Organic electroluminescent materials and devices

Abstract

Devices such as organic light emitting diodes with increased efficiency are provided. The present invention discloses a compound having a metal coordination complex structure with at least two ligands coordinated to a metal, the compound having a first substituent R at one position around the ligand. 1 a first distance between the metal and R 1 is defined as the distance between one of the atoms in 1 the atom in the compound is the atom furthest from the metal; the first distance is longer than any other atom-metal distance between the metal and any other atom in the compound; a sphere having a radius r has its center at the metal, and the radius r is such that the sphere is located at the R 1 When the first distance is defined as the smallest radius that allows enclosing all atoms that are not part of the radius r, the first distance is at least 2.9 Å longer than the radius r.

Description

[Technical Field]

[0001] This application claims priority under Section 119(e)(1) of the United States Patent Act to U.S. Provisional Application No. 62 / 352,119 filed June 20, 2016, U.S. Provisional Application No. 62 / 516,329 filed June 7, 2017, U.S. Provisional Application No. 62 / 352,139 filed June 20, 2016, U.S. Provisional Application No. 62 / 450,848 filed January 26, 2017, U.S. Provisional Application No. 62 / 479,795 filed March 31, 2017, and U.S. Provisional Application No. 62 / 480,746 filed April 3, 2017, by reference to the entirety thereof.

[0002] This disclosure relates to compounds for use as phosphorescent materials and to devices such as organic light-emitting diodes containing such compounds. More specifically, this disclosure relates to organometallic complexes having a larger aspect ratio in one direction to increase efficiency and to their use in OLEDs. [Background technology]

[0003] Organic optoelectronic devices are becoming increasingly desirable for several reasons. Because many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. In addition, due to the inherent properties of organic materials, such as flexibility, they can be well-suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photocells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials. For example, the wavelength of light emitted by the organic light-emitting layer can generally be easily adjusted with appropriate dopants.

[0004] OLEDs utilize a thin organic film that emits light when a voltage is applied to the entire device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in Patent Documents 1, 2, and 3, which are incorporated herein by reference in their entirety.

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

[0006] An example of a green light-emitting molecule is shown below: [ka] This is tris(2-phenyl)iridium, represented as Ir(ppy)3, which has the following properties:

[0007] In these drawings and subsequent drawings in this specification, the inventors depict the coordination bond from nitrogen to a metal (here, Ir) as a straight line.

[0008] As used herein, the term “organic” includes polymer materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecule” can actually be quite large. Small molecules can contain repeating units in some contexts. For example, using long-chain alkyl groups as substituents does not exclude molecules from the “small molecule” class. Small molecules may be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of said backbone. Small molecules can also serve as the core portion of a dendrimer, which consists of a series of chemical shells constructed on a core portion. The core portion of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be “small molecules,” and all dendrimers currently used in the field of OLEDs are considered to be small molecules.

[0009] In this specification, “top” means the part furthest from the substrate, while “bottom” means the part closest to the substrate. When the first layer is described as being “placed on top of” the second layer, the first layer is located further from the substrate. There may be other layers between the first and second layers unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as being “placed on top of” the anode, even if there are various organic layers in between.

[0010] As used herein, “solution processable” means that it can be dissolved, dispersed or transported in any liquid medium, either in solution or suspension form, and / or deposited from said medium.

[0011] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the light-emitting material. A ligand may be referred to as "auxiliary" if it is not considered to contribute to the photoactive properties of the light-emitting material, although auxiliary ligands can alter the properties of photoactive ligands.

[0012] As will be generally understood by those skilled in the art when used herein, the first “highest occupied molecular orbital” (HOMO) or “lowest empty molecular orbital” (LUMO) energy level is “greater” or “higher” than the second HOMO or LUMO energy level, if the first energy level is close to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. “Higher” HOMO or LUMO energy levels appear to be closer to the top of such a diagram than “lower” HOMO or LUMO energy levels.

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

[0014] Further details and the definitions described above regarding OLEDs can be found in Patent Document 4, which is incorporated herein by reference in its entirety. [Overview of the project]

[0015] According to aspects of this disclosure, a compound having a metal-coordinate complex structure having at least two ligands coordinated to a metal is disclosed. The compound has a first substituent R at one location around the ligand. 1It has; the first distance is between the metal and R 1 Defined as the distance between one of the atoms in the R, the atom is R 1 Among the atoms in the compound, the one furthest from the metal; the first distance is longer than any other atom-metal distance between the metal and any other atom in the compound; a sphere having radius r has its center in the metal, and the radius r is such that the sphere is located in the compound. 1 If defined as the smallest radius that can enclose all atoms that are not part of the first distance, then the first distance is at least 2.9 Å longer than the radius r.

[0016] In another embodiment, an OLED is disclosed comprising: an anode; a cathode; and an organic layer comprising a compound disposed between the anode and the cathode and having a metal-coordinate complex structure. The compound can function as a light-emitting element in an organic light-emitting device at room temperature; the compound has at least two ligands coordinated to the metal; and the compound has a first substituent R at one location around the ligand. 1 It has; the first distance is the distance between the metal and the R that is furthest away from the metal. 1 The distance between atoms in the compound; the first distance is longer than any distance between the metal and any other atom in the compound; a sphere having radius r has its center the metal, and the radius r is such that the sphere is R in the compound 1 If defined as the smallest radius that would allow the enclosing of all atoms that are not part of the first distance, then the first distance is at least 2.9 Å longer than the radius r.

[0017] In another embodiment, an OLED is disclosed comprising: an anode; a cathode; and an emissive layer disposed between the anode and the cathode, comprising a phosphorescent compound. The phosphorescent compound has an intrinsic emission spectrum having a full width at half maximum (FWHM) value of 40 nm or less. The OLED emits an emission of 0.1 mA / cm² at room temperature when a voltage is applied across the device. 2 It has an EQE of at least 25% as measured.

[0018] According to another aspect, a consumer product including an OLED is disclosed. The OLED includes an anode; a cathode; and an organic layer disposed between the anode and the cathode and including a compound having a metal coordination complex structure. The compound can function as a light emitter in an organic light emitting device at room temperature; the compound has at least two ligands coordinated to the metal; the compound has a first substituent R at one location around the ligand 1 including; a first distance is the distance between the metal and the atom in R that is farthest away from the metal 1 wherein; the first distance is longer than any distance between the metal and any other atom in the compound; a sphere having a radius r has its center at the metal, and the radius r is defined as the smallest radius that allows the sphere to enclose all atoms that are not part of the R portion in the compound, the first distance is at least 2.9 Å longer than the radius r. 1

[0019] According to another aspect, a consumer product including an OLED is disclosed, the OLED includes an anode; a cathode; and a light emitting layer disposed between the anode and the cathode and including a phosphorescent compound; the phosphorescent compound has an intrinsic emission spectrum with a FWHM value of 40 nm or less and has at least 25% EQE measured at room temperature, 0.1 mA / cm 2 when a voltage is applied across the device. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0021] [Figure 2] FIG. 2 shows an inverted organic light emitting device having no separate electron transport layer.

[0022] [Figure 3] FIG. 3 shows an example of a 2-phenylpyridine-based iridium phosphorescent emitter.

[0023] [Figure 4] Figure 4 shows an example of a pyridine structure in which the transition dipole moment vector (dashed line) is substituted at position 4, which is along the long axis of the molecule.

[0024] [Figure 5] Figure 5 shows an example of a phenylpyridine ligand that enables long-axis alignment with the TDM vector, represented by the dashed lines, for substitutions at R1, R2, R3, and R4.

[0025] [Figure 6] Figure 6 shows the structure in which the nitrogen-bonded CN ligand of trans is bound to a diketone that introduces C2 rotational symmetry.

[0026] [Figure 7] Figure 7 is a schematic diagram of the nitrogen axis of the transformer, and the TDM vector and major axis in which this axis is located, showing the preferred alignment.

[0027] [Figure 8] Figure 8 shows a schematic diagram of the C3 or pseudo-C3 symmetric structure and the R1, R2, and R3 molecular long axes, as well as the preferred alignment of the TDM vector having this C3 plane of rotation.

[0028] [Figure 9] Figure 9 shows one possible ligand substitution pattern that enables molecular long axis and TDM alignment with a C3 rotation plane for fac-tris-bidentate organometallic emitters.

[0029] [Figure 10] Figure 10 shows an example of a bottom-emission OLED device stack for determining EQE without optical enhancement.

[0030] [Figure 11]Figure 11 shows the experimental setup for an angle-dependent photoluminescence experiment used to measure the alignment of the light emitter.

[0031] [Figure 12] Figure 12 shows experimental data comparing horizontally oriented luminescent compound 152 with randomly (isotropically) oriented luminescent tris(2-phenylpyridine)iridium. [Modes for carrying out the invention]

[0032] Generally, an OLED includes at least one organic layer positioned between the anode and cathode and electrically connected to them. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons move to the oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. Light is emitted via a photoemission mechanism when the exciton relaxes. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may occur, but these are generally considered undesirable.

[0033] Early OLEDs used light-emitting molecules ("fluorescent") that emitted light from their singlet state, as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated in its entirety by reference. Fluorescence emission generally occurs within a timeframe of less than 10 nanoseconds.

[0034] More recently, OLEDs with light-emitting materials that emit light from a triplet state ("phosphorescence") have been demonstrated. See, in their entirety, Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Vol. 395, pp. 151-154, 1998 ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, pp. 4-6 (1999) ("Baldo-II"). Phosphorescence is described in further detail in U.S. Patent No. 7,279,704, paragraphs 5-6, which is incorporated by reference.

[0035] Figure 1 shows an organic light-emitting device 100. The figure is not necessarily to a constant scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light-emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as examples of materials, are described in further detail in US7,279,704, sections 6-10, which are incorporated by reference.

[0036] Further examples are available for each of these layers. For example, flexible and transparent substrate-anode combinations are disclosed in U.S. Patent No. 5,844,363, which is incorporated in its entirety by reference. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication 2003 / 0230980, which is incorporated in its entirety by reference. Examples of luminescent and host materials are disclosed in Thompson et al., U.S. Patent No. 6,303,238, which is incorporated in its entirety by reference. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication 2003 / 0230980, which is incorporated in its entirety by reference. U.S. Patents 5,703,436 and 5,707,745, which are incorporated in their entirety by reference, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with a transparent, conductive, sputtered-deposited ITO layer covering it. The theory and use of blocking layers are described in more detail in U.S. Patents 6,097,147 and U.S. Patent Application Publication 2003 / 0230980, which are incorporated in their entirety by reference. An example of an injection layer is provided in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference. A description of a protective layer can be found in U.S. Patent Application Publication 2004 / 0174116, which is incorporated in its entirety by reference.

[0037] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the described layers in order. The most common OLED configuration has a cathode positioned above the anode, and since device 200 has a cathode 215 positioned below the anode 230, device 200 is sometimes referred to as an "inverted" OLED. The same materials described for device 100 may be used in the corresponding layers of device 200. Figure 2 provides an example of how some layers may be omitted from the structure of device 100.

[0038] The simple layered structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention may be used in relation to a wide variety of other structures. The specific materials and structures described are substantially illustrative, and other materials and structures may be used. Functional OLEDs may be realized by combining the various layers described in various ways, or layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Many of the examples provided herein describe various layers as containing a single material, but it is understood that combinations of materials, such as host and dopant mixtures, or more generally, mixtures, may be used. Furthermore, layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 225 transports holes and injects them into the light-emitting layer 220, and may be described as a hole transport layer or hole injection layer. In one embodiment, the OLED may be described as having an “organic layer” positioned between the cathode and the anode. The organic layer may consist of a single layer or may further consist of multiple layers of different organic materials, as described, for example, with respect to Figures 1 and 2.

[0039] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of polymer materials, as disclosed in U.S. Patent No. 5,247,190 by Friend et al., which is incorporated in whole by reference. Further examples include OLEDs having a single organic layer. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 by Forrest et al., which is incorporated in whole by reference. OLED structures may deviate from the simple layered structures illustrated in Figures 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 by Forrest et al., which is incorporated in whole by reference, and / or a recessed structure as described in U.S. Patent No. 5,834,893 by Bulovic et al.

[0040] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal deposition, such as those described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference; inkjet deposition; organic vapor deposition (OVPD), such as those described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated by reference; and organic vapor jet printing (OVJP), such as those described in U.S. Patent No. 7,431,968, which are incorporated by reference. Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal deposition. Preferred patterning methods include those described in U.S. Patents No. 6,294,398 and No. 6,468,819, which are incorporated in whole by reference, as well as patterning related to some deposition methods such as inkjet and OVJD. Other methods may be used. The material to be deposited may be modified to suit a particular deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbon atoms, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbon atoms may be used, with 3 to 20 carbon atoms being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures because asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0041] Devices fabricated according to embodiments of the present invention may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors and / or gases. The barrier layer may be deposited on, below, or next to the substrate, electrodes, or on any other part of the device, including edges. The barrier layer may consist of a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include single-phase and multi-phase compositions. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymer and non-polymer materials as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For a material to be considered a "mixture," the polymer and non-polymer materials constituting the barrier layer must be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymer material to non-polymer material can be in the range of 95:5 to 5:95. The polymer and non-polymer materials can be made from the same precursor material. In one example, a mixture of polymer and non-polymer materials essentially consists of polymer silicon and inorganic silicon.

[0042] Devices fabricated according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical products or intermediate components include display screens and lighting devices (such as discrete light source devices or lighting panels) that can be used by end-user product manufacturers. Such electronic component modules may optionally include drive electronics and / or power supplies. Devices fabricated according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more incorporated electronic component modules (or units). Such consumer products include any type of product that includes one or more light sources and / or one or more of a certain type of display device. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and / or signal transmission lights, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonally), 3-D displays, virtual reality or augmented reality displays, cars, video walls including multiple displays arranged side-by-side, theater or stadium screens, and billboards. Devices manufactured according to the present invention can be controlled using various control mechanisms, including passive matrices and active matrices. Many of the devices are intended for use within a human-comfortable temperature range, such as 18 to 30 degrees Celsius, more preferably room temperature (20 to 25 degrees Celsius), but can also be used outside this temperature range, for example, -40 to +80 degrees Celsius.

[0043] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use these materials and structures. More generally, organic devices such as organic transistors may use these materials and structures.

[0044] In this specification, the terms "halo," "halogen," or "halide" include fluorine, chlorine, bromine, and iodine.

[0045] In this specification, the term "alkyl" means both linear and branched alkyl groups. Preferred alkyl groups include those containing 1 to 15 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Furthermore, the alkyl groups may be substituted.

[0046] In this specification, the term "cycloalkyl" means a cyclic alkyl group. Preferred cycloalkyl groups include those containing 3 to 10 ring carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl. Furthermore, the cycloalkyl groups may be substituted.

[0047] In this specification, the term "alkenyl" means both linear and branched alkenyl groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl groups may be substituted.

[0048] In this specification, the term "alkynyl" means both linear and branched alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be substituted.

[0049] In this specification, the terms "aralkyl" and "arylalkyl" are interchangeable and mean alkyl groups having aromatic groups as substituents. Furthermore, the aralkyl groups may be substituted.

[0050] In this specification, the term “heterocyclic group” means aromatic and non-aromatic ring groups. A heteroaromatic ring group also means a heteroaryl group. Preferred heterononaromatic ring groups are at least one heteroatom containing 3 to 7 ring atoms and include cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers such as tetrahydrofuran and tetrahydropyran. Furthermore, the heterocyclic group may be substituted.

[0051] In this specification, the terms “aryl” or “aromatic group” mean monocyclic and polycyclic systems. A polycyclic system may have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are “condensed”), at least one of which is aromatic, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6 carbon atoms, 10 carbon atoms, or 12 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthlene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl group may be substituted.

[0052] In this specification, the term “heteroaryl” means a monocyclic heteroaromatic group that may contain 1 to 5 heteroatoms. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are co-located by two adjacent rings (the rings are “condensed”), at least one of which is a heteroaryl, and for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups contain 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiaidine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, and Examples include nzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzoflopyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, with dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azavolin, 1,3-azavolin, 1,4-azavolin, borazine, and aza analogs thereof. Furthermore, the heteroaryl group may be substituted.

[0053] The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl atoms may be unsubstituted or substituted with one or more substituents selected from deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof.

[0054] In this specification, "substituted" indicates that a substituent other than H is bonded to a related position such as carbon. Therefore, for example, R 1 If R is a one-substitution, 1 It must be something other than H. Similarly, R 1 If R is a disubstituted, 1 Two of them must be other than H. Similarly, R 1 If R is unsubstituted, 1 It is hydrogen at all substitution positions.

[0055] In this specification, the term "aza" in fragments such as aza-dibenzofuran and aza-dibenzothiophene means that one or more CH groups in each fragment can be replaced by nitrogen atoms. For example, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline, without limiting it. Those skilled in the art will readily conceive of other nitrogen analogs of the aza derivatives described above, and all such analogs are intended to be encompassed by the terms used herein.

[0056] When a molecular fragment is described as a substituent or as being attached to another part, it should be understood that its name may be written as either the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the whole molecule (benzene, naphthalene, dibenzofuran). In this specification, even if the substituent or attached fragment is described differently, these are considered equivalent.

[0057] In this disclosure, we describe a method for achieving emitter transition dipole alignment to improve OLED device performance. By increasing the horizontal alignment of the vectors of the transition dipole moments, which are crucial for photon emission in individual emitters, outcoupling is increased, thereby increasing efficiency. Increasing the aspect ratio of the emitter molecules enables anisotropic coordination of emitters in OLED EMLs through increased linearity or planarity. The correlation between the transition dipole moment and this linear major axis or plane allows for the conversion of emitter orientation to transition dipole orientation, enabling improved optical outcoupling. These changes can improve optical outcoupling and device efficiency by up to 50% compared to randomly oriented emitters.

[0058] Alignment of Emission Transition Dipole Moment: The methods described herein improve OLED performance by maximizing photo-outcoupling through molecular alignment. Despite the extremely high exciton conversion efficiency and emission quantum yield achieved by phosphorescent OLED materials, device efficiency is ultimately limited by photo-extraction efficiency. The extraction of photons emitted from the emissive layer (EML) of an OLED stack is highly dependent on the direction of photon emission. Photons propagating perpendicular to the device substrate have a high probability of extraction. On the other hand, photons propagating at a high angle to the direction orthogonal to the substrate are more likely to be lost or not extracted due to internal reflection, waveguide modes, and coupling to surface plasmon modes.

[0059] In individual luminescent compounds, light emission occurs perpendicular to the transition dipole moment (TDM) from the triplet state to the ground state. Thus, increasing the number of luminescent compound molecules whose TDM vectors are aligned horizontally with respect to the OLED substrate leads to higher light extraction efficiency, and consequently, higher device efficiency (external quantum efficiency - EQE). This horizontal orientation factor can be statistically described for an ensemble of luminescent molecules by the ratio θ of the horizontal component of the TDM vector to the sum of the vertical component (TDM⊥) and the horizontal component (TDM||). In other words, θ = TDM|| / (TDM⊥+TDM||). The ratio θ will be referred to below as the horizontal dipole ratio (HDR).

[0060] The horizontal dipole ratio θ can be measured by angle-dependent photoluminescence measurements. As a polarization function, the TDM vector orientation can be determined for a given sample by comparing the measured emission pattern with a computationally modeled pattern of a photoexcited thin film sample. The horizontal dipole ratio θ has a very significant effect on the resulting device efficiency. In a typical bottom-emission device structure (shown in Figure 10) without microcavities or other optical enhancements and with a material refractive index of approximately 1.5–2.0, a randomly oriented emitter (θ=0.67) exhibits quantitative emission and charge recombination efficiency (very low current density <1 mA / cm²). 2 Assuming that this is achievable, a maximum device EQE of approximately 28% can be achieved. For a perfectly horizontal light-emitting element with θ=1, an EQE of over 40% is achievable in an OLED device with 100% PLQY and 100% charge recombination efficiency.

[0061] Generally, the increase in luminescence outcoupling depends on two factors: (1) the triplet-to-ground state TDM vector alignment in the luminescent compound molecule; and (2) the molecular alignment of the luminescent material within the EML structure. Thus, it is necessary to control both factors in a coordinated manner to effectively achieve TDM vector alignment and enhance OLED performance. Furthermore, neither factor is separate from the other; rather, they represent the distribution of alignment. Near-degenerate luminescence optical transitions can result in differently oriented TDM vector distributions, which are described by Boltzmann statistics. Structurally, the molecular alignment of the luminescent material in an amorphous EML medium results in a distribution of luminescent material alignment, which can vary across the EML layer. Thus, performance enhancement of the device can be achieved through preferential luminescence from a single optical transition within the device EML and strong alignment of this transition.

[0062] Single TDM vector molecular alignment: To achieve a straight (aligned) TDM vector within the device, a preferential (selective) luminescent alignment must be injected into the host and luminescent materials. This can primarily be achieved through high aspect ratio luminescent molecules. It has been observed that in nominal amorphous films fabricated by methods such as thermal deposition, spin coating, inkjet printing, and organic vapor jet printing, high aspect ratio rod-shaped or disc-shaped structures can be preferentially oriented.

[0063] In luminescent materials with a single preferential emission transition, a rod-like structure can be selected to optimize the alignment of the TDM vector while further minimizing the molecular weight. This can be achieved in luminescent materials with the same structure as tris(2-phenylpyridine)iridium (Ir(ppy)3, Figure 3) by generating a long molecular axis extending through the iridium metal center. The orientation of the long molecular axis can depend on the orientation of the TDM vector, as described below.

[0064] Regarding Figure 4, in the case of a light emitter where the TDM vector is roughly aligned with the iridium-nitrogen bond (indicated by the dashed arrow), the pyridine 4th position (R in Figure 4) 1 The molecular long axis can be generated by appropriate substitution at ). For example, aryl, heteroaryl, alkyl, or cycloalkyl substituents can be introduced at this position to promote the formation of a high aspect ratio rod-like structure through which the molecular long axis roughly passes over the iridium-nitrogen bond and the substituent. We aim to align the TDM vector axis with this high aspect ratio molecular long axis, so that the angle between these two axes is preferably less than 30°, more preferably less than 10°. 1 The preferred length is in the range of 3 Å to 15 Å, more preferably in the range of 4 Å to 9 Å. By wisely selecting substituents and applying the above molecular design, we can achieve an HDR of up to 0.85 and thereby a significant increase in EQE.

[0065] Similarly, the rod-like structure can be used in luminescent molecules containing a single preferred TDM vector that roughly divides the bidentate luminescent ligand (see Figure 5, shown by the dashed line). In this case, the molecular long axis that roughly divides the bidentate luminescent ligand can be generated by elongation using aryl, heteroaryl, alkyl, or cycloalkyl substitutions at the pyridine 3 and 4 positions, in combination with substitutions at the 5th and 6th positions of phenyl. For example, alkyl substitution at the 4th position of pyridine and condensed heteroaryl substitutions at the 5th and 6th positions of phenyl result in net elongation in the direction of the TDM vector. Similarly, twisted aryl substitution at the 6th position of phenyl results in more rod-like elongation along this TDM vector axis. We aim to align the TDM vector axis with this high aspect ratio molecular long axis, with the angle between these two axes preferably less than 30°, more preferably less than 10°. Substituent R 1 / R 2 and R 3 / R 4The preferred length is in the range of 3 Å to 15 Å, more preferably in the range of 4 Å to 9 Å. Since this substitution pattern induces a larger planar shape and can be aligned with the EML surface, we anticipate further improved HDR up to 0.9.

[0066] Ligand Energy Gap: In homoreptic iridium emitters, the three bidentate ligands are all the same, and the degeneracy of the three optical transitions results in random transition dipole orientation. In homoreptic emitters, emission can also be dispersed between degenerate or near-degenerate transitions. These transitions can be concentrated on different ligands, thereby largely resulting in orthogonal TDM vectors. This leads to overall scrambling of any emission alignment that may be obtained from molecular alignment.

[0067] It is noteworthy that very small energy gaps between nearly identical phenylpyridine ligands result in high isotropic luminescence in Ir(ppy)3 type emitters, even in strongly oriented rod-shaped structures. In these cases, Boltzmann statistics primarily describe the possibility of luminescence from near-degenerate transitions. Thus, it is evident that the localization of luminescence transitions is highly sensitive to the energy gaps between the various transitions being discussed. To strongly localize luminescence and improve TDM alignment, the preferred energy gap between the luminescence ligands of the luminescence center and the auxiliary ligands is higher than 0.05 eV, and more preferably 0.10 eV.

[0068] Furthermore, any preferred alignment induced by a major axis located along one of the ligands that does not primarily contribute to the emission transition can result in a low horizontal dipole ratio θ. This case, where one of the aforementioned alignment motifs is applied to one of the luminescent auxiliary ligands, should be avoided as it can result in an HDR value lower than 0.67 (isotropic orientation).

[0069] Symmetry and Geometry of TDM Vectors: When a large energy gap cannot be obtained through energy tuning of the luminescence and auxiliary ligand structures, symmetry and molecular geometry are used to generate highly aligned luminescence from multiple ligands, as in the case of many high-energy blue and green emitters. Note the highly orthogonal nature of the degenerate TDM vector of Ir(ppy)3, and the perfectly parallel nature of that of diketone-coordinated red emitters with symmetric luminescence ligands. In the case of degenerate luminescence, these perpendicular and parallel relationships cause negation and enhancement of arbitrarily aligned luminescence due to molecular alignment in EML, respectively.

[0070] In these diketone-coordinated iridium emitters, the preferential trans orientation of the iridium-nitrogen bond results in C2 axis symmetry in the structure. See Figure 6. We propose using this C2 axis to enhance the alignment induced by the extension of the TDM vector axis. See Figure 7. The non-ketone ligand is designed to have (1) a TDM vector and (2) a steric long axis aligned with the Ir-N bond, and the C2 symmetry enhances the alignment by parallel TDM vectors on the two emitter ligands. This enables very high HDR values ​​exceeding 0.85.

[0071] With respect to the Tris-substituted compounds, it is preferable that the luminescence is concentrated in each of the three ligands, and that the plane containing the three rotationally symmetric compounds, (1) the TDM vector, and (2) the major axis be aligned in a straight line, such that they are equal or nearly equal. In these homoreptic fac compounds, this C3 plane roughly bisects the angle between the two metal ligand bonds of each bidentate ligand. See Figure 8. Thus, the TDM vector of these complexes roughly bisects this angle, and the angle between the C3 plane and the TDM vector is less than 20°, more preferably less than 10°.

[0072] If a change in aspect ratio induces a preferential horizontal alignment of this plane, the resulting planar or nearly planar alignment of the three TDM vectors contributes to achieving efficiency. Lengthening each ligand along this C3 plane results in a very flat structure with a high aspect ratio. One such structure is shown in Figure 9, where R is alkyl, cycloalkyl, aryl, or heteroaryl. The same R can also be placed in a similar position on the pyridine ring. The molecular aspect ratio is determined by the radius between the metal center and the end of the R group, which is preferably longer than 4 Å and more preferably longer than 8 Å. Furthermore, it is preferable to have a vector between the metal center and the end of the R group in the C3 plane where the angle between the vector and the plane is less than 20°, more preferably less than 10°.

[0073] It is possible to develop an emissive device containing two identical emissive ligands, or more generally, two ligands that primarily contribute to luminescence, where the major axis and TDM vector are not orthogonal. For each ligand, the major axis and TDM vector can be collinear, as described above. When this major axis of one ligand is at a large angle (φ) with respect to that of the second emissive ligand, an enhancement of device efficiency can be observed. In this case, since the emissive molecular alignment can be described by the orientation distribution in amorphous EML, a bent shape of 90° < φ < 180°, due to the major axis formed between the two ligands and both TDM vectors being roughly in a straight line, results in an enhancement of device efficiency. This is achieved by the TDM vector preferably bisecting the bidentate ligand and being slightly outside the ligand plane. We propose using a near-degenerate or degenerate luminescent ligand with a pseudo-symmetric orientation of TDM to achieve an HDR value greater than 0.7, more preferably 0.8.

[0074] Host-Induced Dopant Alignment: Since the alignment of luminescent molecules within EMLs arises from various interactions between the luminescent molecules and the EML material and the deposition medium (vacuum, air, inert gas, solvent, etc.), the interaction between the host and the luminescent material is expected to have an effect on the resulting orientation of the luminescent TDM vector. Electrostatic interactions act to flatten high aspect ratio luminescent molecules within the EML structure, while other strong host-luminescent interactions can be used to influence alignment. These interactions may include pie stacking, hydrogen bonding, the use of strongly interacting functional groups (including polar groups, nonpolar groups, fluorinated groups, or alkyl groups that can interact between host / dopant or drive intercalation or separation effects), and donor-acceptor pie interactions acted upon by interactions between electron-rich and electron-deficient aromatic moieties.

[0075] Optimizing the luminescent-host interaction that induces dopant alignment strongly depends on the planarity of the dopant and / or host molecules. In particular, if strong pie-stacking interactions result in alignment, increased planarity of these molecules is expected to result in stronger interactions, and thereby a higher degree of alignment. In this case, it is preferable to cleverly introduce two-plane twists of the pie plane, increasing the number of two aligning aromatic rings within the molecule and increasing the overall planarity of the dopant. Through the same strategy, it is also desirable to increase not only the planarity of the host molecule but also the conjugation length, the charge transfer properties in the host, and the intermolecular and intramolecular hydrogen bonding. These differences in host-induced luminescent alignment can be directly measured by photoluminescence techniques in a luminescent:host sample for luminescent:mCP (where mCP is 1,3-bis(N-carbazolyl)benzene, a disordered, unoriented host).

[0076] It is also preferable to introduce these linear or template motifs into the electron blocking layer (EBL) or other underlying layers to such an extent that the underlying layers of the device stack affect the alignment of the host or dopant material near the interface.

[0077] According to aspects of this disclosure, compounds having a metal-coordinate complex structure are disclosed, which can function as light-emitting elements in an OLED at room temperature. For the purposes of this description, room temperature means a temperature range of 20°C to 25°C. The compound has at least two ligands coordinated to the metal; the compound has a first substituent R at one location around the ligand 1 It has; the first distance is between the metal and R 1 Defined as the distance between one of the atoms in the R, the atom is R 1 Among the atoms in the compound, the one furthest from the metal; the first distance is longer than any other atom-metal distance between the metal and any other atom in the compound; the sphere having radius r has its center in the metal, and the radius r is such that the sphere is R in the compound. 1 If the first distance is defined as the smallest radius that allows enclosing all atoms except those in the phenyl ring, then the first distance is at least 2.9 Å longer than the radius r, where 2.9 Å represents the diameter of the phenyl ring. The sphere defined above is the R enclosed by the sphere. 1 No atoms within the sphere shall be excluded. In this specification, “enclosed by the sphere” means that the atoms are located at a distance of radius r or less from the metal.

[0078] In some embodiments of the compound, the first distance is at least 4.3 Å longer than the radius r. In some embodiments of the compound, the first distance is at least 7.3 Å longer than the radius r.

[0079] In some embodiments of the compound, the compound has a second substituent R at one location around the ligand. 2 It further has a second distance between the metal and R 2Defined as the distance between one of the atoms in the R, the atom is R 2 Among the atoms in the compound, the one furthest from the metal; the radius r is such that the spherical shape is R in the compound. 1 or R 2 The second distance is at least 1.5 Å longer than r, if it is the smallest radius that allows enclosing all atoms that are not part of the r.

[0080] The second substituent R 2 In some embodiments of compounds having R 1 and R 2 , are on different ligands. In some embodiments of the compound, the second distance is at least 2.9 Å longer than r. In some embodiments, the second distance is at least 4.3 Å longer than r. In some embodiments, the second distance is at least 7.3 Å longer than r. In some embodiments, both the first distance and the second distance are at least 4.3 Å longer than r. In some embodiments, both the first distance and the second distance are at least 7.3 Å longer than r.

[0081] The second substituent R 2 In some embodiments of compounds having R 1 It is bonded to an aromatic ring having a first coordination atom, R 2 The first coordinating atom is bonded to an aromatic ring having a second coordinating atom, and the first coordinating atom is in a trans configuration with respect to the metal and the second coordinating atom.

[0082] In some embodiments of the compound, the compound has a third substituent R at one location around the ligand. 3 It further has; the third distance is between the metal and R 3 Defined as the distance between one of the atoms in the R, the atom is R 3 Among the atoms in the compound, the one furthest from the metal; the radius r is such that the spherical shape is R in the compound. 1 , R 2 , or R 3The third distance is at least 1.5 Å longer than r, if it is the smallest radius that allows enclosing all atoms that are not part of the r.

[0083] The third substituent R 3 In some embodiments of compounds having the substituent R 1 , R 2 , and R 3 These are located on different ligands. In some embodiments of the compound, the third distance is at least 2.9 Å longer than r. In some embodiments, the third distance is at least 4.3 Å longer than r. In some embodiments, the third distance is at least 7.3 Å longer than r.

[0084] Table 1 below shows the maximum linear lengths for various substituents defined along the long axis. This maximum linear length is defined as the distance between the two furthest apart atoms along the long axis of a particular substituent. Using the values ​​shown, estimate to what extent a given substituent at one point around a ligand in the coordination complex extends beyond the radius r of the sphere surrounding all atoms in the coordination complex that are not part of the particular substituent. For example, the first substituent R 1 In the embodiment of the coordination complex having only the first substituent R, the distance between the first distance and the radius r is given by the first substituent R, using Table 1. 1 Depending on the specific chemical group contained therein, it can be estimated. The embodiment of the coordination complex is such that in the complex, one or more ligands contain the second substituent R 2 and the third substituent R 3 If additional substituents such as the above are present, use Table 1 to determine the substituent R 2 or R 3By considering the specific substituents contained in the fragments, the distance between the second or third distance and the radius r can be estimated. The difference between the two substituents can be calculated using Table 1 below. For example, if the first substituent is phenyl and the second substituent is tolyl, the second substituent is one CC bond (i.e., 1.5 Å) longer than the first substituent. In another example, if the second substituent is biphenyl, the second substituent is C-C6H5 (i.e., 4.3 Å) longer than the first substituent. Any two or more of the following fragments can be linked together, and the distance can be calculated simply by adding these values ​​to the total length of the single CC bond used to connect them. [Table 1]

[0085] The third substituent R 3 In some embodiments of the compound having, the first distance, the second distance, and the third distance are all at least 4.3 Å longer than r. In some embodiments, the first distance, the second distance, and the third distance are all at least 7.3 Å longer than r. In some embodiments, the first distance, the second distance, and the third distance are each independently at least one of the distances shown in Table 1 longer than r. In some further embodiments, the first distance, the second distance, and the third distance are all at least one of the distances shown in Table 1 longer than r.

[0086] The third substituent R 3 In some embodiments of the compound having, the compound has an octahedral coordination geometry comprising three bidentate ligands; each of the three bidentate ligands has two coordination atoms and a central point fractionated between the two coordination atoms; the three central points fractionate a first face; R 1 , R 2 , and R 3Each atom within has a point-to-plane distance of less than 5 Å from the first plane. The "point-to-plane" distance means the shortest distance between a plane and a point that is not on that plane.

[0087] R 3 In some embodiments of compounds having R 1 , R 2 , and R 3 Any atom in the material has a point-to-plane distance of less than 4 Å with respect to the first plane. In some embodiments, R 1 , R 2 , and R 3 Any atom in the material has a point-to-plane distance of less than r with respect to the first plane.

[0088] In some embodiments of the compound, the compound has a transition dipole moment axis; and the transition dipole moment axis and R 1 The angle between the axis along the first distance is less than 40°. The "transition dipole moment axis" is the axis along the transition dipole moment. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 30°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 20°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 15°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 10°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 35°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 25°. In some embodiments, the angle between the transition dipole moment axis and the axis along the first distance is less than 5°.

[0089] R 1 The first distance at is R 2 The second distance and R 3Significantly longer than the third distance in R 2 or R 3 In some embodiments of the aforementioned compound that lacks R, the free energy difference between the luminescence that accumulates on three different ligands is taken into consideration. 1 To compare the free energies of ligands having R 1 A first homoreptic metal complex comprising the same ligand as the ligand having will have a triplet energy at least 0.02 eV lower than a second homoreptic metal complex comprising any of the other ligands in the compound. In other embodiments, the triplet energy of the first homoreptic metal complex is at least 0.05 eV lower than the triplet energy of the second homoreptic metal complex. In other embodiments, the triplet energy of the first homoreptic metal complex is at least 0.1 eV lower than the triplet energy of the second homoreptic metal complex. In other embodiments, the triplet energy of the first homoreptic metal complex is at least 0.15 eV lower than the triplet energy of the second homoreptic metal complex.

[0090] In some embodiments of the above compound, substituent R 1 , R 2 , and R 3 Each of these is independently selected from the following group: [ka] [ka] [ka] [ka]

[0091] In some embodiments of the above-mentioned compounds, the compounds can function as phosphorescent, fluorescent, or delayed-fluorescent materials in an organic light-emitting device at room temperature.

[0092] In some embodiments of the above-mentioned compound, the compound can emit light from a triplet excited state to a ground singlet state at room temperature.

[0093] In some embodiments of the above-mentioned compound, the compound has a metal-carbon bond.

[0094] In some embodiments of the compound, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, Ag, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt.

[0095] In some embodiments of the above-mentioned compounds, the compounds have a neutral charge.

[0096] In some embodiments of the compound, the ligands in the compound are different from each other.

[0097] In some embodiments of the compound, the compound has an octahedral coordination geometry consisting of three bidentate ligands, two tridentate ligands, one tetradentate ligand and one bidentate ligand, or one hexadent ligand.

[0098] In some embodiments of the compound, the compound has a tetrahedral coordination geometry consisting of two bidentate ligands or one tetradentate ligand.

[0099] In some embodiments of the compound, the compound includes a first benzene ring coordinated to the metal, and the first benzene ring is fused with a second aromatic ring. In some embodiments, the second aromatic ring is fused with a third aromatic ring. In some embodiments, the third aromatic ring is fused with a fourth aromatic ring.

[0100] In some embodiments of the compound, the compound is of the formula M(L 1 ) x (L 2 ) y (L 3 ) z ; L 1 , L 2 , and L 3 may be the same or different; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x + y + z is the oxidation state of the metal M; L 1 , L 2 , and L 3 are each independently selected from the group consisting of:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0101] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, substituent R is located within the same ring. a , R b , R c , and R d At least one pair of these elements combine and condense to form a ring.

[0102] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, the substituent R between two nearby rings is a , R b , R c , and R d At least one pair of these elements combine and condense to form a ring.

[0103] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, the compound is Ir(L 1 )2(L 2 It is expressed by the formula ).

[0104] The aforementioned Ir(L 1 )2(L 2 In some embodiments of the compound represented by the formula, L 1 The following: [ka] It is expressed by an expression selected from the group consisting of; L 2 The following: [ka] It is represented as follows. In some embodiments, L 2 The following: [ka] It is represented by; In the formula, R e , R f , R h , and R i These are independently selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl; Re , R f , R h , and R i At least one of them has at least two carbon atoms; R g This is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0105] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, the compound is Ir(L 1 )(L 2 )(L 3 ), Ir(L 1 )2(L 2 ), and Ir(L 1 It is expressed as an expression selected from a group consisting of 3; L 1 , L 2 , and L 3 These are different and each is independently selected from the following groups. [ka] [ka]

[0106] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, the compound is Pt(L 1 )2 or Pt(L 1)(L 2 It is expressed by the formula ). In some embodiments, L 1 is, other L 1 or L 2 It combines with it to form a tetradentate ligand.

[0107] Said M(L 1 ) x (L 2 ) y (L 3 ) z In some embodiments of the compound represented by the formula, the compound is M(L 1 )2 or M(L 1 )(L 2 It is expressed by the formula ) where M is Ir, Rh, Re, Ru, or Os; L 1 and L 2 These are all different tridentate ligands.

[0108] In some embodiments of the above compound, the compound is selected from the group consisting of the following: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0109] According to other aspects of this disclosure, an OLED is disclosed. The OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, comprising a compound having a metal coordination complex structure; The compound can function as a light-emitting element in an organic light-emitting device at room temperature; The compound comprises at least two ligands coordinated to the metal; The compound has a first substituent R at one location around the ligand. 1 Having; The first distance is the distance between the metal and the R that is furthest away from the metal. 1 It is the distance between atoms within it; The first distance is longer than any distance between the metal and any other atom in the compound; A sphere having radius r has the metal at its center, and the radius r is such that the sphere is R in the compound. 1 If defined as the smallest radius that would allow the enclosing of all atoms that are not part of the first distance, then the first distance is at least 2.9 Å longer than the radius r.

[0110] In some embodiments of the OLED, the organic layer is a light-emitting layer, and the compound having a metal coordination complex structure is either a light-emitting dopant or a non-light-emitting dopant.

[0111] In some embodiments of the OLED in which the organic layer further comprises a host, the host comprises a triphenylene containing a benzo-condensed thiophene or a benzo-condensed furan; Any substituent in the host is independently C n H 2n+1 , OC n H 2n+1 ,OAr1,N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, and C n H 2n -A non-condensed substituent selected from the group consisting of Ar1, or the host is unsubstituted; n is between 1 and 10; Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs.

[0112] In some embodiments of the OLED in which the organic layer further comprises a host, the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0113] In some embodiments of the OLED in which the organic layer further includes a host, the host is selected from the group consisting of the following: [ka] [ka]

[0114] In some embodiments of the OLED in which the organic layer further comprises a host, the host comprises a metal complex.

[0115] In some embodiments of the OLED, the compound having a metal coordination complex structure has an HDR of at least 0.7. In some embodiments of the OLED, the compound having a metal coordination complex structure has an HDR of at least 0.75. In some embodiments of the OLED, the compound having a metal coordination complex structure has an HDR of at least 0.8. In some embodiments of the OLED, the HDR of the compound having a metal coordination complex structure is at least 0.85. In some embodiments of the OLED, the HDR of the compound having a metal coordination complex structure is at least 0.9. In some embodiments of the OLED, the HDR of the compound having a metal coordination complex structure is at least 0.95.

[0116] In some embodiments of the OLED, the organic layer further comprises a host; the compound has at least 5% higher HDR compared to the exact same device having mCP (1,3-bis(N-carbazolyl)benzene) as the host. In some embodiments of the OLED, the compound has at least 10% higher HDR compared to the exact same device having mCP as the host. In some embodiments of the OLED, the compound has at least 20% higher HDR compared to the exact same device having mCP as the host. In some embodiments of the OLED, the compound has at least 30% higher HDR compared to the exact same device having mCP as the host. In some embodiments of the OLED, the compound has at least 40% higher HDR compared to the exact same device having mCP as the host.

[0117] In other aspects of the present disclosure, an OLED is disclosed, the OLED comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode, comprising a phosphorescent compound; the phosphorescent compound having an intrinsic emission spectrum having an FWHM value of 45 nm or less, and when a voltage is applied across the device, the OLED emits light at room temperature, 0.1 mA / cm². 2And it has an EQE of at least 25%. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 43 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 41 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 39 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 37 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 35 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 33 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 31 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 29 nm or less. In some embodiments, the FWHM value of the intrinsic emission spectrum of the phosphorescent compound is 27 nm or less. In some embodiments, the OLED has an EQE of at least 27%. In some embodiments, the OLED has an EQE of at least 29%. In some embodiments, the OLED has an EQE of at least 31%. In some embodiments, the device lifetime to 95% brightness is 20 mA / cm². 2 400nm≦λ measured max For a <500nm light emitter, the duration was 8 hours and the current was 80mA / cm². 2 500nm≦λ measured max For a <590nm light emitter, the duration was 30 hours and the current was 80mA / cm². 2 590nm≦λ measured max For a <750nm light emitter, the time is 150 hours. In some embodiments, the device lifetime to 95% brightness is 20 mA / cm². 2 400nm≦λ measured max For a <500nm light emitter, the duration was 12 hours and the current was 80mA / cm². 2 500nm≦λ measured maxFor a <590nm light emitter, the duration was 45 hours and the current was 80mA / cm². 2 590nm≦λ measured max For a <750nm light emitter, the lifespan is 225 hours. In some embodiments, the device lifetime to 95% brightness is 20 mA / cm². 2 400nm≦λ measured max For a <500nm light emitter, the duration was 16 hours and the current was 80mA / cm². 2 500nm≦λ measured max For a <590nm light emitter, the duration was 60 hours and the current was 80mA / cm². 2 590nm≦λ measured max For a <750nm light emitter, the time is 300 hours. In some embodiments, the device lifetime to 95% brightness is 20 mA / cm². 2 400nm≦λ measured max For a <500nm light emitter, the duration was 20 hours and the current was 80mA / cm². 2 500nm≦λ measured max For a <590nm light emitter, the duration was 75 hours and the current was 80mA / cm². 2 590nm≦λ measured max For a <750nm light emitter, the time is 375 hours.

[0118] The intrinsic emission spectrum of a phosphorescent compound is defined as the photoluminescence spectrum of a thin film of a <1% to 10% doped emitter, thermally deposited on the same host material used in the OLED laminate. A person skilled in the art will recognize that the doping rate should be limited to a regime that minimizes quenching and broadening due to aggregation. It is noteworthy that this emission spectrum can exhibit slight broadening or narrowing in the OLED due to optical and chemical factors.

[0119] It has been found that benzoannulation, an aromatic cyclization reaction at the ring containing the ligand, significantly reduces the photoluminescence full width at half maximum (FWHM) of the emitter. Narrowing the photoluminescence spectrum of the emitter improves the performance of devices such as EQEs. For example, when compound A (FWHM: in solution, 65 nm) is condensed with an additional benzene ring, the aromatic compound B has an FWHM of 19 nm, which is considerably narrower than compound A. Similarly, in a solid-state PMMA thin film, compound B has an FWHM of 21 nm, which is 47 nm narrower than compound A (FWHM: 68 nm) in a 5% doped PMMA solid film. [ka]

[0120] In some embodiments of the OLED, the phosphorescent compound is a metal coordination complex, and the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, Ag, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt.

[0121] In some embodiments of the OLED in which the phosphorescent compound is a metal-coordinate complex, the phosphorescent compound is a benzene ring coordinated to the metal; the benzene ring is condensed by a second aromatic ring. In some embodiments, the second aromatic ring is condensed by a third aromatic ring. In some embodiments, the third aromatic ring is condensed by a fourth aromatic ring.

[0122] The phosphorescent compound in the OLED exhibits an intrinsic emission spectrum having an FWHM value of 45 nm or less, and emits light when a voltage is applied across the device at room temperature and 0.1 mA / cm². 2In some embodiments of the OLED having an EQE of at least 25% as measured, the phosphorescent compound has an HDR of at least 0.7. In some embodiments of the OLED, the phosphorescent compound has an HDR of at least 0.75. In some embodiments of the OLED, the phosphorescent compound has an HDR of at least 0.8. In some embodiments of the OLED, the phosphorescent compound has an HDR of at least 0.85. In some embodiments of the OLED, the phosphorescent compound has an HDR of at least 0.9. In some embodiments of the OLED, the phosphorescent compound has an HDR of at least 0.95.

[0123] In some embodiments of the OLED, the phosphorescent compound in the OLED has an intrinsic emission spectrum having an FWHM value of 45 nm or less, and has an EQE of at least 25% at room temperature when a voltage is applied across the device, the light-emitting layer further comprises a host; the compound has a horizontal dipole ratio increased by at least 5% when compared to the exact same device having mCP(1,3-bis(N-carbazolyl)benzene) as the host. In some embodiments, the compound has a horizontal dipole ratio increased by at least 10% when compared to the exact same device having mCP(1,3-bis(N-carbazolyl)benzene) as the host.

[0124] In some embodiments of the OLED, the phosphorescent compound in the OLED has an intrinsic emission spectrum having an FWHM value of 45 nm or less, and an EQE of at least 25% at room temperature when a voltage is applied across the device, the phosphorescent compound is a compound having a metal-coordinate complex structure; the compound can function as a light emitter in an organic light-emitting device at room temperature; the compound has at least two ligands coordinated to the metal; and the compound has a first substituent R at one location around the ligand 1 It has; the first distance is the distance between the metal and the R that is furthest away from the metal. 1is the distance between the metal and an atom in the compound; the first distance is longer than any distance between the metal and any other atom in the compound; a sphere having a radius r has its center at the metal, and the radius r is defined as the smallest radius that allows the sphere to enclose all atoms that are not part of R in the compound 1 in the compound, when defined as such, the first distance is at least 2.9 Å longer than the radius r.

[0125] According to another aspect of the present disclosure, a consumer product including an OLED is disclosed. The OLED includes an anode; a cathode; and an organic layer disposed between the anode and the cathode and including a compound having a metal coordination complex structure; the compound can function as a light emitter in an organic light emitting device at room temperature; the compound includes at least two ligands coordinated to the metal; the compound has a first substituent R at one location around the ligand 1 and the first distance is the distance between the metal and the atom in R that is farthest from the metal<## 1 in the compound, the first distance is longer than any distance between the metal and any other atom in the compound; a sphere having a radius r has its center at the metal, and the radius r is defined as the smallest radius that allows the sphere to enclose all atoms that are not part of R in the compound 1 in the compound, when defined as such, the first distance is at least 2.9 Å longer than the radius r.

[0126] According to another aspect of the present disclosure, a consumer product including an OLED is disclosed. The OLED includes an anode; a cathode; and an organic layer disposed between the anode and the cathode and including a phosphorescent compound; the phosphorescent compound has an intrinsic emission spectrum with a FWHM value of 45 nm or less and has an EQE of at least 25% measured at room temperature at 0.1 mA / cm 2 when a voltage is applied across the device.

[0127] In some embodiments, the consumer products described above include a flat panel display, a computer monitor, a medical monitor, a television, a bulletin board, an indoor or outdoor lighting and / or signaling light, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display, a 3-D display, a virtual reality or augmented reality display, a vehicle, a large area wall, a theater or stadium screen, or a billboard, and are selected from the group consisting of these.

[0128] Examples

[0129] As shown previously, the average transition dipole moment (TDM) alignment of a given representative EML structure can be determined by angular-dependent photoluminescence measurements. The angular dependence of p-polarized emission is very sensitive to the HDR. Thus, the HDR of the EML sample 300 doped with the emitter can be determined by comparing the angular dependence of p-polarized emission e measured as a function of the detection angle φ as shown in FIG. 11 with the angular dependence simulated based on the optical properties of the sample and the contributions of the two in-plane and out-of-plane transition dipole modes.

[0130] Photoluminescence measurements of Compound 152 confirm an increased horizontal alignment of the TDM with the substitution pattern described above. As shown in FIG. 12, the substitution pattern of Compound 152 produces an EML (HDR = 0.73) that is preferentially horizontally aligned, in contrast to the randomly oriented nature of tris(2-phenylpyridine)iridium (HDR = 0.67).

[0131] Synthesis of Compound 152

[0132] Step 1

Chemical formula

[0133] Process 2 [ka] 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 under N2 at 110°C for 12 hours. The reaction mixture was then cooled to room temperature, and the product was extracted by DCM. The organic phase was separated and recovered. The solvent was removed, and the residue was spread on Celite and purified by silica gel column elution with toluene / heptane 70 / 30 (v / v). The product was further purified by recrystallization from toluene / MeOH to obtain compound 152 (0.7 g).

[0134] Synthesis of compound 153 [ka] 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 under N2 at 110°C for 12 hours. The reaction mixture was then cooled to room temperature, and the product was extracted by DCM to separate the organic phase. The solvent was removed, and the residue was spread on Celite and purified by silica gel column elution with toluene / heptane 70 / 30 (v / v). The product was further purified by recrystallization from toluene / MeOH to obtain compound 153 (0.64 g).

[0135] Synthesis of compound 154

[0136] Process 1 [ka] 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 the mixture was stirred for 16 hours. A saturated NaHCO3 (20 mL) solution was added. The organic phase was separated and recovered. The solvent was removed, the residue was spread on Celite, and purified by elution using a silica gel column with 70 / 30 toluene / heptane to obtain the product CC-Br (0.6 g).

[0137] Process 2 [ka] CC-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 for 16 hours under N2. After the reaction was cooled to room temperature, the product was extracted with DCM. The organic phase was separated and recovered. The solvent was removed, and the residue was applied to celite and purified by a silica gel column eluted with 70 / 30 toluene / heptane. The product was further purified by recrystallization with toluene / MeOH to give compound 154 (1.0 g).

[0138] Synthesis of Compound 155

[0139] Step 1 [Chemical formula] Under nitrogen, 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 in a mixture of DME (150 ml) and water (20 ml) to obtain a colorless suspension. Pd(PPh3)4 (0.909 g, 0.786 mmol) was added to the reaction mixture, and then the reaction mixture was degassed and heated to 95 °C for 12 hours. Then, it was cooled to room temperature, the organic layer was separated and evaporated. The residue was subjected to silica gel column chromatography eluted with heptane / THF 9 / 1 (v / v), and crystallized with heptane to give 10 g of a white solid (yield 58%).

[0140] Step 2 [Chemical formula] Under nitrogen, 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 to obtain a dark-colored solution. The reaction mixture was heated to 80°C under nitrogen for 12 hours, cooled, diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered, and evaporated. Purification by silica gel column chromatography eluted with heptane / THF9 / 1 (v / v) yielded a white solid, which was then crystallized from heptane to obtain a colorless crystalline material (9.1 g, yield 81%).

[0141] Process 3 [ka] Under nitrogen, 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 in a mixture of DME (150 ml) and water (25 ml) to obtain a red suspension. The reaction mixture was degassed under nitrogen and heated under reflux. After heating overnight, approximately 80% conversion was achieved. Further addition of phenylboronic acid and catalyst did not improve the conversion. The solution was purified by silica gel column chromatography eluted with heptane / THF9 / 1, and then crystallized from heptane to obtain a white solid (6.2 g, 70% yield).

[0142] Process 4 [ka] Under a nitrogen atmosphere, 4,5-bis(methyl-d3)-2-phenylpyridine (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 obtain a red solution. The reaction mixture was heated under reflux for 1 hour, after which a precipitate formed. An additional 30 mL of ethoxyethanol was added, and reflux was continued for 48 hours, after which the reaction mixture was cooled to room temperature. The crude material was used in the next step without further purification.

[0143] Process 5 [ka] Under a nitrogen atmosphere, iridium dimers suspended in ethoxyethanol were 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. The mixture was stirred under nitrogen at 55°C for 24 hours and evaporated. The yellow residue was subjected to silica gel column chromatography eluted with a gradient mixture of heptane / toluene to obtain 5 g of the target complex (yield 36%).

[0144] Process 6 [ka] 5 g of acac complex (6.72 mmol) was dissolved in 20 mL of DCM, and then 16.80 ml of HCl in ether (33.6 mmol) was added all at once. The mixture was stirred for 10 minutes and then evaporated. The residue was ground with methanol. The solid was filtered and washed with methanol and heptane to obtain a yellow solid (4.55 g, 100% yield).

[0145] Process 7 [ka] In 50 ml of a DCM / methanol 1 / 1(v / v) mixture, Ir dimer (4.55 g, 3.34 mmol) and (((trifluoromethyl)sulfonyl)oxy)silver (2.062 g, 8.03 mmol) were suspended, stirred at room temperature for 72 hours, filtered through Celite, evaporated to obtain a yellow solid (4.75 g, yield 83%).

[0146] Process 8 [ka] A mixture of trifurate (3 g, 3.5 mmol) and 8-(4-(2,2-dimethylpropyl-1,1-d2)pyridine-2-yl)-2-(methyl-d3)benzofl[2,3-b]pyridine (2.56 g, 7.7 mmol) was stirred in 30 mL of methanol at 65°C for 5 days under nitrogen. The material was then cooled and the methanol evaporated. The residue was subjected to silica gel column chromatography eluted in toluene with 2% ethyl acetate to obtain two isomers of the product (high R). f A 1.7g complex having low R f (0.7g of complex containing [the specified element]). Low R f The complex having this property is the target compound 155.

[0147] Device Examples

[0148] The example devices were all performed under high vacuum (<10 -7The devices were fabricated by thermal deposition in Torr. The anode electrode was 750 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (8-hydroxyquinoline lithium) and 1,000 Å Al. Immediately after fabrication, each device was sealed in a nitrogen glove box (H2O and O2 <1 ppm) with a glass lid sealed with epoxy resin, and a moisture getter was placed in the package. The organic laminate of the device example consisted of, in order from the ITO surface, a 100 Å HAT-CN as a hole injection layer (HIL); a 450 Å HTM as a hole transport layer (HTL); and an emissive layer (EML) with a thickness of 400 Å. The emissive layer contained H-host (H1):E-host (H2) in a ratio of 6:4 and 12 wt% green emissive. As ETL, 350 Å Liq(8-hydroxyquinoline lithium) was doped with 40% ETM. The device structure is shown in Table 2 below. Table 2 shows a schematic representation of the device structure. The chemical structure of the device material is shown below. [ka] [ka]

[0149] Regarding the manufactured device, DC 80mA / cm² 2 The EL, JVL, and lifetime were measured during testing. Device performance is shown in Table 3. Voltage, LE, EQE, PE, and LT97% were all relative to the comparison compound. [Table 2] Schematic device structure [Table 3] Device Performance

[0150] Comparing compounds 152 and 153 with the comparative examples, the efficiencies of both compounds are higher than those of the comparative examples. This is likely because compounds 152 and 153 have higher horizontal emitting dipole orientation than the comparative examples. The extended planar substituents with high electrostatic potential expand the interacting surface area between the Ir complex and the host molecule, thereby stacking Ir complexes parallel to the film surface and increasing the outcoupling efficiency. Furthermore, both compounds 152 and 153 exhibit an efficiency of 80 mA / cm². 2 LT in 97% This is superior to that of the comparative example, suggesting that the extended substituents not only increase efficiency but also enhance the stability of the complex in the device.

[0151] Table 4 below provides a summary of device data recorded at 9000 nits for each device example. The EQE value is based on device C-2. [Table 4] The data in Table 4 shows that devices using the inventive compound as a light-emitting material achieved higher efficiency, albeit with the same color, compared to the comparative example. Notably, the only difference between the inventive compound (compound 154) and the comparative compound (CC-1) is that the inventive compound has a phenyl moiety that substitutes for 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 suggest that a larger aspect ratio of the light-emitting molecule is important for achieving higher device efficiency. Combination with other materials

[0152] Materials described herein as useful for specific layers in organic light-emitting devices may be used in combination with a wide variety of other materials present in the device. For example, the light-emitting dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other possible layers. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that may be useful in combination.

[0153] Conductive dopants: Charge transport layers are doped with conductive dopants, significantly altering the density of charge carriers and thereby changing their conductivity. Conductivity is increased by generating charge carriers in the matrix material or, depending on the type of dopant, and changes in the Fermi level of the semiconductor can also be achieved. Hole transport layers can be doped with p-type conductive dopants, while n-type conductive dopants are used in electron transport layers.

[0154] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO 06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US2012146012 [ka] HIL / HTL:

[0155] The hole injection / transport material used in the embodiments of the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of materials include: phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acids and silane derivatives; MoO x This includes, but is not limited to, metal oxide derivatives such as; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonnitrile; metal complexes; and crosslinkable compounds.

[0156] Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to, the general structures shown below. [ka]

[0157] Ar 1 From Ar 9Each of these is a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiaidine, oxadiazine, indole, benzimidazole, indazole, and A group consisting of aromatic heterocyclic compounds such as xazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzophropyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenofenodipyridine; and a group consisting of 2 to 10 cyclic structural units that are the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and which are bonded to each other directly or via at least one of an oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit, and aliphatic cyclic group. Each Ar can be unsubstituted, or it can be substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof.

[0158] In one aspect, Ar 1 From Ar9 teeth, [ka] They are independently selected from the group consisting of [the specified elements]. In the formula, k is an integer from 1 to 20; X 101 From X 108 is C (including CH) or N; Z 101 is NAr 1 , O, or S; Ar 1 It has the same base as defined above.

[0159] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formulas. [ka] In the formula, Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 k' is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal; and k'+k'' is the maximum number of ligands that can adhere to the metal.

[0160] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os and Zn. In a further embodiment, the metal complex is Fc + For the / Fc couple, it has a minimum oxidation potential of less than approximately 0.6V in solution.

[0161] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. CN102702075、DE102012005215、EP01624500、EP01698613、EP01806334、EP01930964、EP01972613、EP01997799、EP02011790、EP02055700、EP02055701、EP1725079、EP2085382、EP2660300、EP650955、JP07-073529、JP2005112765、JP2007091719、JP2008021687、JP2014-009196、KR20110088898、KR20130077473、TW201139402、US06517957、US20020158242、US20030162053、US20050123751、US20060182993、US20060240279、US20070145888、US20070181874、US20070278938、US20080014464、US20080091025、US20080106190、US20080124572、US20080145707、US20080220265、US20080233434、US20080303417、US2008107919、US20090115320、US20090167161、US2009066235、US2011007385、US20110163302、US2011240968、US2011278551、US2012205642、US2013241401、US20140117329、US2014183517、US5061569、US5639914、WO05075451、WO07125714、WO08023550、WO08023759、WO2009145016、WO2010061824、WO2011075644、WO2012177006、WO2013018530、WO2013039073、WO2013087142、WO2013118812、WO2013120577、WO2013157367、WO2013175747、WO2014002873、WO2014015935、WO2014015937、WO2014030872、WO2014030921、WO2014034791、WO2014104514、WO2014157018 [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] EBL:

[0162] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons emitted from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the light-emitting element closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below. host:

[0163] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may also contain a host material that uses the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

[0164] Examples of metal complexes used as host materials preferably have the following general formula. [ka] In the formula, Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 is independently selected from C, N, O, P and S; L 101 k' is another ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal; and k'+k'' is the maximum number of ligands that can adhere to the metal.

[0165] In one embodiment, the metal complex is the following complex. [ka] In the formula, (ON) is a bidentate ligand having a metal coordinated to atoms O and N.

[0166] In another embodiment, Met is selected from Ir and Pt. In a further embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0167] Other organic compounds used as host materials include the group of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiaidine, oxadiazine, indole, benzimidazole A group consisting of aromatic heterocyclic compounds such as ethanol, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzophropyridine, phlodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenofenodipyridine; and a group consisting of 2 to 10 cyclic structural units that are the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and are bonded to each other directly or via at least one of an oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit, and aliphatic cyclic group. Each option in each group may be unsubstituted, or may be substituted with a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof.

[0168] In one embodiment, the host compound contains at least one of the following groups in its molecule. [ka] In the formula, R 101 From R 107 k is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof, and if it is aryl or heteroaryl, it has the same definition as that of Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20; k''' is an integer from 0 to 20. X 101 From X 108 This is selected from C (including CH) or N. Z 101 and Z 102 is NR 101 It is either O or S.

[0169] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR201301 15564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090 167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US201 2075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US201402 25088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO20 09066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO201212 8298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472

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[0170] One or more additional luminescent dopants may be used in conjunction with the compounds of this disclosure. Examples of additional luminescent dopants are not particularly limited, and any compound can be used as long as the compound is typically used as a luminescent material. Suitable luminescent materials include, but are not limited to, compounds that can generate light through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0171] Non-limiting examples of light-emitting materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. CN103694277、CN1696137、EB01238981、EP01239526、EP01961743、EP1239526、EP1244155、EP1642951、EP1647554、EP1841834、EP1841834B、EP2062907、EP2730583、JP2012074444、JP2013110263、JP4478555、KR1020090133652、KR20120032054、KR20130043460、TW201332980、US06699599、US06916554、US20010019782、US20020034656、US20030068526、US20030072964、US20030138657、US20050123788、US20050244673、US2005123791、US2005260449、US20060008670、US20060065890、US20060127696、US20060134459、US20060134462、US20060202194、US20060251923、US20070034863、US20070087321、US20070103060、US20070111026、US20070190359、US20070231600、US2007034863、US2007104979、US2007104980、US2007138437、US2007224450、US2007278936、US20080020237、US20080233410、US20080261076、US20080297033、US200805851、US2008161567、US2008210930、US20090039776、US20090108737、US20090115322、US20090179555、US2009085476、US2009104472、US20100090591、US20100148663、US20100244004、US20100295032、US2010102716、US2010105902、US2010244004、US2010270916、US20110057559、US20110108822、US20110204333、US2011215710、US2011227049、US2011285275、US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US 2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US73 32232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586 , US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO200201 5645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842 , WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO20 11044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO201317 4471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450,

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[0172] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons emitting from the light-emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or a longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to restrict light emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than the light-emitting material closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more hosts closest to the HBL interface.

[0173] In one embodiment, the compound used in the HBL contains the same molecule as the one used as the host described above.

[0174] In another embodiment, the compound used in the HBL contains at least one of the following groups in its molecule. [ka] In the formula, k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0175] An electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, as long as it is typically used for electron transport.

[0176] In one embodiment, the compound used in the ETL contains at least one of the following groups in its molecule. [ka] JPEG0007834954000087.jpg23129In formula, R 101 Ar is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphinol, and combinations thereof, and if it is aryl or heteroaryl, it has the same definition as Ar mentioned above. 1 From Ar 3 It has the same definition as Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 This is selected from C (including CH) or N.

[0177] In another embodiment, the metal complex used in the ETL may include, but is not limited to, the following general formulas. [ka] In the formula, (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N, or N, N; L 101 ' is another ligand; k' is an integer value from 1 to the maximum number of ligands that can adhere to the metal.

[0178] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the literature disclosing these materials. CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2 005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, U S20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US20 11210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO20 09148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO 2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535. [ka] [ka] [ka] Charge Generation Layer (CGL)

[0179] In tandem or stacked OLEDs, the transport layer (CGL) plays a crucial role in performance, consisting of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively, after which the bipolar current gradually stabilizes. Typical CGL materials include n-type and p-type conductive dopants used in the transport layer.

[0180] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms may be partially or completely deuterated. Therefore, any specifically mentioned substituents, such as but not limited to methyl, phenyl, and pyridyl, can be in non-deuterated, partially deuterated, and fully deuterated versions. Similarly, classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, and heteroaryl, can also be in non-deuterated, partially deuterated, and fully deuterated versions.

[0181] The various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. The various theories of why the invention works are not intended to limit it. [Prior art documents] [Patent Documents]

[0182] [Patent Document 1] U.S. Patent No. 5,844,363 [Patent Document 2] U.S. Patent No. 6,303,238 [Patent Document 3] U.S. Patent No. 5,707,745 [Patent Document 4] U.S. Patent No. 7,279,704 [Explanation of Symbols]

[0183] 100 Organic Light-Emitting Devices 110 circuit boards 115 Anodes 120 Hole injection layer 125 Hole transport layer 130 electron blocking layer 135 Emitting layer 140 Hole Blocking Layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 Cathode 162 First conductive layer 164 Second conductive layer 170 Barrier layer 200 Inverted OLEDs, devices 210 circuit boards 215 Cathode 220 Emitting layer 225 Hole transport layer 230 anodes 300 EML samples

Claims

1. A material for an luminescent layer having a metal coordination complex structure, The aforementioned light-emitting layer material can function as a light-emitting element in an organic light-emitting device at room temperature. The aforementioned light-emitting layer material is M(L １ ) ｘ (L ２ ) ｙ (L ３ ) ｚ It is expressed by the formula, x is 1, 2, or 3, y is 0, 1, or 2, z is 0, 1, or 2, When y and z are 1 or 2, L １ , L ２ , and L ３ are different, x + y + z is the oxidation state of the metal M, The aforementioned metal is Ir or Pt, The light-emitting layer material has at least two ligands coordinated to the metal, The aforementioned light-emitting layer material has a first substituent R at one location around the ligand. １ It has, The first distance is the distance between the metal and the R that is furthest away from the metal. １ It is the distance between atoms inside, The first distance is longer than any distance between the metal and any other atom in the light-emitting layer material, radius r １ A sphere having the metal at its center and radius r １ The spherical shape is the R in the light-emitting layer material. １ If the first distance is defined as the smallest radius that allows all atoms that are not part of the first distance to be enclosed, then the radius r １ It is at least 2.9 Å longer than that, The aforementioned light-emitting layer material has a second substituent R at one location around the ligand. ２ It further possesses, The second distance is the distance between the metal and the R that is furthest away from the metal. ２ It is the distance between atoms inside, radius r ２ However, the spherical shape is the R in the light-emitting layer material. １ or R ２ If the second distance is the smallest radius that allows enclosing all atoms except those in the r region, then the radius r ２ It is at least 1.5 Å longer than that, L １ , L ２ , and L ３ However, each is independently selected from the following group: 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (In the formula, X １ ~X １７ Each is independently selected from the group consisting of carbon and nitrogen. Z １ Z ２ , and Z ３ Each is independently selected from the group consisting of carbon and nitrogen. X is BR', NR', PR', O, S, Se, C=O, S=O, SO ２ Selected from the group consisting of CR'R'', SiR'R'', and GeR'R'', R' and R'' may condense or bond to form a ring. R ａ , R ｂ , R ｃ , and R ｄ This represents the maximum number of substitutions possible from a mono-substitution, or represents no substitutions. R', R'', R ａ , R ｂ , R ｃ , R ｄ , R ｅ 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, phosphine, and combinations thereof. Any two R ａ , R ｂ , R ｃ , and R ｄ These may condense or bond to form a ring or a polydentate ligand. The aforementioned R ａ , R ｂ , R ｃ , and R ｄ At least one of them is R １ (Includes.) The first substituent R １ However, it is selected from the group consisting of substituents 2 to 104 below, The second substituent R ２ A material for an emissive layer, characterized in that it is selected from the group consisting of substituents 1 to 104 described below. 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】

2. The aforementioned R １ and R ２ The light-emitting layer material according to claim 1, wherein the ligands are different.

3. The first distance and the second distance are both r １ or r ２ The light-emitting layer material according to claim 1, which is at least 4.3 Å longer than the specified length.

4. The aforementioned R １ However, it is bonded to an aromatic ring having a first coordination atom, and the R ２ However, it is bonded to an aromatic ring having a second coordination atom, The light-emitting layer material according to claim 1, wherein the first coordination atom is in a trans configuration with respect to the metal and respect to the second coordination atom.

5. The aforementioned light-emitting layer material has a third substituent R at one location around the ligand. ３ It further possesses, The third distance is the distance between the metal and the R that is furthest away from the metal. ３ It is the distance between atoms inside, radius r ３ The spherical shape is R in the light-emitting layer material. １ , R ２ , or R ３ If the third distance is the smallest radius that allows enclosing all atoms except those in the same region, then the radius r ３ The light-emitting layer material according to claim 1, which is at least 1.5 Å longer than the specified length.

6. The substituent R １ , R ２ , and R ３ However, they are on different ligands, The luminescent layer material has an octahedral coordination geometry including three bidentate ligands, and each of the three bidentate ligands has two coordination atoms and a central point divided between the two coordination atoms. The three aforementioned center points divide the first surface, R １ , R ２ , and R ３ The light-emitting layer material according to claim 5, wherein each atom in the material has a point-to-plane distance of less than 5 Å with respect to the first surface.

7. The substituent R １ , R ２ , and R ３ Any atom inside has a radius r with respect to the first surface. 3 A light-emitting layer material according to claim 6, having a point-to-plane distance of less than 1.

8. The aforementioned light-emitting layer material has a transition dipole moment axis, The light-emitting layer material according to claim 1, wherein the angle between the transition dipole moment axis and the axis along the first distance is less than 40°.

9. The light-emitting layer material includes a first benzene ring coordinated to the metal, The material for a light-emitting layer according to claim 1, wherein the first benzene ring is condensed by a second aromatic ring.

10. Substituent R within the same ring ａ , R ｂ , R ｃ , and R ｄ At least one pair of these elements bond and condense to form a ring; or substituent R between two nearby rings ａ , R ｂ , R ｃ , and R ｄ The light-emitting layer material according to claim 1, wherein at least one pair of these elements are bonded and condensed to form a ring.

11. The light-emitting layer material according to claim 1, wherein the light-emitting layer material is selected from the group consisting of the following. 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【change】 【Chemistry 27】 【Chemistry 28】

12. A-scatter, Cathode and, An organic light-emitting device (OLED) comprising an organic layer disposed between the anode and the cathode, and containing a material for a light-emitting layer having a metal coordination complex structure, An organic light-emitting device (OLED) characterized in that the light-emitting layer material is the light-emitting layer material according to any one of claims 1 to 11.

13. A consumer product characterized by comprising an organic light-emitting device (OLED) as described in claim 12.

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