KR20200118376A - Organic electroluminescent materials and devices - Google Patents

Abstract

Disclosed is a novel compound comprising a ligand LA of chemical formula I, chemical formula II, chemical formula III or chemical formula IV. A device manufactured according to embodiments of the present invention can be included in a wide variety of electronic component modules (or units).

Description

Organic electroluminescent materials and devices {ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES}

Cross-reference to related events

This application is filed on November 5, 2019, for U.S. Provisional Application No. 62/930,837. Claims priority under § 1.119(e). This application is also a part-continuing applicant of co-pending U.S. Patent Application No. 15/706,186 filed Sep. 5, 2017, claiming priority to U.S. Provisional Application No. 62/403,424 filed Oct. 3, 2016. Partial Continuing Applicants of U.S. Patent Application No. 15/825,297 filed on November 29, 2018, Partial Continuing Applicants of U.S. Patent Application No. 15/950,351 filed April 11, 2018, U.S. Patent Application No. filed on April 4, 2019 It is a continuing partial application of 16/375,467.

Field

The present disclosure relates generally to organometallic compounds and formulations, and to a variety of uses thereof, including use as emitters in devices such as organic light emitting diodes and related electronic devices.

Optoelectronic devices using organic materials are becoming increasingly important for several reasons. Because many of the materials used to make such devices are relatively inexpensive, organic optoelectronic devices have the potential in terms of cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for certain applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells and organic photodetectors. In the case of OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can be easily adjusted with an appropriate dopant in general.

OLEDs use thin organic films that emit light when a voltage is applied across the device. OLED is an increasingly important technology for applications such as flat panel displays, lighting and backlighting. Various OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which patent documents are incorporated herein by reference in their entirety.

One application for phosphorescent emitting molecules is full color displays. Industry standards for such displays require pixels that are tuned to emit a specific color referred to as "saturated" color. In particular, these criteria require saturated red, green and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, emission from a white backlight is filtered using an absorption filter to produce red, green and blue emission. The same technique can also be used for OLEDs. The white OLED can be a single EML device or a stack structure. Color can be measured using CIE coordinates well known in the art.

One example of a green emitting molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy) ₃ , having the structure:

In this formula and the following formulas herein, the applicant shows a coordination bond from nitrogen to a metal (here, Ir) in a straight line.

As used herein, the term “organic” includes not only polymeric materials that can be used to fabricate organic optoelectronic devices, but also small molecule organic materials. “Small molecule” refers to any organic material that is not a polymer, and “small molecule” may actually be quite large. Small molecules may contain repeat units in some situations. For example, the use of a long chain alkyl group as a substituent does not exclude a molecule from the "small molecule" type. Small molecules can also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core moiety of a dendrimer consisting of a series of chemical shells created on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules", and all dendrimers currently used in the OLED field are believed to be small molecules.

As used herein, “top” means furthest away from the substrate, and “bottom” means closest to the substrate. When the first layer is described as being "disposed over" the second layer, the first layer is disposed away from the substrate. Other layers may exist between the first layer and the second layer unless the first layer is specified as being “in contact with” the second layer. For example, even if there are various organic layers between the cathode and the anode, the cathode may be described as being "disposed above" the anode.

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

When the ligand is believed to directly contribute to the photoactive properties of the emissive material, the ligand may be referred to as “photoactive”. Although auxiliary ligands may alter the properties of the photoactive ligand, the ligand may be referred to as being “supplementary” if it is believed that the ligand does not contribute to the photoactive properties of the emissive material.

As used herein, and as generally understood by one of skill in the art, when the first energy level is closer to the vacuum energy level, the first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” The (LUMO) energy level is “greater” or “higher” than the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Likewise, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). In a typical energy level diagram with a vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The “higher” HOMO or LUMO energy level appears closer to the top of the diagram than the “lower” HOMO or LUMO energy level.

As used herein, and as generally understood by one of ordinary skill in the art, when the absolute value of the first work function is greater, the first work function is “greater” or “higher” than the second work function. Since the work function is generally measured as a negative number with respect to the vacuum level, this means that the "higher" work function is more negative. In a typical energy level diagram with a vacuum level at the top, the “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different convention than work functions.

More details and the foregoing definitions of OLEDs can be found in US Pat. No. 7,279,704, the entirety of which is incorporated herein by reference.

summary

In one embodiment, the present disclosure provides a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV:

의 구조의 "

"로 표시된 부분에 융합되며; X⁵ 내지 X¹²는 각각 독립적으로 C 또는 N이고; Z 및 Y는 각각 독립적으로 O, S, Se, NR', CR'R", SiR'R" 및 GeR'R"로 이루어진 군에서 선택되고; R^B 및 R^C는 각각 독립적으로 이의 관련된 고리에 대한 무치환, 일치환 또는 최대까지 허용되는 치환을 나타내며; R^B, R^C, R, R' 및 R" 각각은 독립적으로 수소, 또는 본원에 정의된 일반적인 치환기로 이루어진 군에서 선택되는 치환기이고; 2개의 치환기가 결합 또는 융합하여 고리를 형성할 수 있으며; 리간드 L_A는 각각의 화학식 I, 화학식 II, 화학식 III 및 화학식 IV의 2개의 표시된 점선을 통해 금속 M에 착물화하고; 리간드 L_A는 다른 리간드와 결합하여, 세자리, 네자리, 다섯자리 또는 여섯자리 리간드를 형성할 수 있다.In the formula, Ring B is independently a 5- or 6-membered carbocyclic or heterocyclic ring; X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR; At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the moiety indicated by "; X ⁵ to X ¹² are each independently C or N; Z and Y are each independently O, S, Se, NR', CR'R", SiR'R" and GeR'R" is selected from the group consisting of; R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring; Each of R ^B , R ^C , R, R'and R" is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; two substituents may be bonded or fused to form a ring; Ligand L _A complexes to metal M via two marked dotted lines of Formula I, Formula II, Formula III and Formula IV, respectively; Ligand L _A binds to other ligands, resulting in three, four, five or six Can form site ligands.

In another aspect, the present disclosure provides a combination of compounds comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV as described herein.

In another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV as described herein.

In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV as described herein.

1 shows an organic light emitting device.
2 shows an inverted structure organic light emitting device that does not have a separate electron transport layer.
3 is a plot of the photoluminescence (PL) of Example Compounds 1 and 2 and Comparative Example Compound 1 of the present invention taken in a 2-methylTHF solution at room temperature.

details

Typically, OLEDs comprise one or more organic layers disposed between and electrically connected to an anode and a cathode. When current is applied, the anode injects holes into the organic layer(s), and the cathode injects electrons. The injected holes and electrons move toward oppositely charged electrodes, respectively. When electrons and holes are localized on the same molecule, “excitons”, which are localized electron-hole pairs with excited energy states, are produced. Light is emitted when excitons are relaxed through a light emission mechanism. In some cases, excitons may be localized on excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, can also occur, but are generally considered undesirable.

Early OLEDs used emissive molecules that emit light (“fluorescence”) from a singlet state as disclosed in, for example, US Pat. No. 4,769,292, the patent document being incorporated by reference in its entirety. Fluorescence emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs with emitting materials that emit light from the triplet state ("phosphorescence") have been presented. See Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; (“Baldo-I”)] and in Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II")] is incorporated by reference in its entirety. Phosphorescence is described in more detail in columns 5-6 of US Pat. No. 7,279,704, which is incorporated by reference.

1 shows an organic light emitting device 100. The drawings are not necessarily drawn to scale. The device 100 includes 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 compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing layers in the order described. The properties and functions of these various layers, as well as exemplary materials, are described in more detail in US 7,279,704 at columns 6-10, which are incorporated by reference.

More examples for each of these layers are also available. For example, a flexible and transparent substrate-anode combination is disclosed in US Pat. No. 5,844,363, which patent document is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, and this patent document is in its entirety. Included for reference. Examples of emissive and host materials are disclosed in US Pat. No. 6,303,238 (Thompson et al.), which patent document is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in US Patent Application Publication No. 2003/0230980, and this patent document is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes, including compound cathodes having a thin layer of metal such as Mg:Ag with a layered transparent, electrically conductive sputter-deposited ITO layer. Has been. The theory and use of the barrier layer are described in more detail in US Pat. No. 6,097,147 and US Patent Application Publication No. 2003/0230980, and these patent documents are incorporated by reference in their entirety. Examples of injection layers are provided in US Patent Application Publication No. 2004/0174116, which patent document is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which patent document is incorporated by reference in its entirety.

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

The simple stacked structures shown in FIGS. 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention may be used in connection with a variety of other structures. The specific materials and structures described are for illustrative purposes only, and other materials and structures may be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or layers can be omitted entirely based on design, performance and cost factors. Other layers not specifically described may also be included. Materials different from those specifically described may be used. While many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally mixtures, may be used. Also, the layer may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in the device 200, the hole transport layer 225 transports holes and injects holes into the light emitting layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between the cathode and the anode. This organic layer may comprise a single layer, or may further comprise a plurality of layers of different organic materials as described in connection with FIGS. 1 and 2 for example.

Structures and materials not specifically described, such as OLEDs (PLEDs) comprising polymeric materials as disclosed in U.S. Patent No. 5,247,190 (Friend et al.), can also be used, which patent document is incorporated by reference in its entirety. As a further example, an OLED with a single organic layer can be used. OLEDs can be stacked, for example, as described in US Pat. No. 5,707,745 (Forrest et al.), which patent document is incorporated herein by reference in its entirety. The OLED structure can deviate from the simple stacked structure shown in FIGS. 1 and 2. For example, the substrate may be an out-coupled structure such as a mesa structure as described in U.S. Patent No. 6,091,195 (Forrest et al.) and/or a pit structure as described in U.S. Patent No. 5,834,893 (Bulovic et al.). It may include an angled reflective surface to improve out-coupling, and these patent documents are incorporated herein by reference in their entirety.

Unless stated to the contrary, any layer of various embodiments may be deposited by any suitable method. In the case of organic layers, preferred methods include thermal evaporation, ink-jet, US Pat. No. 6,337,102 (Forrest et al.) as described in US Pat. Nos. 6,013,982 and 6,087,196 (these patent documents are incorporated by reference in their entirety) ( Organic vapor deposition (OVPD) as described in this patent document is incorporated by reference in its entirety) and organic vapor jet printing (OVJP) as described in U.S. Patent No. 7,431,968 (this patent document is incorporated by reference in its entirety). Evaporation is mentioned. Other suitable deposition methods include spin coating and other solution based processes. The solution-based process is preferably carried out in nitrogen or an inert atmosphere. For other layers, a preferred method includes thermal evaporation. Preferred patterning methods include vapor deposition through a mask, cold welding and ink-jet and organic vapor jet printing (OVJP) as described in U.S. Patents 6,294,398 and 6,468,819 (these patent documents are incorporated by reference in their entirety). Includes pattern formation associated with some deposition methods such as. Other methods can also be used. The material to be deposited can be modified to have compatibility with a specific deposition method. For example, substituents such as branched or unbranched, preferably alkyl and aryl groups containing 3 or more carbons can be used in small molecules to improve their solution processing capability. Substituents having 20 or more carbons can be used, with 3 to 20 carbons being a preferred range. Since the asymmetric material may have a lower tendency to recrystallize, a material with an asymmetric structure may have better solution processability than a material with a symmetric structure. Dendrimer substituents can be used to improve the solution processing capability of small molecules.

A device manufactured according to an embodiment of the present invention may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from being damaged by exposure to harmful species in an environment containing moisture, vapor and/or gas. The barrier layer may be deposited over any other portion of the device including the edge, over the electrode or over the substrate, under the substrate, or next to the substrate. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include a composition having a plurality of phases as well as a composition having a single phase. Any suitable material or combination of materials may be used in the barrier layer. The barrier layer may include inorganic or organic compounds or both. Preferred barrier layers comprise mixtures of polymeric and non-polymeric materials as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are incorporated herein in its entirety. Included for reference. In order to be considered a “mixture”, the above-described polymeric and non-polymeric materials comprising the barrier layer must be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymer to non-polymeric material may range from 95:5 to 5:95. Polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated according to embodiments of the present invention may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate parts include display screens, light-emitting devices, such as individual light source devices or lighting panels that can be used by end consumer product manufacturers. Such electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present invention may be incorporated into a wide variety of consumer products including one or more electronic component modules (or units) therein. A consumer product is disclosed comprising an OLED comprising a compound of the present disclosure in an organic layer within the OLED. Such consumer products will include any kind of product including one or more light source(s) and/or one or more of some kind of visual display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signaling lights, head-up displays, fully or partially transparent displays, flexible displays, rollable displays. , Foldable display, stretchable display, laser printer, telephone, mobile phone, tablet, phablet, personal digital assistant (PDA), wearable device, laptop computer, digital camera, camcorder, viewfinder, micro display (2 inches diagonally) Displays), 3D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays tiled together, theater or stadium screens, light therapy devices and signage. A variety of control mechanisms, including passive and active matrices, can be used to control devices fabricated in accordance with the present invention. Many devices are intended to be used in a comfortable temperature range for humans, such as 18 to 30° C., more preferably at room temperature (20 to 25° C.), but outside this temperature range, such as -40 to +80° C. Can also be used.

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 can use the materials and structures. More generally, organic devices, such as organic transistors, may use the above materials and structures.

The terms “halo”, “halogen” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)-R _S ).

The term “ester” refers to a substituted oxycarbonyl (-OC(O)-R _S or -C(O)-OR _S ) radical.

The term "ether" refers to the -OR _S radical.

The terms "sulfanyl" or "thio-ether" are used interchangeably and refer to the -SR _S radical.

The term "sulfinyl" refers to the -S(O)-R _S radical.

The term "sulfonyl" refers to the -SO ₂ -R _S radical.

The term “phosphino” refers to a -P(R _S ) ₃ radical, and each R _S may be the same or different.

The term “silyl” refers to a -Si(R _S ) ₃ radical, and each R _S may be the same or different.

The term “boryl” refers to a -B(R _s ) ₂ radical or a Lewis adduct thereof -B(R _s ) ₃ radical, wherein R _s may be the same or different.

In each of the above, R _S may be hydrogen or a substituent, and the substituent is deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , Cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R _S is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The term “alkyl” refers to and includes both straight or branched chain alkyl radicals. Preferred alkyl groups are those containing 1 to 15 carbon atoms, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiroalkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl And the like. Additionally, the cycloalkyl group may be optionally substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or cycloalkyl radical having one or more carbon atoms each substituted by a heteroatom. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl group is optionally substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups containing one or more carbon-carbon double bonds in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups containing one or more carbon-carbon double bonds within the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having one or more carbon atoms substituted by heteroatoms. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. Additionally, alkenyl, cycloalkenyl, or heteroalkenyl groups are optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkene radicals. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, an alkynyl group is optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, aralkyl groups are optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing one or more heteroatoms. Optionally, one or more heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteroaromatic cyclic radicals can also be used interchangeably with heteroaryl. Preferred heteronon-aromatic cyclic groups contain one or more heteroatoms, and cyclic amines such as morpholino, piperidino, pyrrolidino and the like, and cyclic ethers/thio- such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. They are those containing 3 to 7 ring atoms including ethers. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” refers to and includes both single ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (these rings are “fused”), wherein at least one of the rings is an aromatic hydrocarbyl group, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particular preference is given to aryl groups having 6 carbons, 10 carbons or 12 carbons. Suitable aryl groups are phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl , Triphenyl, triphenylene, fluorene and naphthalene. Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” includes both single ring heteroaromatic groups and polycyclic aromatic ring systems comprising one or more heteroatoms. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N is a preferred heteroatom. The heteroaromatic single ring system is preferably a single ring having 5 or 6 ring atoms, and the ring may have 1 to 6 heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two carbons are common to two adjacent rings (these rings are “fused”), wherein at least one of the rings is heteroaryl, for example, Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl. The hetero polycyclic aromatic ring system may have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups are 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, oxathia Gin, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine , Pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, Preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine , 1,4-azaborine, borazine and aza-analogues thereof. Additionally, the heteroaryl group may be optionally substituted.

Among the aryl groups and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine , Triazine, and benzimidazole, and their respective aza-analogues are of particular interest.

As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl and heteroaryl are independently unsubstituted, or Independently substituted with one or more common substituents.

In many cases, general substituents are deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, Aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

In some cases, preferred general substituents are deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, It is selected from the group consisting of sulfanyl, boryl, and combinations thereof.

In some cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

In other cases, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substituted” refer to substituents other than H bonded to the relevant position, such as carbon or nitrogen. For example, when R ¹ represents a monocyclic ring, one R ¹ must be other than H (ie, substitution). Similarly, if R ¹ represents a disubstituted, then two of R ¹ must be other than H. Similarly, when R ¹ represents unsubstituted, R ¹ may be hydrogen relative to the available valency of the ring atom, such as the carbon atom of benzene and the nitrogen atom of pyrrole, or simply having a fully charged valency. It may indicate nothing about the ring atom, such as the nitrogen atom of pyridine. The maximum number of substitutions possible in a ring structure depends on the total number of valences available on the ring atom.

As used herein, “combination of these” refers to the combination of one or more elements of the corresponding list to form a known or chemically stable arrangement that one of ordinary skill in the art would envision from that list. For example, alkyl and deuterium may be combined to form partially or wholly deuterated alkyl groups; Halogen and alkyl can be combined to form halogenated alkyl substituents; Halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one case, the term substitution includes combinations of 2 to 4 of the listed groups. In other cases, the term substitution includes a combination of 2 to 3 groups. In another case, the term substitution includes a combination of two groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those that contain up to 40 atoms that are not hydrogen or deuterium, or those that contain up to 30 atoms that are not hydrogen or deuterium. . In many cases, the preferred combination of substituents will contain up to 20 atoms that are not hydrogen or deuterium.

"Aza" in the fragments described herein, ie azadibenzofuran, azadibenzothiophene, etc., means that one or more of the CH groups in each aromatic ring may be substituted with a nitrogen atom, for example Azatriphenylene includes, but is not limited to, both dibenzo[ f,h ]quinoxaline and dibenzo[ f,h ]quinoline. One of skill in the art can readily contemplate other nitrogen analogs of the aza-derivatives described above, all of which are intended to cover the terms described herein.

As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006/095951, and U.S. Patent Application Publication No. US 2011/0037057, which are incorporated herein by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. have. In addition, Ming Yan, et al ., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al ., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated herein by reference in their entirety, each of which describes an efficient route for deuteration of methylene hydrogens in benzylamine and substitution of aromatic ring hydrogens with deuterium. Is described.

When a molecular segment is described as being a substituent or otherwise described as being bound to another moiety, its name is as if it were a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g. It should be understood that it may be described as, for example, benzene, naphthalene, dibenzofuran). As used herein, different ways of designating such substituents or bonded segments are considered equivalent.

In some cases, pairs of adjacent substituents may optionally be bonded or fused to a ring. Preferred rings are 5, 6 or 7 membered carbocyclic or heterocyclic rings, including both when part of the ring formed by a pair of substituents is saturated and when part of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" refers to the 2,2' position in biphenyl, or naphthalene, so long as the two substituents concerned may be on the same ring side by side, or they are capable of stabilizing a stable fused ring system. It means that it may be on two neighboring rings with the two closest available substitutable positions, such as the 1,8 position in

Compounds of the present disclosure

In one embodiment, the present disclosure provides a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV:

의 구조의 "

"로 표시된 부분에 융합되며; X⁵ 내지 X¹²는 각각 독립적으로 C 또는 N이고; Z 및 Y는 각각 독립적으로 O, S, Se, NR', CR'R", SiR'R" 및 GeR'R"로 이루어진 군에서 선택되고; R^B 및 R^C는 각각 독립적으로 이의 관련된 고리에 대한 무치환, 일치환 또는 최대까지 허용되는 치환을 나타내며; R^B, R^C, R, R' 및 R" 각각은 독립적으로 수소, 또는 본원에 정의된 일반적인 치환기로 이루어진 군에서 선택되는 치환기이고; 2개의 치환기가 결합 또는 융합하여 고리를 형성할 수 있으며; 리간드 L_A는 각각의 화학식 I, 화학식 II, 화학식 III 및 화학식 IV의 2개의 표시된 점선을 통해 금속 M에 착물화하고; 리간드 L_A는 다른 리간드와 결합하여, 세자리, 네자리, 다섯자리 또는 여섯자리 리간드를 형성할 수 있다.In the formula, Ring B is independently a 5- or 6-membered carbocyclic or heterocyclic ring; X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR; At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the moiety indicated by "; X ⁵ to X ¹² are each independently C or N; Z and Y are each independently O, S, Se, NR', CR'R", SiR'R" and GeR'R" is selected from the group consisting of; R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring; Each of R ^B , R ^C , R, R'and R" is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; two substituents may be bonded or fused to form a ring; Ligand L _A complexes to metal M via two marked dotted lines of Formula I, Formula II, Formula III and Formula IV, respectively; Ligand L _A binds to other ligands, resulting in three, four, five or six Can form site ligands.

In some embodiments of the compound, the maximum number of N in the ring in ligand L _A is 2.

In some embodiments of the compound, each of R ^B , R ^C , R, R'and R" is independently hydrogen or a substituent selected from the group consisting of preferred general substituents as defined herein.

In some embodiments of the compound, Ring B is a 6 membered ring. In some embodiments, Ring B is a 6 membered ring, and each R is H.

In some embodiments of the compound, the ligand L _A is selected from the group consisting of:

In the formulas, the relevant conditions for formulas I and II apply to formulas VI and VII.

In any of the embodiments of the aforementioned compounds, each of X ¹ to X ⁴ is independently C or CR.

In some embodiments of the compound, at least one of X ¹ to X ⁴ in each formula is N.

In some embodiments of the compound, each of X ⁵ to X ⁸ is C.

In some embodiments of the compound, each of X ⁹ to X ¹² is C.

In some embodiments of the compound, each of X ⁵ to X ¹² is C.

In some embodiments of the compound, at least one of X ⁵ to X ¹² in each formula is N.

In some embodiments of the compound, at least one of X ⁵ to X ⁸ in each formula is N.

In some embodiments of the compound, at least one of X ⁹ to X ¹² in each formula is N.

In some embodiments of the compound, for each occurrence Z independently forms a direct bond to X ¹ . In some embodiments, for each occurrence Z independently forms a direct bond to X ² . In some embodiments, for each occurrence Z independently forms a direct bond to X ³ . In some embodiments, for each occurrence Z independently forms a direct bond to X ⁴ . In some embodiments, for each occurrence Z is independently O or S.

In some embodiments of the compound, each R ^C in each of Formulas I, II, III and IV is H. In some embodiments, at least one R ^B in each of Formulas I, II, III, IV, VI and VII is independently an alkyl or cycloalkyl group. In some embodiments, at least one R ^B in each of Formulas I, II, III and IV is independently a tertiary alkyl group.

In some embodiments of the compound, Y for each occurrence is independently O or S.

In some embodiments of the compound, ligand L _A is selected from group A of ligands consisting of:

.

.

In some embodiments of the compound, the compound comprises a ligand L _A selected from ligand group B consisting of:

.

.

In some embodiments of the compound, when ligand L _A is selected from ligand group A and ligand group B, for each formula each of R ^B , R ^C , R, R′, and R” is independently hydrogen, or herein It is a substituent selected from the group consisting of preferred general substituents defined in.

In some embodiments of the compound, when the ligand L _A is selected from ligand group B, the R ^B substituent is in a position para to the metal and is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof.

In some embodiments of the compound, when ligand L _A is selected from ligand group B, the R ^B substituent is in the para position to the metal and is tertiary alkyl. In some embodiments, the R ^B substituent is in the para position to the metal and is tert-butyl.

In some embodiments of the compound wherein ligand L _A is selected from ligand group A, for each formula in ligand group A, X ¹ to X ⁴ are independently C or CR. In some embodiments, for each formula in Ligand Group A, each R is independently H. In some embodiments, for each formula in Ligand Group A, each of X ⁵ to X ⁸ is independently C. In some embodiments, each of X ⁹ to X ¹² is independently C for each formula in Ligand Group A. In some embodiments, for each formula in Ligand Group A, each of X ⁵ to X ¹² is independently C. In some embodiments, at least one of X ⁵ to X ¹² for each formula in Ligand Group A is independently N. In some embodiments, at least one of X ⁵ to X ⁸ for each formula in Ligand Group A is independently N. In some embodiments, at least one of X ⁹ to X ¹² is independently N for each formula in Ligand Group A. In some embodiments, for each formula in Ligand Group A, each R ^C is independently H. In some embodiments, at least one R ^B for each formula in Ligand Group A is independently alkyl, cycloalkyl, or a combination thereof. In some embodiments, at least one R ^B for each formula in Ligand Group A is independently a tertiary alkyl group. In some embodiments, for each occurrence Z is independently O or S.

In some embodiments of the compound, the compound comprises a substituted or unsubstituted acetylacetonate ligand. In some embodiments of the compound, the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag and Au. In some embodiments of the compound, the metal M is selected from the group consisting of Ir and Pt. In some embodiments of the compound, the compound comprises a ligand L _A selected from the group consisting of:

In the formula, each of R ^B may be the same or different, and each of R ^C may be the same or different, and for each case R ^B and R ^C are independently selected from the group consisting of the general substituents defined herein .

를 베이스로 하는 L _{Ai -1}, 구조 2

를 베이스로 하는 L _{Ai -2}, 구조 3

를 베이스로 하는 L _{Ai -3}, 구조 4

를 베이스로 하는 L _{Ai -4}, 구조 5

를 베이스로 하는 L _{Ai -5}, 구조 6

를 베이스로 하는 L _{Ai -6}, 구조 7

를 베이스로 하는 L _{Ai -7}, 구조 8

를 베이스로 하는 L _{Ai -8}, 구조 9

를 베이스로 하는 L _{Ai -9}, 구조 10

를 베이스로 하는 L _{Ai -10}, 구조 11

를 베이스로 하는 L _{Ai -11}, 구조 12

를 베이스로 하는 L _{Ai -12}, 구조 13

를 베이스로 하는 L _{Ai -13}, 구조 14

를 베이스로 하는 L _{Ai -14}, 구조 15

를 베이스로 하는 L _{Ai -15}, 구조 16

를 베이스로 하는 L _{Ai -16}, 구조 17

를 베이스로 하는 L _{Ai -17}, 구조 18

를 베이스로 하는 L _{Ai -18}, 구조 19

를 베이스로 하는 L _{Ai -19}, 구조 20

를 베이스로 하는 L _{Ai -20}, 구조 21

를 베이스로 하는 L _{Ai -21}, 구조 22

를 베이스로 하는 L _{Ai -22}, 구조 23

를 베이스로 하는 L _{Ai -23}, 구조 24

를 베이스로 하는 L _{Ai -24}, 구조 25

를 베이스로 하는 L _{Ai -25}, 구조 26

를 베이스로 하는 L _{Ai -26}, 구조 27

를 베이스로 하는 L _{Ai -27}, 구조 28

를 베이스로 하는 L _{Ai -28}, 구조 29

를 베이스로 하는 L _{Ai -29}, 구조 30

를 베이스로 하는 L _{Ai -30}, 구조 31

를 베이스로 하는 L _{Ai -31}, 구조 32

를 베이스로 하는 L _{Ai -32}, 구조 33

를 베이스로 하는 L _{Ai -33}, 구조 34

를 베이스로 하는 L _{Ai -34}, 및 구조 35

를 베이스로 하는 L _{Ai -35}로 이루어진 군에서 선택되는 리간드 L_A를 포함하며, 여기서 i는 1 내지 1336의 정수이고, 각각의 i에 대해, R_E, R_F 및 G는 하기와 같이 정의되며:In some embodiments of the compound, the compound is structure 1

L _{Ai -1 based on} , structure 2

L _{Ai -2 based on} , structure 3

L _{Ai -3 based on} , structure 4

L _{Ai -4 based on} , structure 5

L _{Ai -5 based on} , structure 6

L _{Ai -6 based on} , structure 7

L _{Ai -7 based on} , structure 8

L _{Ai -8 based on} , structure 9

L _{Ai -9 based on} , structure 10

L _{Ai -10 based on} , structure 11

L _{Ai -11 based on} , structure 12

L _{Ai -12 based on} , structure 13

L _{Ai -13 based on} , structure 14

L _{Ai -14 based on} , structure 15

L _{Ai -15 based on} , structure 16

L _{Ai -16 based on} , structure 17

L _{Ai -17 based on} , structure 18

L _{Ai -18 based on} , structure 19

L _{Ai -19 based on} , structure 20

L _{Ai -20 based on} , structure 21

L _{Ai -21 based on} , structure 22

L _{Ai -22 based on} , structure 23

L _{Ai- 23 based on} , structure 24

L _{Ai -24 based on} , structure 25

L _{Ai -25 based on} , structure 26

L _{Ai -26 based on} , structure 27

L _{Ai -27 based on} , structure 28

L _{Ai -28 based on} , structure 29

L _{Ai -29 based on} , structure 30

L _{Ai- 30 based on} , structure 31

L _{Ai -31 based on} , structure 32

L _{Ai -32 based on} , structure 33

L _{Ai -33 based on} , structure 34

L _{Ai -34 based on} , and structure 35

It includes a ligand L _A selected from the group consisting of L _{Ai -35} based on, where i is an integer from 1 to 1336, and for each i , R _E , R _F and G are defined as follows :

Wherein R _E and R _F have the following structure:

;

;

In the formula, G ¹ to G ¹⁴ have the following structure:

.

.

The compound has the formula M(L _A ) _p (L _B ) _q (L _C ) _r , wherein L _B and L _C are each bidentate ligand; Where p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; In some embodiments of the compound in which p+q+r is the oxidation state of metal M, L _B and L _C are each independently selected from the group consisting of the following ligand group C:

In the formula, each of Y ¹ to Y ¹³ is independently selected from the group consisting of carbon and nitrogen; Y'is selected from the group consisting of BR _e , NR _e , PR _e , O, S, Se, C=O, S=O, SO ₂ , CR _e R _f , SiR _e R _f and GeR _e R _f ;

R _e and R _f may be fused or bonded to form a ring;

Each of R _a , R _b , R _c , and R _d independently represents an unsubstituted, mono- or up to maximum permissible substitution for its associated ring;

Each of R _a , R _b , R _c , R _d , R _e and R _f is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; Two adjacent substituents of R _a , R _b , R _c , and R _d may be fused or bonded to form a ring or a multidentate ligand.

The compound has the formula M(L _A ) _p (L _B ) _q (L _C ) _r , wherein L _B and L _C are each bidentate ligand; Where p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; In some embodiments of the compound in which p+q+r is the oxidation state of metal M, L _B and L _C may each independently be selected from the group consisting of the following ligand group D:

.

.

In some embodiments of the compound, the compound has the formula M(L _A ) _p (L _B ) _q (L _C ) _r , wherein L _B and L _C are each a bidentate ligand; Where p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; p+q+r is the oxidation state of metal M. In some embodiments, L _B is selected from the group consisting of L _B1 to L _B263 shown below having the general formula of L _{B k} , wherein k is an integer from 1 to 263:

.

.

In some embodiments, L _B is selected from the group consisting _{of: L B1, L B2, L} B18, L B28, L B38, L B108, L B118, L B122, L B124, L B126, L B128, L _{B130, L B32, L B134,} L B136, L B138, L B140, L B142, L B144, L B156, L B58, L B160, L B162, L B164, L B168, L B172, L B175, L B204, _{L B206, L B214, L B216} , L B218, L B220, L B222, L B231, L B233, L B235, L B237, L B240, L B242, L B244, L B246, L B248, L B250, L B252 , L _{B254, B256} L, L _{B258, B260} L, L _{B262, B263} and L.

In some embodiments, L _B is selected from the group consisting _{of: L B1, L B2, L} B18, L B28, L B38, L B108, L B118, L B122, L B124, L B126, L B128, L _{B132, B136} L, L _{B138, B142} L, L _{B156, B162} L, L _{B204, B206} L, L _{B214, B216} L, L _{B218, B220} L, L _{B231, B233} L, and L _B237.

의 구조를 베이스로 하는 넘버링 일반식 L_{C j- I}를 갖는 L_C1-I 내지 L_C768-I의 화합물로 이루어지고, L_{C j -II}는

의 구조를 베이스로 하는 넘버링 일반식 L_{C j- II}를 갖는 L_C1-II 내지 L_C768-II의 화합물로 이루어지며, 여기서 L_{C j -I} 및 L_{C j -II}에 대해 R^1' 및 R^2'는 각각 독립적으로 하기와 같이 정의되며:L _B and L _C are each a bidentate ligand; p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; p+q+r is the oxidation state of the metal M, in some embodiments of the compound having the formula M(L _A ) _p (L _B ) _q (L _C ) _r , L _C is L _{C j -I} and L _{C j -II} may be selected from the group consisting of, where j is an integer from 1 to 768, and L _{C j -I} is

_Consists of a compound of L _C1-I to L _C768-I having the numbering general formula L _{C j- I} based on the structure of, L _{C j -II} is

_Consists of compounds of L _C1-II to L _C768-II having the numbering general formula L _{C j- II} based on the structure of, wherein R ^1′ and R for L _{C j -I} and L _{C j -II} ^{2 'is} defined as follows, each independently:

Wherein R ^D1 to R ^D192 have the following structure:

.

.

In some embodiments of the compound, the ligands L _{C j- I} and L _{C j- II} consist only of these ligands, wherein the corresponding R ^1′ and R ^2′ are selected from the following structures: R ^D1 , R ^D3 , R ^D4 , R ^D5 , R ^D9 , R ^D10 , R ^D17 , R ^D18 , R ^D20 , R ^D22 , R ^D37 , R ^D40 , R ^D41 , R ^D42 , R ^D43 , R ^D48 , R ^D49 , R ^D50 , R ^D54 , R ^D55 , R ^D58 , R ^D59 , R ^D78 , R ^D79 , R ^D81 , R ^D87 , R ^D88 , R ^D89 , R ^D93 , R ^D116 , R ^D117 , R ^D118 , R ^D119 , R ^D120 , R ^D133 , R ^{D134, D135} R, R ^{D136, D143} R, R ^{D144, D145} R, R ^{D146, D147} R, R ^{D149, D151} R, R ^{D154, D155} R, R ^{D161, D175} R, R and ^D190.

In some embodiments of the compound, the ligands L _{C j- I} and L _{C j- II} consist only of these ligands, wherein the corresponding R ^1′ and R ^2′ are selected from the following structures: R ^D1 , R ^D3 , ^{R D4, R D5, R D9} , R D17, R D22, R D43, R D50, R D78, R D116, R D118, R D133, R D134, R D135, R D136, R D143, R D144, R D145 , R ^D146 , R ^D149 , R ^D151 , R ^D154 , R ^D155 , and R ^D190 .

In some embodiments of the compound, the ligand L _C is selected from the group consisting of:

.

.

In some embodiments of the compound, the compound is Ir(L _A ) ₃ , Ir(L _A )(L _B ) ₂ , Ir(L _A ) ₂ (L _B ), Ir(L _A ) ₂ (L _C ), and Ir(L _A )(L _B )(L _C ) has a formula selected from the group consisting of; In the formula, L _A , L _B , and L _C are different from each other, L _B may be selected from the group consisting of L _B1 to L _B263 as defined herein, and L _C is L _{C j -I} and L _{C j} may be selected from the group consisting of _-II, where j is an integer from 1 to 768, _{j -I} L _C is made of a compound in a _{C1 L-I} to _{L-C768 I} as defined herein, L _{C j - II} consists of compounds of L _C1-II to L _C768-II as defined herein.

In some embodiments of the compound, the compound has the formula Pt(L _A )(L _B ); In the formula, L _A and L _B may be the same or different, and L _B may be selected from the group consisting of L _B1 to L _B263 as defined herein. In some embodiments, L _A and L _B are joined to form a four-dentate ligand.

In some embodiments, the compound of the general formula _{Ir (L A i - m)} Ir to the _third base (L _{A 1 - 1) 3} to _{Ir (L A 1336 - 35)} 3, the formula Ir (L _{A i - m) (L B k) Ir} (L a 1 to ₂ for the base _{- 1) (L B 1)} 2 to _{Ir (L a 1336 - 35)} (L B 263) 2, the formula Ir (L _{a i - m) 2} (L _{C jI)} to Ir (L _{a 1} to the base _{- 1) 2 (L C 1} -I) to _{Ir (L a 1336 - 35)} 2 (L C 768-I), and formula Ir _{(L a i - m) 2} Ir of the _{(C j L-II)} to the base _{(L a 1 - 1) 2} (L C 1-II) to _{Ir (L a 1336 - 35)} 2 (L C 768- _II ) is selected from the group consisting of, in the formula, i is an integer of 1 to 1336, m is an integer of 1 to 35, j is an integer of 1 to 768, k is an integer of 1 to 263, each _{L a i - m, L B} k, L C jI, and L _{C j-II} are as defined above.

In some embodiments of the compound, to from L _{B k} is only the structure comprising the: L _B1, L _B2, L _B18, L _B28, L _B38, L _B108, L _B118, L _B122, L _B124, L _B126, L _{B128 , L B130, L B32, L} B134, L B136, L B138, L B140, L B142, L B144, L B156, L B58, L B160, L B162, L B164, L B168, L B172, L B175, L _{B204, L B206, L B214,} L B216, L B218, L B220, L B222, L B231, L B233, L B235, L B237, L B240, L B242, L B244, L B246, L B248, L B250, L _{B252, B254} L, L _{B256, B258} L, L _{B260, B262} and L.

In some embodiments of the compound, to from L _{B k} is only the structure comprising the: L _B1, L _B2, L _B18, L _B28, L _B38, L _B108, L _B118, L _B122, L _B126, L _B128, L _B132 , L _{B136, B138} L, L _{B142, B156} L, L _{B162, B204} L, L _{B206, B214} L, L _{B216, B218} L, L _{B220, B231} L, L _{B233, B237} and L.

In some embodiments of the compound, only those L _{C j- I} and L _{C j- II} structural ligands are included, where the corresponding R ^1′ and R ^2′ are defined as being selected from the following structures: R ^D1 as defined herein , R ^D3 , R ^D4 , R ^D5 , R ^D9 , R ^D10 , R ^D17 , R ^D18 , R ^D20 , R ^D22 , R ^D37 , R ^D40 , R ^D41 , R ^D42 , R ^D43 , R ^D48 , R ^D49 , R ^D50 , R ^D54 , R ^D55 , R ^D58 , R ^D59 , R ^D78 , R ^D79 , R ^D81 , R ^D87 , R ^D88 , R ^D89 , R ^D93 , R ^D116 , R ^D117 , R ^D118 , R ^D119 , R ^D120 , ^D133 R, R ^{D134, D135} R, R ^{D136, D143} R, R ^{D144, D145} R, R ^{D146, D147} R, R ^{D149, D151} R, R ^{D154, D155} R, R ^{D161, D175} R, R and ^D190.

In some embodiments of the compound, only those L _{C j- I} and L _{C j- II} structural ligands are included, where the corresponding R ^1′ and R ^2′ are defined as being selected from the following structures: R ^D1 as defined herein ^{, R D3, R D4, R} D5, R D9, R D17, R D22, R D43, R D50, R D78, R D116, R D118, R D133, R D134, R D135, R D136, R D143, R ^D144 , R ^D145 , R ^D146 , R ^D149 , R ^D151 , R ^D154 , R ^D155 , and R ^D190 .

In some embodiments of the compound comprising the ligand L _{C j -I} , only the following structures are included among L _{C j- I} : L _C1-1 , L _C4-1 , L _C9-1 , L _C10 as defined herein _-1 , L _C17-1 , L _C50-1 , L _C55-1 , L _C116-1 , L _C143-1 , L _C144-1 , L _C145-1 , L _C190-1 , L _C230-1 , L _{C231 -1} , L _C232-1 , L _C277-1 , L _C278-1 , L _C279-1 , L _C325-1 , L _C412-1 , L _C413-1 L _C414-1 , and L _C457-1 .

In some embodiments, the compound is selected from the group consisting of:

.

.

In some embodiments, the compound is selected from the group consisting of:

.

.

In another embodiment, the compound is selected from the group consisting of:

.

.

OLED and device of the present disclosure

In another aspect, the present disclosure also provides an OLED comprising a first organic layer comprising a compound as disclosed in the above compound section of the present disclosure. In some embodiments, the OLED is an anode; Cathode; And an organic layer disposed between the anode and the cathode, wherein the organic layer includes a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV:

의 구조의 "

"로 표시된 부분에 융합되며; X⁵ 내지 X¹²는 각각 독립적으로 C 또는 N이고; Z 및 Y는 각각 독립적으로 O, S, Se, NR', CR'R", SiR'R" 및 GeR'R"로 이루어진 군에서 선택되고; R^B 및 R^C는 각각 독립적으로 이의 관련된 고리에 대한 무치환, 일치환 또는 최대까지 허용되는 치환을 나타내며; R^B, R^C, R, R' 및 R" 각각은 독립적으로 수소, 또는 본원에 정의된 일반적인 치환기로 이루어진 군에서 선택되는 치환기이고; 2개의 치환기가 결합 또는 융합하여 고리를 형성할 수 있으며; 리간드 L_A는 각각의 화학식의 2개의 표시된 점선을 통해 금속 M에 착물화하고; 리간드 L_A는 다른 리간드와 결합하여, 세자리, 네자리, 다섯자리 또는 여섯자리 리간드를 형성할 수 있다.In the formula, Ring B is independently a 5- or 6-membered carbocyclic or heterocyclic ring; X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR; At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the moiety indicated by "; X ⁵ to X ¹² are each independently C or N; Z and Y are each independently O, S, Se, NR', CR'R", SiR'R" and GeR'R" is selected from the group consisting of; R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring; Each of R ^B , R ^C , R, R'and R" is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; two substituents may be bonded or fused to form a ring; Ligand L _A complexes to metal M via the two indicated dotted lines of each formula; Ligand L _A can bind with other ligands to form a three-, four-, five- or six-dentate ligand.

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

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescence emitter. In some embodiments, the OLED comprises an RGB pixel arrangement, or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal of less than 10 inches or an area of less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of 10 inches or more or an area of 50 square inches or more. In some embodiments, the OLED is a lighting panel.

In some embodiments, the compound may be a light emitting dopant. In some embodiments, the compound is phosphorescent, fluorescent, thermally activated delayed fluorescence, i.e., TADF (also referred to as type E delayed fluorescence; for example, U.S. Patent Application Publication No. 2019/, incorporated herein by reference in its entirety. Luminescence can be generated through triplet-triplet extinction or a combination of these processes, see U.S. Application No. 15/700,352, published March 14, 2019 as 0081248). In some embodiments, the luminescent dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound may be homoligand (each ligand is the same). In some embodiments, the compound may be heteroligand (at least one ligand is different from the others).

When there is more than one ligand coordinated to the metal, the ligands may all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligand(s). In some embodiments, all ligands can be different from each other. This is also the case in embodiments in which a ligand coordinated to a metal can be linked to another ligand that is coordinated to a metal to form a three-, four-, five- or six-dentate ligand. Thus, when the coordination binding ligands are linked to each other, in some embodiments all of the ligands may be the same, and in some other embodiments, one or more of the other ligands linked may be different from the other ligand(s).

In some embodiments, the compound can be used as a phosphorescence sensitizer in an OLED, wherein one or more layers of the OLED contain one or more fluorescent and/or delayed fluorescent emitters in the form of acceptors. In some embodiments, the compound can be used as a component of Exiplex used as a sensitizer. As a phosphorescence sensitizer, the compound must be able to transfer energy to the acceptor, and the acceptor either releases energy or transfers additional energy to the final emitter. The acceptor concentration may range from 0.001% to 100%. The acceptor can be the same layer as the phosphorescent sensitizer or one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, release can occur from any or all sensitizers, acceptors and final emitters.

In some embodiments, a compound of the present disclosure is neutrally charged.

According to another aspect, formulations comprising the compounds described herein are also disclosed.

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

The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) a bipolar material, b) an electron transport material, c) a hole transport material, or d) a wide band gap material that has little role in charge transport. In some embodiments, the host may comprise a metal complex. The host may be a triphenylene-containing benzo-fused thiophene or a benzo-fused furan. Any substituent in the host is independently C _n H _2n+1 , OC _n H _2n+1 , OAr ₁ , N(C _n H _2n+1 ) ₂ , N(Ar ₁ )(Ar ₂ ), CH=CH- C _n H _2n+1 , C≡CC _n H _2n+1 , Ar ₁ , Ar ₁ -Ar ₂ , and C _n H _2n -Ar ₁ may be a non-fused substituent selected from the group consisting of, or the host is a substituent Does not have In the above substituents, n may range from 1 to 10; Ar ₁ and Ar ₂ may be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example, it may be a Zn-containing inorganic material such as ZnS.

Hosts are triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran and aza-dibenzosele It may be a compound containing at least one chemical group selected from the group consisting of nopene. The host may comprise a metal complex. The host may be a specific compound selected from the host group consisting of the following formula and combinations thereof, but is not limited thereto:

Additional information on possible hosts is provided below.

In some embodiments, the light emitting region may comprise a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV:

의 구조의 "

"로 표시된 부분에 융합되며; X⁵ 내지 X¹²는 각각 독립적으로 C 또는 N이고; 고리 내 N의 최대 수는 2이고; Z 및 Y는 각각 독립적으로 O, S, Se, NR', CR'R", SiR'R" 및 GeR'R"로 이루어진 군에서 선택되고; R^B 및 R^C는 각각 독립적으로 이의 관련된 고리에 대한 무치환, 일치환 또는 최대까지 허용되는 치환을 나타내며; R^B, R^C, R, R' 및 R" 각각은 독립적으로 수소, 또는 중수소, 할로겐, 알킬, 시클로알킬, 헤테로알킬, 헤테로시클로알킬, 아릴알킬, 알콕시, 아릴옥시, 아미노, 실릴, 알케닐, 시클로알케닐, 헤테로알케닐, 알키닐, 아릴, 헤테로아릴, 아실, 카르복실산, 에테르, 에스테르, 니트릴, 이소니트릴, 술파닐, 술피닐, 술포닐, 포스피노, 보릴 및 이들의 조합으로 이루어진 군에서 선택되는 치환기이고; 2개의 치환기가 결합 또는 융합하여 고리를 형성할 수 있으며; 리간드 L_A는 각각의 화학식의 2개의 표시된 점선을 통해 금속 M에 착물화하고; 리간드 L_A는 다른 리간드와 결합하여, 세자리, 네자리, 다섯자리 또는 여섯자리 리간드를 형성할 수 있다.In the formula, Ring B is independently a 5- or 6-membered carbocyclic or heterocyclic ring; X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR; At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the moiety indicated by "; X ⁵ to X ¹² are each independently C or N; the maximum number of N in the ring is 2; Z and Y are each independently O, S, Se, NR', CR' Is selected from the group consisting of R", SiR'R" and GeR'R"; R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring; Each of R ^B , R ^C , R, R'and R" is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , Cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof It is a substituent selected from the group consisting of; Two substituents can be bonded or fused to form a ring; Ligand L _A is complexed to metal M through two indicated dotted lines in each formula; Ligand L _A is another ligand Can form a three-, four-, five- or six-dentate ligand.

In some embodiments of the luminescent region, the compound can be a luminescent dopant or a non-luminescent dopant.

In some embodiments of the luminescent region, the luminescent region further comprises a host, wherein the host is a metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, And at least one chemical group selected from the group consisting of aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

In some embodiments, the host may be selected from the group consisting of host groups as defined herein.

According to another aspect, a consumer product is disclosed comprising an OLED, wherein the OLED comprises an anode; Cathode; And an organic layer disposed between the anode and the cathode, wherein the organic layer includes a compound comprising a ligand L _A of Formula I, Formula II, Formula III or Formula IV:

의 구조의 "

"로 표시된 부분에 융합되며; X⁵ 내지 X¹²는 각각 독립적으로 C 또는 N이고; 고리 내 N의 최대 수는 2이고; Z 및 Y는 각각 독립적으로 O, S, Se, NR', CR'R", SiR'R" 및 GeR'R"로 이루어진 군에서 선택되고; R^B 및 R^C는 각각 독립적으로 이의 관련된 고리에 대한 무치환, 일치환 또는 최대까지 허용되는 치환을 나타내며; R^B, R^C, R, R' 및 R" 각각은 독립적으로 수소, 또는 중수소, 할로겐, 알킬, 시클로알킬, 헤테로알킬, 헤테로시클로알킬, 아릴알킬, 알콕시, 아릴옥시, 아미노, 실릴, 알케닐, 시클로알케닐, 헤테로알케닐, 알키닐, 아릴, 헤테로아릴, 아실, 카르복실산, 에테르, 에스테르, 니트릴, 이소니트릴, 술파닐, 술피닐, 술포닐, 포스피노, 보릴 및 이들의 조합으로 이루어진 군에서 선택되는 치환기이고; 2개의 치환기가 결합 또는 융합하여 고리를 형성할 수 있으며; 리간드 L_A는 각각의 화학식의 2개의 표시된 점선을 통해 금속 M에 착물화하고; 리간드 L_A는 다른 리간드와 결합하여, 세자리, 네자리, 다섯자리 또는 여섯자리 리간드를 형성할 수 있다. In the formula, Ring B is independently a 5- or 6-membered carbocyclic or heterocyclic ring; X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR; At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the moiety indicated by "; X ⁵ to X ¹² are each independently C or N; the maximum number of N in the ring is 2; Z and Y are each independently O, S, Se, NR', CR' Is selected from the group consisting of R", SiR'R" and GeR'R"; R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring; Each of R ^B , R ^C , R, R'and R" is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , Cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof It is a substituent selected from the group consisting of; Two substituents can be bonded or fused to form a ring; Ligand L _A is complexed to metal M through two indicated dotted lines in each formula; Ligand L _A is another ligand Can form a three-, four-, five- or six-dentate ligand.

In yet another aspect of the present disclosure, formulations comprising the novel compounds disclosed herein are described. The blend may include one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport layer material disclosed herein.

The present disclosure includes any chemical structure including the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. That is, the compounds of the present invention, or monovalent or polyvalent variants thereof, may be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules and supramolecules or supermolecules. As used herein, "a monovalent variant of a compound" refers to a moiety that is identical to a compound except that one hydrogen has been removed and replaced by a bond to the remaining chemical structure. As used herein, “multivalent variant of a compound” refers to a moiety that is the same as a compound except that one or more hydrogens have been removed and replaced by bond(s) to the remaining chemical structure. In the case of supramolecular, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

Combination with other substances

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

Conductive Dopant:

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

Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

HIL/HTL:

The hole injection/transport material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is generally used as a hole injection/transport material. Non-limiting examples of substances include phthalocyanine or porphyrin derivatives; Aromatic amine derivatives; Indolocarbazole derivatives; Polymers containing fluorohydrocarbons; Polymers with conductive dopants; Conductive polymers such as PEDOT/PSS; Self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; Metal oxide derivatives such as MoO _x ; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; Metal complexes and crosslinkable compounds.

Non-limiting examples of aromatic amine derivatives used in HIL or HTL include the following structural formulas:

Each of Ar ¹ to Ar ⁹ is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene. Group consisting of; Dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, Imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadia Gin, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine Aromatic heterocyclic compounds such as xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine Group consisting of; And groups of the same type or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and through at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. It is selected from the group consisting of 2 to 10 cyclic structural units bonded or directly bonded to each other. Each Ar may be unsubstituted, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, Alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, Ar ¹ to Ar ⁹ are independently selected from the group consisting of the formula:

Where k is an integer from 1 to 20; X ¹⁰¹ to X ¹⁰⁸ are C (including CH) or N; Z ¹⁰¹ is NAr ¹ , O or S; Ar ¹ has the same group as defined above.

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

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

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 aspect, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V versus Fc ⁺ /Fc couple.

Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, JP2008021687, JP2014-009196, KR20110088898, KR2013390077473, US200601, US20040279, US20040279, US200937 US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US20090115320, US20090167161, US2009066235, US2011007385,2012205, and US2011007385, US201420205 WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120 577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.

EBL:

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

Host:

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

Examples of metal complexes used as host preferably have the following formula:

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

이며, 여기서 (O-N)은 원자 O 및 N에 배위 결합된 금속을 갖는 두자리 리간드이다.In one embodiment, the metal complex is

Where (ON) is a bidentate ligand having a metal coordinarily bonded to atoms O and N.

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

In one embodiment, the host compound is an aromatic hydrocarbon cyclic compound such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene and The group consisting of azulene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolo Dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, Oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, p Thalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodi The group consisting of pyridine; And groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and through at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. It is selected from the group consisting of 2 to 10 cyclic structural units bonded or directly bonded to each other. Each option in each group may be unsubstituted or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl , Alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and at least one of the groups selected from the group consisting of combinations thereof do.

In one embodiment, the host compound contains one or more of the following groups in the molecule:

Wherein R ¹⁰¹ is hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, Selected from the group consisting of heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, in the case of aryl or heteroaryl, as described above It has a similar definition to Ar. k is an integer of 0 to 20 or 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are independently selected from C (including CH) or N. Z ¹⁰¹ and Z ¹⁰² are independently selected from NR ¹⁰¹ , O or S.

Non-limiting examples of additional host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US20100084966, US20100187984, US2013, US2012173984, US20120700, US2013, US2012173984, US2013, US2013 WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011133, WO2012, and WO2013, WO2011081423, WO2012, and WO2011081423, WO2013081423, WO2013081423 WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

Additional Emitter:

One or more additional emitter dopants may be used in combination with the compounds of the present disclosure. Examples of additional emitter dopants are not particularly limited, and any compound may be used as long as it is typically used as an emitter material. Examples of suitable emitter materials are phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e. TADF (also referred to as type E delayed fluorescence), triplet-triplet extinction, or a combination of these processes to produce emission. Compounds with, but are not limited to.

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below with references disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155 , EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, TW201332980, US06699599, US200449, US20065634, US200,2005, US200,656,200, US200, and2005 , US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007034863, US2007104979, US20078022007450, US2007034863, US2007034863, US2007104979, US200805334980, US20071384,278, US200805334800 , US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US2010024400 4, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US201365666, US20136566, US2013656, US2013656, US2013656 US6835469, US6921915, US7279704, US7332232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, WO06081973, WO06121811, WO07018067, WO06081973, WO06121811, WO07018067, WO07108362, WO0711598,200, WO200355, WO07115970, WO3355, WO07115970, WO3355 WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011107491, WO2011044988, WO2011051404, WO2011051404, WO2011107491, WO2012020327, WO201216327, WO201403471, WO20140347, WO2014112450.

HBL:

The hole blocking layer HBL may be used to reduce the number of holes and/or excitons leaving the emission layer. The presence of such a blocking layer in the device can lead to significantly higher efficiency and/or longer lifetime compared to similar devices without a blocking layer. Also, a blocking layer can be used to confine the light emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one embodiment, the compound used for HBL contains the same molecule or functional group used as the host described above.

In another embodiment, the compound used for HBL contains one or more of the following groups in the molecule:

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

ETL:

The electron transport layer ETL may include a material capable of transporting electrons. The electron transport layer may be unique (not doped) or may be doped. Doping can be used to improve conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound can be used as long as they are usually used to transport electrons.

In one embodiment, the compound used for ETL comprises one or more of the following groups in the molecule:

Wherein R ¹⁰¹ is hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, Selected from the group consisting of heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, in the case of aryl or heteroaryl, as described above It has a similar definition to Ar. Ar ¹ to Ar ³ have similar definitions to Ar described above. k is an integer from 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are selected from C (including CH) or N.

In another embodiment, the metal complexes used in ETL include, but are not limited to, the formula:

Where (ON) or (NN) is a bidentate ligand having a metal coordinarily bonded 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 to which the metal can be attached.

Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918 , JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US201284150111, US2012193612, US201284150, US2003, US2014566014, US2012, US2014, US2003 , WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

Charge Generation Layer (CGL):

In a tandem or stacked OLED, CGL plays an essential role in performance, which consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The electrons and holes consumed in CGL are refilled by electrons and holes injected from the cathode and anode, respectively; After that, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductive dopants used in the transport layer.

In any of the aforementioned compounds used in each layer of the OLED device, the hydrogen atom may be partially or completely deuterated. Thus, any specifically listed substituents such as, but not limited to, methyl, phenyl, pyridyl, and the like can be in their deuterated, partially deuterated and fully deuterated forms. Likewise, types of substituents such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, and the like may also be in their deuterated, partially deuterated and fully deuterated forms.

Experiment

Synthesis of Example Compound 1 of the present invention having the formula of Ir(L _A66-1 ) ₂ L _C17

[Reaction Scheme]

1-(4-( tert -butyl)naphthalen-2-yl)-8-isobutylbenzo[4,5] in 2-ethoxyethanol (125 mL) and deionized ultrafiltration (DIUF) water (80 mL) A solution of thieno[2,3- c ]pyridine (8.43 g, 19.9 mmol, 2.1 equiv) was sparged with nitrogen for 10 minutes. Iridium(III) chloride hydrate (3.019 g, 9.54 mmol, 1.0 eq) was added and the reaction mixture was heated at 95° C. for 18 hours. The solution was cooled to 50° C., the solid was filtered, washed with DIUF water (125 mL) and methanol (125 mL), and dried in air to wet the solvent di- μ -chloro-tetrakis-[(1-(4 -( tert -butyl)naphthalen-2-yl)-1'-yl)-8-iso-butylbenzo[4,5]thieno[2,3- c ]pyridin-6-yl]diiridium(III) Got it.

Next, di- μ -chloro-tetrakis-[(1-(4-( tert -butyl)naphthalen-2-yl)-1'-yl)-8-iso in 2-ethoxyethanol (150 mL) To a solution of butylbenzo[4,5]thieno[2,3- c ]pyridin-6-yl]iridium(III) (10.23 g, 4.77 mmol, 1.0 equiv), 3,7-di-ethyl via syringe Nonane-4,6-dione (5.516 g, 26.0 mmol, 5.45 eq) was added, and the reaction mixture was sparged with nitrogen for 10 minutes. Powdered potassium carbonate (5.317 g, 38.5 mmol, 8.07 eq) was added, and the reaction mixture was stirred at room temperature for 72 hours. DIUF water (150 mL) was added and the mixture was stirred for 30 minutes. The suspension was filtered, and the solid was washed with DIUF water (250 mL) and methanol (200 mL), and then air dried. The crude red solid (16.6 g) was chromatographed on silica gel (843 g) layered with basic alumina (468 g), eluting with 40% dichloromethane in hexane, and bis[(1-(4-( tert -Butyl)naphthalen-2-yl)-1'-yl)-8-isobutylbenzo[4,5]thieno[2,3- c ]pyridin-2-yl]-(3,7-diethylnonane -4,6-dinato-κ ₂ O,O') iridium (II) was obtained.

Synthesis of Example Compound 2 of the Invention:

8-isobutyl-1-(naphthalen-2-yl)benzo[4,5]thieno[2,3- c ]pyridine (2.40 g, 6.53 mmol, 2.2 eq) and iridium(III) chloride tetrahydrate (1.1 g, 2.97 mmol, 1.0 eq) was charged into a 40 mL reaction vial. 2-Ethoxyethanol (15 mL) and DIUF water (5 mL) were added, and the reaction mixture was stirred at 90° C. for about 60 hours. ¹ H-NMR analysis indicated complete consumption of the starting ligand. The mixture was cooled to room temperature and diluted with DIUF water (5 mL). The solid was filtered, washed with methanol (20 mL), and di- μ -chloro-tetrakis[1-(naphthalen-2-yl)-3'-yl)-8-isobutyl-benzo[4,5] Thieno[2,3- c ]pyridin-2-yl)]-diiridium(III) (1.42 g, 52% yield) was obtained as an orange solid.

3,7-diethylnonane-4,6-dione (1.180 g, 5.56 mmol, 8 eq), crude di- μ -chloro-tetrakis[1-(naphthalen-2-yl)-3'-yl) -8-isobutyl-benzo[4,5]thieno[2,3- c ]pyridin-2-yl)]-diiridium(III) (1.39 g, 0.722 mmol, 1.0 equiv), dichloromethane (1 mL ) And methanol (25 mL) was charged into a 40 mL vial. Powdered potassium carbonate (1.152 g, 8.34 mmol, 12 eq) was added, and the mixture was sparged with nitrogen for 5 minutes. After heating at 45° C. overnight, the reaction was cooled to room temperature and diluted with DIUF water (50 mL). After stirring for 10 minutes, the red-orange solid was filtered, washed with water (20 mL), then methanol (100 mL), and dried under vacuum. The solid was dissolved in dichloromethane (200 mL) and dry loaded onto Celite (50 g). The product was chromatographed on basic alumina to obtain bis[(1-(naphthalen-2-yl)-3'-yl)-8-isobutyl-benzo[4,5]thieno[2,3-c]pyridine- 2-day)]-(3,7-diethyl-4,6-nonanedineto-κ ₂ O,O') iridium (III) (0.705 g, 97.2% purity, 43% yield) red-orange solid Obtained as.

Synthesis of Comparative Example 1 Compound:

8-isobutyl-1-(naphthalen-1-yl)benzo[4,5]thieno[2,3-c]pyridine (1.695 g) in 2-ethoxyethanol (12 mL) and DIUF water (4 mL) , 4.61 mmol, 2.0 eq) was sparged with nitrogen for 10 minutes. Iridium(III) chloride hydrate (0.73 g, 2.31 mmol, 1.0 eq) was added and the reaction mixture was heated at 100° C. for 18 hours. The reaction was stopped and cooled to room temperature. The resulting red solid was filtered, washed with methanol (3 x 5 mL), and the crude estimated intermediate, di- μ -chloro-tetrakis[1-(naphthalen-1-yl)-2'-yl) -8-Isobutyl-benzo[4,5]thieno[2,3-c]pyridin-1-yl)]-diiridium(III) (estimated 1.153 mmol, wet) was obtained as a red solid.

Next, crude di- μ -chloro-tetrakis[1-(naphthalen-1-yl)-2'-yl)-8-isobutyl-benzo[4,5]thieno[2,3-c] Pyridine-1-yl)]-diiridium(III) (estimated 1.153 mmol, 1.0 eq) was suspended in methanol (12 mL) and dichloromethane (1 mL). 3,7-diethylnonane-4,6-dione (0.98 g, 4.61 mmol, 4.0 eq) and powdered potassium carbonate (0.96 g, 6.92 mmol, 6.0 eq) were added, and the reaction mixture was 50 for 2 hours. Heating at °C forms a new red suspension. The reaction was cooled to room temperature and diluted with water (10 mL). The solid was filtered, washed with water (2 x 3 mL) and methanol (3 x 1 mL). The red solid was purified on a silica gel column, eluting with a gradient of 0-50% dichloromethane in heptane, and bis[(1-(naphthalen-1-yl)-2'-yl)-8-isobutyl-benzo[4 ,5] thieno[2,3- c ]pyridin-1-yl)]-(3,7-diethyl-4,6-nonanedineto-κ ₂ O,O') iridium (III) was obtained. .

Photoluminescence (PL) spectra of the compounds of Inventive Example I, Inventive Example 2, and Comparative Example 1 were taken in 2-methylTHF solution at room temperature, and the data are plotted in FIG. 3. PL intensity was normalized to the maximum of the first emission peak. Both of Example 1 and Comparative Example 1 of the present invention exhibited saturated red color. Compared with Comparative Example 1, Example 1 of the present invention exhibited a much narrower light emission. It can be seen that the intensity of the second PL peak of Example 1 of the present invention is lower than that of Comparative Example 1. Saturated emission color, narrower emission spectrum, more specifically a lower contribution from the second emission peak, provides improved device performance such as high electroluminescence efficiency and lower power consumption.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may include variations derived from the specific and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that there is no intention to limit the various theories as to why the invention works.

Claims (20)

Compounds comprising ligand L _A of formula I, formula II, formula III or formula IV:

In the formula,
Ring B is independently a 5 or 6 membered carbocyclic or heterocyclic ring;
X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR;
At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the portion marked with ";
Each of X ⁵ to X ¹² is independently C or N;
Z and Y are each independently selected from the group consisting of O, S, Se, NR', CR'R", SiR'R" and GeR'R";
R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring;
Each of R ^B , R ^C , R, R'and R" is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , Cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof It is a substituent selected from the group consisting of, Two substituents may be bonded or fused to form a ring;
Ligand L _A complexes to metal M through the two indicated dotted lines of each formula;
Ligand L _A can combine with other ligands to form a three-, four-, five- or six-dentate ligand. The method of claim 1, wherein each of R ^B , R ^C , R, R'and R" is independently hydrogen, or deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, A compound that is a substituent selected from the group consisting of cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof. The compound of claim 1, wherein Ring B is a 6-membered ring. The compound of claim 1, wherein each of X ¹ to X ⁴ is independently C or CR. The compound of claim 1, wherein at least one of X ¹ to X ⁴ in each formula is N. The compound of claim 1, wherein each of X ⁵ to X ¹² is C. The compound of claim 1, wherein at least one of X ⁵ to X ¹² in each formula is N. The compound of claim 1, wherein for each occurrence Z is independently O or S. The compound of claim 1, wherein at least one R ^B in each formula is independently an alkyl or cycloalkyl group. The compound of claim 1, wherein the ligand L _A is selected from the group consisting of the following structures:

. The compound of claim 1, wherein the metal M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag and Au. The compound according to claim 1, comprising a ligand L _A selected from the group consisting of:

In the formula, each of R ^B may be the same or different, and each of R ^C may be the same or different,
For each occurrence R ^B and R ^C are independently deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroal Kenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof. The method of claim 1, wherein the compound is structure 1

L _{Ai -1 based on} , structure 2

L _{Ai -2 based on} , structure 3

L _{Ai -3 based on} , structure 4

L _{Ai -4 based on} , structure 5

L _{Ai -5 based on} , structure 6

L _{Ai -6 based on} , structure 7

L _{Ai -7 based on} , structure 8

L _{Ai -8 based on} , structure 9

L _{Ai -9 based on} , structure 10

L _{Ai -10 based on} , structure 11

L _{Ai -11 based on} , structure 12

L _{Ai -12 based on} , structure 13

L _{Ai -13 based on} , structure 14

L _{Ai -14 based on} , structure 15

L _{Ai -15 based on} , structure 16

L _{Ai -16 based on} , structure 17

L _{Ai -17 based on} , structure 18

L _{Ai -18 based on} , structure 19

L _{Ai -19 based on} , structure 20

L _{Ai -20 based on} , structure 21

L _{Ai -21 based on} , structure 22

L _{Ai -22 based on} , structure 23

L _{Ai- 23 based on} , structure 24

L _{Ai -24 based on} , structure 25

L _{Ai -25 based on} , structure 26

L _{Ai -26 based on} , structure 27

L _{Ai -27 based on} , structure 28

L _{Ai -28 based on} , structure 29

L _{Ai -29 based on} , structure 30

L _{Ai- 30 based on} , structure 31

L _{Ai -31 based on} , structure 32

L _{Ai -32 based on} , structure 33

L _{Ai -33 based on} , structure 34

L _{Ai -34 based on} , and structure 35

It includes a ligand L _A selected from the group consisting of L _{Ai -35} based on, where i is an integer from 1 to 1336, and for each i , R _E , R _F and G are defined as follows :

Where R _E and R _F are structures

Has,
Here, G ¹ to G ¹⁴ are structures

Compound having. The compound of claim 1, wherein the compound has the formula M(L _A ) _p (L _B ) _q (L _C ) _r , wherein L _B and L _C are each bidentate ligand; Where p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; p+q+r is a compound in the oxidation state of metal M. The compound of claim 14, wherein L _B and L _C are each independently selected from the group consisting of:

In the formula,
Each of Y ¹ to Y ¹³ is independently selected from the group consisting of carbon and nitrogen; Y'is selected from the group consisting of BR _e , NR _e , PR _e , O, S, Se, C=O, S=O, SO ₂ , CR _e R _f , SiR _e R _f and GeR _e R _f ;
R _e and R _f may be fused or bonded to form a ring;
Each of R _a , R _b , R _c and R _d independently represents an unsubstituted, mono- or up to maximum permissible substitution for its associated ring;
Each of R _a , R _b , R _c , R _d , R _e and R _f is independently hydrogen, or hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, Alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl and these It is a substituent selected from the group consisting of a combination of;
Two adjacent substituents of R _a , R _b , R _c and R _d may be fused or bonded to form a ring or a multidentate ligand. 14. The method of claim 13 wherein the compound of the general formula _{Ir (L A i - m)} 2 Ir of the (L _{C jI)} to the base _{(L A 1 - 1) 2} (L C 1-I) to Ir (L _{A 1336 - 35) 2 (L C 768} -I), and formula _{Ir (L a i - m)} 2 (L C j-II Ir (L a 1 to the _{base) - 1) 2 (L C} 1-II ) to _{Ir (L a 1336 - 35)} 2 ( is selected from the group consisting of L _{C 768-II),} wherein, i is an integer from 1 to 1336, m is an integer from 1 to 35, j is 1 to Is an integer of 768, where L _{C j -I} is

_Consists of a compound of L _C1-I to L _C768-I having the numbering general formula L _{C j- I} based on the structure of, L _{C j -II} is

_Consists of compounds of L _C1-II to L _C768-II having the numbering general formula L _{C j- II} based on the structure of, wherein R ^1′ and R for L _{C j -I} and L _{C j -II} ^{2 'is} defined as follows, each independently:

Here, R ^D1 to R ^D192 are structures

Compound having. The compound of claim 1 selected from the group consisting of:

. The compound of claim 1 selected from the group consisting of:

. Compounds selected from the group consisting of:

. Anode;
Cathode; And
Organic layer disposed between anode and cathode
Including,
The organic layer is an organic light emitting device (OLED) comprising a compound comprising a ligand L _A of the following formula (I), (II), (III) or (IV):

In the formula,
Ring B is independently a 5 or 6 membered carbocyclic or heterocyclic ring;
X ¹ to X ⁴ are each independently selected from the group consisting of C, N and CR;
At least one pair of adjacent X ¹ to X ⁴ is each C, and formula V

Of the structure of "

Fused to the portion marked with ";
Each of X ⁵ to X ¹² is independently C or N;
Z and Y are each independently selected from the group consisting of O, S, Se, NR', CR'R", SiR'R" and GeR'R";
R ^B and R ^C each independently represent an unsubstituted, monosubstituted or maximum permissible substitution for its associated ring;
Each of R ^B , R ^C , R, R'and R" is independently hydrogen, or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , Cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof It is a substituent selected from the group consisting of, Two substituents may be bonded or fused to form a ring;
Ligand L _A complexes to metal M through the two indicated dotted lines of each formula;
Ligand L _A can combine with other ligands to form a three-, four-, five- or six-dentate ligand.

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