect, metal complexes am:

[0310] Here, (ON) is a bidentate ligand having a metal coordinately bonded to atoms O and N.

[0311] In another aspect, Met is selected from Ir and Pt. In an additional aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0312] Examples of other organic compounds used as hosts include aromatic hydrocarbon cyclic compounds, such as the group consisting of benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; Aromatic heterocyclic compounds, e.g., dibenzothiophene, dibenzofuran, dibenzoselenopene, furan, thiophene, benzofuran, benzothiophene, benzoselenopene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazol, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazolin, quinoxaline, naphthiridine, phthalazine, pteridine, xanthen, acridine, The group consisting of phenazine, phenothiazine, phenoxazine, benzopuropyridine, purodipyridine, benzothienopyridine, thienodipyridine, benzoselenofenofyridine and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units that are of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and are directly bonded to each other or bonded by one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. Each group may be further substituted with a substituent 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.

[0313] In one aspect, the host compound includes at least one of the following groups in the molecule:

[0314]

[0315] Here, R 101 to R 107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and if it is aryl or heteroaryl, it has a definition similar to that of Ar described above. k is an integer from 0 to 20 or from 1 to 20; k"' is an integer from 0 to 20. X 101 To X 108 is selected from C (including CH) or N.

[0316] Z 101 and Z 102 is NR 101 , is selected from O or S.

[0317] Non-limiting examples of host materials that can be used in OLEDs with the host compounds disclosed herein are exemplified below together with the references disclosing these materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472.

[0318]

[0319]

[0320]

[0321]

[0322]

[0323] Additional emitter:

[0324] One or more additional emitter dopants may be used with the compounds of the present disclosure. Examples of additional emitter dopants are not particularly limited, and any compound that is typically used as an emitter material may be used. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing luminescence by phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also called E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes.

[0325] Non-limiting examples of emitter materials that can be used in OLEDs with the materials disclosed herein are exemplified below together with the references 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, 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.,

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332] HBL:

[0333] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer within the device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Additionally, the blocking layer can be used to localize emission to desired areas of the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than one or more of the hosts closest to the HBL interface.

[0334] In one aspect, the compound used in HBL contains the same molecule or the same functional group used as the aforementioned host.

[0335] In another aspect, the compound used in HBL contains at least one of the following groups in its molecule:

[0336]

[0337] Here, k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0338] ETL:

[0339] The electron transport layer (ETL) may comprise a material capable of transporting electrons. The electron transport layer may be native (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used for transporting electrons.

[0340] In one aspect, compounds used in ETL contain one or more of the following groups in their molecules:

[0341]

[0342] Here, 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, phosphino, and combinations thereof, and if it is aryl or heteroaryl, it has a definition similar to that of the aforementioned Ar. 1 or Ar 3 has a definition similar to the aforementioned Ar. k is an integer from 1 to 20. X 101 To X 108 It is selected from C (including CH) or N.

[0343] In another aspect, metal complexes used in ETL include, but are not limited to, the following chemical formulas:

[0344]

[0345] Here, (ON) or (NN) is a bidentate ligand having a metal coordinately bonded to atoms O, N, or N,N; L 101 is another ligand; k' is an integer value of the maximum number of ligands that can be attached to the metal, ranging from 1 to 1.

[0346] Non-limiting examples of ETL materials that can be used in OLEDs with the materials disclosed herein are exemplified below together with the references disclosing these materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535.

[0347]

[0348]

[0349]

[0350] Charge generation layer (CGL)

[0351] In tandem or stacked OLEDs, the CGL plays an essential role in performance and consists of an n-doping layer and a p-doping layer for the injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and the electrodes. Electrons and holes consumed in the CGL are recharged by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a rectified state. Typical CGL materials include n and p conductive dopants used in the transport layers.

[0352] In any of the above-described compounds used in each layer of an OLED device, hydrogen atoms may be partially or completely deuterinated. Accordingly, any specifically listed substituents such as methyl, phenyl, pyridyl, etc. (not limited to) may be non-deuterinated, partially deuterinated, and completely deuterinated versions thereof. Likewise, substituents of a class such as alkyl, aryl, cycloalkyl, heteroaryl, etc. (not limited to) may also be non-deuterinated, partially deuterinated, and completely deuterinated versions thereof.

[0353] It should be understood that the various embodiments described herein are merely illustrative and are not intended to limit the scope of the invention. For example, most of the materials and structures described herein may 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, which will be obvious to those skilled in the art. Those skilled in the art will understand that the various theories applied to the invention are not intended to be limiting.

Claims

Claim 1 Compounds having a chemical formula selected from the group consisting of: In the above formula, rings A, B, C, D, E, and F are each pentar or hexaar carbon-ring or heterocyclic rings; in Chemical Formula I: AB, CD, and EF are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB, CD, and EF are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to ring E, and ring C is in a trans position with respect to ring F; in Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB and CD are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to the oxygen atom, and ring C is in a trans position with respect to the oxygen atom; in Chemical Formula III: L 1 and L 3 Each is independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; If n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; If n1 or n2 is 0, L 2 or L 4 is not present; Q 1 , Q 2 , Q 3 and Q 4 Each is independently selected from the group consisting of directly bonded and oxygen; arbitrary Z 1 , Z 2 , Z 3 and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 and Q 4 is a direct coupling; in a square planar coordination arrangement, ring A is transposition with respect to ring D, ring B is transposition with respect to ring C, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution, the maximum possible number of substitutions, or no substitution; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; the first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between the atoms of; the second distance is M 1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between the atoms of; the third distance is M 1 The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between the atoms of; the fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between the atoms of; the fifth distance is M 2 The furthest R from 2 M in the atom of 2 The furthest R from 3 The distance between atoms of; the first distance is at least 1.5 Å longer than the second and third distances, respectively; the fourth distance is at least 1.5 Å longer than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are arbitrarily connected or condensed into the ring. Claim 2 In paragraph 1, M 1 is Ir, and M 2 is a compound that is Pt. Claim 3 A compound according to claim 1, wherein rings A, B, C, D, E, and F are each independently selected from the group consisting of phenyl, pyridine, and imidazole. Claim 4 In claim 1, the compounds in which rings A, C, and E in formulas I and III, and rings A and D in formula II are phenyl. Claim 5 A compound according to claim 1, wherein rings B, D, and F in formulas I and III, and rings B and C in formula II are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazol. Claim 6 In paragraph 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each is a compound independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof. Claim 7 A compound according to claim 1, wherein one or more of rings A, B, C, D, E, and F are condensed by another pentagonal or hexagonal ring. Claim 8 In claim 1, in chemical formula I, one or more of (i), (ii), and (iii) apply, and (i) 1 R 1 1 R 2 Connected to, and (ii) 1 R 3 1 R 4 Connected to, and (iii) 1 R 5 is 1 R 6 Connected to; in Chemical Formula II, one or more of (i) and (ii) apply, and (i) 1 R 1 1 R 2 Connected to, and (ii) 1 R 3 1 R 4 A compound that is connected to. Claim 9 A compound according to claim 1, wherein the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of: In the above formula, X 1 to X 13 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" are arbitrarily condensed or connected to form a ring; R a , R b , R c , and R d represents, respectively, an identical substitution, the maximum possible number of substitutions, or a non-substitution; R', R", R a , R b , R c , and R d 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, phosphino, and combinations thereof; R a , R b , R c , and R d Any two of the substituents condense or connect to form a ring. Claim 10 In claim 1, the compound of formula III is a compound selected from the group consisting of the following: Claim 11 In paragraph 1, a compound selected from the group consisting of the following: In the above formula, X is selected from the group consisting of O, Se, and Se; X' is carbon or nitrogen; and R 1' , R 2' , R 3' , and R 4' represents, respectively, an identical substitution, the maximum possible number of substitutions, or no substitution; R 1' , R 2' , R 3' , and R 4' 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, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are arbitrarily connected or condensed into the ring. Claim 12 In paragraph 11, one or more R 1 is in the para position for N coordinating to Ir, and one or more R 4 is a compound in the para position relative to the carbon coordinately bonded to Ir. Claim 13 In Paragraph 11, R 1 and R 1' One or more of and R 4 and R 4' Compounds in which one or more are selected from the group consisting of: Claim 14 In paragraph 1, a compound selected from the group consisting of the following: Claim 15 Organic light-emitting diode (OLED) comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode and comprising a compound having a chemical formula selected from the group consisting of: In the above formula, rings A, B, C, D, E, and F are each pentar or hexaar carbon-ring or heterocyclic rings; in Chemical Formula I: AB, CD, and EF are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB, CD, and EF are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to ring E, and ring C is in a trans position with respect to ring F; in Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB and CD are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to the oxygen atom, and ring C is in a trans position with respect to the oxygen atom; in Chemical Formula III: L 1 and L 3 Each is independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; If n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; If n1 or n2 is 0, L 2 or L 4 is not present; Q 1 , Q 2 , Q 3 and Q 4 Each is independently selected from the group consisting of directly bonded and oxygen; arbitrary Z 1 , Z 2 , Z 3 and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 and Q 4 is a direct coupling; in a square planar coordination arrangement, ring A is transposition with respect to ring D, ring B is transposition with respect to ring C, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution, the maximum possible number of substitutions, or no substitution; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; the first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between the atoms of; the second distance is M 1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between the atoms of; the third distance is M 1 The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between the atoms of; the fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between the atoms of; the fifth distance is M 2 The furthest R from 2 M in the atom of 2 The furthest R from 3 The distance between atoms of; the first distance is at least 1.5 Å longer than the second and third distances, respectively; the fourth distance is at least 1.5 Å longer than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are arbitrarily connected or condensed into the ring. Claim 16 In paragraph 15, the organic layer is a light-emitting layer and the compound is a light-emitting dopant or a non-light-emitting dopant in the OLED. Claim 17 An OLED according to claim 15, wherein the organic layer further comprises a host, and the host comprises one or more chemical groups selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. Claim 18 In paragraph 15, the organic layer additionally includes a host, and the host OLED selected from a group consisting of combinations thereof. Claim 19 A consumer product comprising an organic light-emitting device comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode and comprising a compound having a chemical formula selected from the group consisting of: In the above formula, rings A, B, C, D, E, and F are each pentar or hexaar carbon-ring or heterocyclic rings; in Chemical Formula I: AB, CD, and EF are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB, CD, and EF are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to ring E, and ring C is in a trans position with respect to ring F; in Chemical Formula II: AB, CD, and one acetylacetonate ligand are metal M 1 Forms three bidentate ligands that coordinate with respect to; AB and CD are different from each other; In the octahedral coordination arrangement, ring A is in a trans position with respect to ring D, ring B is in a trans position with respect to the oxygen atom, and ring C is in a trans position with respect to the oxygen atom; in Chemical Formula III: L 1 and L 3 Each is independently selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; If n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of direct bonds, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR', alkyl, and combinations thereof; If n1 or n2 is 0, L2 or L4 does not exist; Q 1 , Q 2 , Q 3 and Q 4 Each is independently selected from the group consisting of directly bonded and oxygen; arbitrary Z 1 , Z 2 , Z 3 and Z 4 If is nitrogen, Q bonded here 1 , Q 2 , Q 3 and Q 4 is a direct coupling; in a square planar coordination arrangement, ring A is transposition with respect to ring D, ring B is transposition with respect to ring C, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each represents a uniform substitution, the maximum possible number of substitutions, or no substitution; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 It is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; the first distance is M 1 The furthest R from 1 M in the atom of 1 The furthest R from 4 It is the distance between the atoms of; the second distance is M 1 The furthest R from 2 M in the atom of 1 The furthest R from 5 It is the distance between the atoms of; the third distance is M 1 The furthest R from 3 M in the atom of 1 The furthest R from 6 It is the distance between the atoms of; the fourth distance is M 2 The furthest R from 1 M in the atom of 2 The furthest R from 4 It is the distance between the atoms of; the fifth distance is M 2 The furthest R from 2 M in the atom of 2 The furthest R from 3 The distance between atoms of; the first distance is at least 1.5 Å longer than the second and third distances, respectively; the fourth distance is at least 1.5 Å longer than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 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, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two of the substituents are arbitrarily connected or condensed into the ring. Claim 20 In paragraph 19, consumer goods selected from the group consisting of flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal information terminals (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, virtual reality or augmented reality displays, automobiles, video walls including multi-displays tiled together, theater or stadium screens, and signage.

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