Organic light-emitting material containing a cyano-substituted ligand

Abstract

To provide metal complexes that can provide improved electroluminescent device performance, such as narrower full width at half maximum, lower voltage values, and higher quantum efficiency.SOLUTION: The present invention provides a metal complex represented by the formula 2-a. (m represents 1, 2 or 3; X represents O, S or Se; R11, R12, R13, R14, R3, R4, Ra, and Rb independently represent H, D, a halogen, a substituted / unsubstituted C1-20 alkyl group, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group or the like; at least one of R3 and R4 is a cyano group, adjacent two substituents may combine with each other, forming a ring).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a compound used in an organic electronic device such as an organic light-emitting device. In particular, it relates to a metal complex containing a cyano group-substituted ligand, an electroluminescent device containing the metal complex, and a formulation of the compound.

Background Art

[0002] Organic electronic devices include, but are not limited to, organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic cells (OPVs), dye-sensitized solar cells (DSSCs), organic photodetectors, organic photosensitive devices, organic field-effect quantum dots (OFQDs), light-emitting electrochemical cells (LECs), organic laser diodes, and organic plasma light-emitting devices.

[0003] In 1987, Tang and VanSlyke of Eastman Kodak reported a two-layer organic electroluminescent device including an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987, 51(12): 913-915). Once a bias is applied to the device, green light is emitted from the device. This invention has laid the foundation for the development of modern organic light-emitting diodes (OLEDs). The most advanced OLEDs may include a plurality of layers such as a charge injection / transport layer, a charge / exciton blocking layer, and one or more light-emitting layers between a cathode and an anode. Since OLEDs are self-luminous solid-state devices, they offer great potential for display and lighting applications. Also, the inherent properties of organic materials, such as their flexibility, have become very suitable for special applications such as manufacturing on flexible substrates.

[0004] OLEDs are classified into three different types according to their emission mechanisms. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs, which use only singlet emission. This limitation hinders the commercialization of OLEDs because the triplets generated in the device are wasted through non-radiative decay pathways, and the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. In 1997, phosphorescent OLEDs using triplet emission from heavy metals containing complexes as emitters were reported by Forrest and Thompson. Therefore, both singlets and triplets can be harvested to achieve 100% IQE. Due to their high efficiency, the discovery and development of phosphorescent OLEDs directly contribute to the commercialization of active matrix OLEDs (AMOLEDs). Recently, Adachi has achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, enabling excitons to transition from triplets to singlets. In TADF devices, the IQE is high due to the generation of singlet excitons by the penetration of triplet excitons through reverse intersystem crossing.

[0005] OLEDs can also be further divided into small molecule and polymer OLEDs according to the form of the materials used. Small molecules refer to either organic or organometallic materials that are not polymers, and even if the molecular weight of small molecules is large as long as they have an exact structure. Dendrimers with a definite structure are recognized as small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with luminescent groups in the side chains. When post-polymerization occurs during the manufacturing process, small molecule OLEDs can become polymer OLEDs.

[0006] Various manufacturing methods of OLEDs are known. Small molecule OLEDs are generally manufactured by vacuum thermal evaporation. Polymer OLEDs are manufactured by solution methods such as spin coating, inkjet printing, and nozzle printing. If the material can be dissolved or dispersed in a solvent, small molecule OLEDs can also be manufactured by solution methods.

[0007] The emission color of an OLED can be realized by the structural design of the light-emitting material. The OLED may include one or more light-emitting layers so as to realize a desired spectrum. In green, yellow, and red OLEDs, phosphorescent materials have already succeeded in commercialization, but blue phosphorescent devices still have problems such as unsaturated blue, short service life, and high operating voltage. Commercially available full-color OLED displays generally use a mixing strategy, using blue fluorescence and yellow, red, or green phosphorescence. Currently, there is a problem that the efficiency of phosphorescent OLEDs rapidly decreases at high brightness. Also, it is desired to have a more saturated emission spectrum, higher efficiency, and longer device service life.

[0008] Cyano group substitution is not always introduced into phosphorescent metal complexes, such as iridium complexes. US20140252333A1 discloses a series of iridium complexes substituted with a series of cyano group-phenyl groups, but the effect of the cyano group is not clearly shown. Also, for example, in US20040121184A1, since the cyano group is a substituent that easily adsorbs electrons, it may be used as an emission spectrum that blueshifts the phosphorescent metal complex. The present invention discloses a series of novel cyano group-substituted metal complexes that unexpectedly exhibit many characteristics such as high efficiency, low voltage, and no obvious blueshift or redshift emission. Most unexpectedly, it has a very narrow emission peak width. These advantages greatly contribute to the improvement of the green light device level and color saturation. Summary of the Invention

[0009] An object of the present invention is to provide a series of technical solutions to solve at least some of the above-mentioned problems.

[0010] One object of the present invention is to provide a metal complex containing a ligand L represented by Formula 1 a [Chemical Formula] Formula 1 (Cy is an aryl group or a heteroaryl group having 5 to 24 ring atoms, which may be substituted or unsubstituted, wherein Cy is bonded to a metal by a metal-carbon bond or a metal-nitrogen bond, X1 to X4 are each independently selected from C, CR x1 or N, and at least one of X1 to X4 is C and is bonded to the Cy, and when there are a plurality of CR x1 in X1 to X4, the R x1 may be the same or different, X5 to X8 are each independently selected from CR x2 or N, and when there are a plurality of CR x2 in X5 to X8, the R x2 may be the same or different, X is selected from the group consisting of O, S, Se, NR x3 , CR x4 R x5 and SiR x6 R x7 ; R x1 , R x2 , R x3 , R x4 , R x5 , R x6 and R x7Each independently is selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxyl group, an ester group, a cyano group, an isocyano group, a thioalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof, said R x1 and R x2 at least one of which is a cyano group, two adjacent substituents may combine to form a ring, X1, X2, X3 or X4 is bonded to the metal by a metal-carbon bond or a metal-nitrogen bond.)

[0011] The present invention aims to provide an electroluminescent device including an anode, a cathode, and an organic layer provided between the anode and the cathode, wherein the organic layer contains the metal complex according to Item 1 of the object.

[0012] The present invention aims to provide a formulation of a compound containing the metal complex according to Item 1 of the object as a third object.

[0013] The present invention aims to provide a compound for preparing the metal complex according to Item 1 of the object as a fourth object.

[0014] The novel metal complex containing a cyano group-substituted ligand according to the present invention may be used as a luminescent material in an electroluminescent device. These novel compounds are used in an electroluminescent device and can provide better device performance such as, for example, a narrower full width at half maximum, a lower voltage value, and a higher quantum efficiency.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0016] OLEDs can be manufactured on various substrates such as glass, plastic, and metal. FIG. 1 shows the organic light-emitting device 100 without being limited exemplarily. The drawings are not necessarily made to scale, and in the figures, some layer structures may be omitted as necessary. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be manufactured by depositing the described layers in sequence. The properties, functions, and exemplary materials of each layer are described in more detail in columns 6 to 10 of US Patent US7279704B2, and all of its contents are incorporated herein by reference.

[0017] There are more examples for each of these layers. Exemplarily, in U.S. Patent No. 5,844,363 incorporated herein by reference in its entirety, a flexible and transparent substrate-anode combination is disclosed. For example, in U.S. Patent Application Publication No. 2003 / 0230980 incorporated herein by reference in its entirety, an example of a p-type doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1. In U.S. Patent No. 6,303,238 by Thompson et al. incorporated herein by reference in its entirety, examples of host materials are disclosed. For example, in U.S. Patent Application Publication No. 2003 / 0230980 incorporated herein by reference in its entirety, an example of an n-type doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1. In U.S. Patents No. 5,703,436 and 5,707,745 incorporated herein by reference in their entireties, examples of cathodes are disclosed that include a composite cathode having a thin metal layer such as Mg:Ag and a sputter-deposited transparent conductive ITO layer coated thereon. In U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980 incorporated herein by reference in their entireties, more specifically, the principles and uses of blocking layers are described. In U.S. Patent Application Publication No. 2004 / 0174116 incorporated herein by reference in its entirety, examples of injection layers are provided. In U.S. Patent Application Publication No. 2004 / 0174116 incorporated herein by reference in its entirety, protective layers are described.

[0018] The above-described layered structure is provided by non-limiting examples. By combining the various layers described above, the functions of the OLED can be realized, or some of the layers can be completely omitted. It may also include other layers not specifically described. Within each layer, a single material or a mixture of various materials can be used to achieve optimal performance. Any of the functional layers may include a plurality of sub-layers. For example, the light-emitting layer may have two different light-emitting materials to achieve a desired emission spectrum.

[0019] In one embodiment, the OLED may be described as having an "organic layer" provided between a cathode and an anode. The organic layer may include one or more layers.

[0020] An OLED also requires a encapsulation layer. As shown in FIG. 2, the organic light-emitting device 200 is shown by way of example without limitation. The difference from FIG. 1 is that an encapsulation layer 102 may be included on the cathode 190 so as to prevent harmful substances from the outside world such as moisture and oxygen. Any material capable of providing an encapsulation function such as glass, or an organic-inorganic hybrid layer may be used as the encapsulation layer. The encapsulation layer should be disposed directly or indirectly outside the OLED element. Multilayer thin-film encapsulation is described in U.S. Patent US7968146B2, the entire content of which is incorporated herein by reference.

[0021] The device manufactured according to an embodiment of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. These consumer products include, for example, flat panel displays, monitors, medical monitors, televisions, billboards, indoor or outdoor lighting lamps and / or signal lamps, head-up displays, all or partially transparent displays, flexible displays, smart phones, flat panel computers, flat panel mobile phones, wearable devices, smart watches, laptop computers, digital cameras, portable video cameras, viewfinders, microdisplays, 3-D displays, in-vehicle displays, and tail lights.

[0022] The materials and structures described herein may also be used in other organic electronic devices listed above.

[0023] "Top" means furthest from the substrate, and "bottom" means closest to the substrate. When it is described that the first layer is provided "above" the second layer, the first layer is provided relatively further from the substrate. Unless the first layer is defined as "contacting" the second layer, other layers may be present between the first layer and the second layer. Exemplarily, even if various organic layers are present between the cathode and the anode, it can still be described that the cathode is "provided above" the anode.

[0024] "The solution is processable" 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 the liquid medium.

[0025] It is believed that a ligand may be called "photosensitive" if it directly facilitates the photosensitive properties of the emissive material. A ligand may be called "auxiliary" if it does not facilitate the photosensitive properties of the emissive material. However, it is believed that an auxiliary ligand can modify the properties of a photosensitive ligand.

[0026] It is believed that the internal quantum efficiency (IQE) of a fluorescent OLED may exceed the 25% spin statistical limit due to the presence of delayed fluorescence. Delayed fluorescence may generally be divided into two types, namely P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

[0027] On the one hand, E-type delayed fluorescence depends not on the collision of two triplets but on the conversion of the excited state between the triplet and the singlet state. Compounds capable of generating E-type delayed fluorescence need to have a very small singlet-triplet gap so as to perform the energy state conversion. Thermal energy can activate the transition from the triplet state to the singlet state. This type of delayed fluorescence is also called thermally activated delayed fluorescence (TADF). A remarkable feature of TADF is that the delayed component improves with the increase in temperature. When the rate of penetration (reverse intersystem crossing) between reverse intersystem crossing (RISC) is fast enough, non-radiative decay from the triplet state is minimized, and the proportion of the excited state of the backfilled singlet can reach 75%. The total proportion of the singlet may be 100%, far exceeding 25% of the spin statistics of excitons by electrons.

[0028] The characteristics of E-type delayed fluorescence can be seen from the excited complex system or a single compound. Without being limited to theory, for E-type delayed fluorescence, the luminescent material needs to have a small singlet-triplet energy gap (ΔE S-T ). Organic non-metal-containing donor-acceptor luminescent materials have the potential to achieve this. The emission of these materials is usually characterized as donor-acceptor charge transfer (CT) type emission. In these donor-acceptor type compounds, the spatial separation between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) generally results in a small ΔE S-T . These states may include CT states. Usually, donor-acceptor luminescent materials are constructed by combining an electron donor part (for example, an amine group or a carbazole derivative) and an electron acceptor part (for example, an N-containing six-membered aromatic ring).

[0029] Regarding the definition of the terminology of substituents

[0030] As used herein, halogen or halide includes fluorine, chlorine, bromine, and iodine.

[0031] The alkyl group includes linear and branched alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, and 3-methylpentyl. Also, the alkyl group may be substituted. The carbon in the alkyl group chain may be substituted with other heteroatoms. Among them, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and neopentyl are preferred.

[0032] As used herein, the cycloalkyl group includes cyclic alkyl groups. Preferred cycloalkyl groups are cycloalkyl groups having 4 to 10 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl group, 2-norbornyl group, and the like. Also, the cycloalkyl group may be substituted. The carbon in the ring may be substituted with other heteroatoms.

[0033] As used herein, the alkenyl group includes linear and branched olefin groups. Preferred alkenyl groups are alkenyl groups having 2 to 15 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group and 3-phenyl-1-butenyl group. Further, the alkenyl group may be substituted.

[0034] As used herein, the alkynyl group includes linear and branched alkynyl groups. Preferred alkynyl groups are alkynyl groups having 2 to 15 carbon atoms. Further, the alkynyl group may be substituted.

[0035] As used herein, an aryl group or an aromatic group takes into account non-condensed and condensed systems. Preferred aryl groups are aryl groups having 6 to 60 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorenyl, pyrene, chrysene, perylene, and azulene, and preferably include phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, and naphthalene. Further, the aryl group may be substituted. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-tribiphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4''-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-dimethylphenyl, mesitylene, and m-tetraphenyl.

[0036] As used herein, a heterocyclic group or a heterocycle takes into account aromatic and non-aromatic cyclic groups. An isoaryl group also refers to a heteroaryl group. Preferred non-aromatic heterocyclic groups have 3 to 7 ring atoms and contain at least one heteroatom such as nitrogen, oxygen, and sulfur. The heterocyclic group may be an aromatic heterocyclic group having at least one heteroatom selected from at least one nitrogen atom, oxygen atom, sulfur atom, and selenium atom.

[0037] As used herein, the heteroaryl group refers to non-condensed and condensed heteroaromatic groups having 1 to 5 heteroatoms. Preferred heteroaryl groups are heteroaryl groups having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoadiazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranpyridine, furodipyridine, benzothienopyridine, thienobipyridine, benzoselenopyridine, and selenobenzopyridine, and preferably include dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazole and their aza analogs. Further, the heteroaryl group may be substituted.

[0038] The alkoxy group is represented by an -O-alkyl group. Examples and preferred examples of the alkyl group are the same as those described above. Examples of alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

[0039] An aryloxy group is represented by -O-aryl group or -O-heteroaryl group. Examples and preferred examples of the aryl group and the heteroaryl group are the same as those described above. Examples of the aryloxy group having 6 to 40 carbon atoms include a phenoxy group and a biphenyloxy group.

[0040] An aralkyl group, as used herein, is an alkyl group having an aryl substituent. The aralkyl group may also be substituted. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among them, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferred.

[0041] In azadibenzofuran, azadibenzothiophene, etc., "aza" refers to the substitution of one or more C-H groups in the corresponding aromatic fragment by nitrogen atoms. For example, azatriphenylene includes dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline, and other analogs having two or more nitrogens in the ring system. A person skilled in the art can easily conceive of other nitrogen analogs of the above-described aza derivatives, and all of these analogs are determined to be included in the technical terms described herein.

[0042] The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, heterocyclic group, aryl group, and heteroaryl group may be unsubstituted, or may be substituted with one or more selected from deuterium, halogen, alkyl group, cycloalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, cyclic amino group, silyl group, alkenyl group, cycloalkenyl group, heteroalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxyl group, ether group, ester group, nitrile group, isonitrile group, thioalkyl group, sulfinyl group, sulfonyl group, phosphine group, and combinations thereof.

[0043] When describing a molecular fragment to be attached to another moiety in the form of a substituent or otherwise, it should be understood that the name can be determined depending on whether it is a fragment (e.g., phenyl group, phenylene group, naphthyl group, dibenzofuranyl group) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different forms of substituent designation or attachment of fragments are considered equivalent.

[0044] In the compounds referred to herein, the hydrogen atoms may be partially or fully substituted with deuterium. Other atoms, such as carbon and nitrogen, may also be substituted with their other stable isotopes. Substitution with other stable isotopes in the compounds may be preferred to improve the efficiency and stability of the device.

[0045] In the compounds referred to in this specification, multiple substitution refers to the range up to the most usable substitution, including double substitution. When a certain substituent in the compounds referred to in this specification means multiple substitution (including double substitution, triple substitution, quadruple substitution, etc.), it means that the substituent may be present at multiple usable substitution positions on its bonding structure, and the substituents present at all of the multiple usable substitution positions may have the same structure or different structures.

[0046] In the compounds referred to in this specification, the description that adjacent substituents may combine to form a ring is recognized to refer to the two groups being bonded to each other by a chemical bond. This is illustrated by the following figures.

Chemical formula

[0047] Also, the description that adjacent substituents may combine to form a ring is recognized to refer to the case where one of the two groups represents hydrogen, and the second group combines with the position where the hydrogen atom is bonded to form a ring. This is illustrated by the following figures.

Chemical formula

[0048] According to one embodiment of the present invention, an L a metal complex having a ligand is disclosed.

Chemical formula

[0049] According to one embodiment of the present invention, Cy is

Chemical formula

[0050] According to one embodiment of the present invention, the metal complex has the general formula M(L a ) m (L b ) n (L c ) q wherein L a is a first ligand that coordinates with metal M, and L b and L c are a second ligand and a third ligand that coordinate with metal M, respectively. L b and L c may be the same or different. L a , L b and L c may combine to form a polydentate ligand. m is 1, 2 or 3, n is 0, 1 or 2, q is 0, 1 or 2, and m + n + q is equal to the oxidation state of M. Metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt. Preferably, metal M is selected from Pt, Os or Ir. L a is independently selected from

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0051] According to one embodiment of the present invention, in the structural formula of the ligand L a , X is selected from O, S or Se.

[0052] According to one embodiment of the present invention, it has a structure represented by any one of Formulas 2 to 10.

Chemical formula

Chemical formula

[0053] According to one embodiment of the present invention, the metal complex has a structure represented by Formula 2-a.

Chemical formula

[0054] According to one embodiment of the present invention, in Formula 2-a, when at least one of R 11 and R 14 is not hydrogen, R 12 and R 13is independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxyl group, an ester group, a cyano group, an isocyano group, a thioalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

[0055] According to one embodiment of the present invention, in Formula 2-a, R 11 and R 14 are both hydrogen, R 12 and R 13 are independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxyl group, an ester group, a cyano group, an isocyano group, a thioalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof, and the sum of the number of carbon atoms in R 12 and R 13 is 1 or less.

[0056] According to one embodiment of the present invention, in Formula 1, at least one of X5 to X8 is CR x2 and the R x2 is a cyano group.

[0057] According to one embodiment of the present invention, in the formula 1, X5 to X8 are each independently CR x2 selected from, and at least one of the said R x2 is a cyano group.

[0058] According to one embodiment of the present invention, R4 may represent mono-substituted, di-substituted, tri-substituted or tetra-substituted. When there are a plurality of R4, they may be the same or different. R4 is selected from the group consisting of deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a cyano group, and combinations thereof, and at least one of R4 is a cyano group.

[0059] According to one embodiment of the present invention, the ligand L a is selected from the group consisting of L a1 to L a575 . For the specific structures of L a1 to L a575 , please refer to claim 8.

[0060] According to one embodiment of the present invention, the ligand L a is selected from the group consisting of L a1 to L a957 . For the specific structures of L a1 to L a957 , please refer to claim 8.

[0061] According to one embodiment of the present invention, the hydrogen in L a may be partially or fully deuterated.

[0062] According to one embodiment of the present invention, the hydrogen in the aryl group of L a may be partially or fully deuterated.

[0063] According to one embodiment of the present invention, L aHydrogen in the alkyl group may be partially or fully deuterated.

[0064] According to one embodiment of the present invention, hydrogen in L a may be partially or fully deuterated. Among them, the ligand L a is selected from the group consisting of L a958 ~L a1019 . For the specific structure of L a958 ~L a1019 , please refer to claim 9.

[0065] According to one embodiment of the present invention, the metal complex has the formula IrL a (L b )2 or Ir(L a )2L b , where L a is one or two selected from L a1 ~L a575 , and L b is one or two selected from the group consisting of L b1 ~L b41 . For the specific structure of L b1 ~L b41 , please refer to claim 10.

[0066] According to one embodiment of the present invention, the metal complex has the formula IrL a (L b )2 or Ir(L a )2L b , where L a is one or two selected from L a1 ~L a1019 , and L b is

Chemical formula

Chemical formula

Chemical formula

[0067] According to one embodiment of the present invention, the metal complex has the formula Ir(L a )2L c , or IrL a (L c )2, where L a is one or two selected from L a1 to L a1019 , and L c is one or two selected from the group consisting of L c1 to L c360 . Among them, for the specific structures of L c1 to L c360 , please refer to Claim 11.

[0068] According to one embodiment of the present invention, the metal complex is selected from the structures represented by any one of Metal Complex 1 to Metal Complex 316, Metal Complexes 1 to 226 have the structure of IrL a (L b )2, where the two L b are the same, and L a and L b respectively correspond to the structures shown in the following table,

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

[0069] According to one embodiment of the present invention, a compound selected from the group consisting of Compounds 1 to 136 is further disclosed. For the specific structures of Compounds 1 to 136, please refer to Claim 13.

[0070] According to one embodiment of the present invention, an electroluminescent device including an anode, a cathode, and an organic layer provided between the anode and the cathode, wherein the organic layer contains a metal complex containing a ligand L represented by Formula 1 is further disclosed. a

Chemical formula

[0071] According to one embodiment of the present invention, in the electroluminescent device, the organic layer is a light-emitting layer, and the metal complex is a light-emitting material.)

[0072] According to one embodiment of the present invention, in the electroluminescent device, the organic layer further includes a host material.)

[0073] According to an embodiment of the present invention, in the electroluminescent element, the organic layer further includes at least two host materials.

[0074] According to an embodiment of the present invention, the host material includes at least one chemical group selected from the group consisting of benzene, biphenyl, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazolyl, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, azadibenzoselenophene, triphenylene, azatriphenylene, fluorenyl, silicon fluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

[0075] According to an embodiment of the present invention, the electroluminescent element is incorporated into an element in the group consisting of consumer products, electronic element modules, organic light emitting elements, and lighting panels.

[0076] According to another embodiment of the present invention, a formulation of a compound containing a metal complex is further disclosed. The specific structure of the metal complex is represented by any one of the above-described embodiments.

[0077] Combinations with other materials

[0078] The materials of the specific layers used in the organic light emitting element described in the present invention can be used in combination with various other materials present in the element. Combinations of these materials are described in detail in paragraphs 0132 to 0161 of US Patent Application US2016 / 0359122A1, the entire content of which is incorporated herein by reference. The materials described or mentioned are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily identify other materials that can be used in combination by referring to the literature.

[0079] In this specification, it is described that the materials of specific layers used in the organic light-emitting device can be used in combination with various other materials present in the device. Exemplarily, the light-emitting dopants disclosed in this specification can be used in combination with various hosts, transport layers, blocking layers, injection layers, electrodes, and other possible layers. The combinations of these materials are described in detail in paragraphs 0080 to 0101 of patent application US2015 / 0349273A1, the entire content of which is incorporated herein by reference. The materials described or mentioned are non-limiting examples of materials that can be used in combination with the compounds disclosed in this specification, and for those skilled in the art, other materials that can be used in combination can be easily identified by referring to the literature.

[0080] In the examples of material synthesis, unless otherwise explained, all reactions are carried out under the protection of nitrogen. All reaction solvents are anhydrous and are used as commercially available products. For the synthesized products, one or more common instruments in this field (including but not limited to nuclear magnetic resonance spectrometers manufactured by Bruker, liquid chromatography, liquid chromatography / mass spectrometers, gas chromatography / mass spectrometers, differential scanning calorimeters, fluorescence spectrometers manufactured by Shanghai ▲Liao▼guang Technology, electrochemical workstations manufactured by Wuhan Kest, sublimation devices manufactured by Anhui Beiyike, etc.) are used to perform structure confirmation and property tests in a method well-known to those skilled in the art. In the examples of the device, for the properties of the device, common instruments in this field (including but not limited to evaporation machines manufactured by Angstrom Engineering, optical test systems manufactured by Suzhou Fushida, service life test systems, ellipsometers manufactured by Beijing Liangtuo, etc.) are also used to perform tests in a method well-known to those skilled in the art. Since those skilled in the art know the relevant content such as the use of the above-mentioned instruments and test methods, the specific data of the samples can be obtained reliably and without being affected, so the above-mentioned relevant content will not be repeatedly explained in this specification.

[0081] Examples of Material Synthesis

[0082] The preparation method of the compounds according to the present invention is not limited. Typically but not limitedly, taking the following compounds as examples, the synthetic routes and preparation methods are as follows.

[0083] Synthesis Example 1: Compound IrL a1 (L b1 )2 (Metal Complex 1) Synthesis

[0084] Step 1:

Chemical Formula

[0085] Step 2:

Chemical Formula

[0086] Step 3:

Chemical formula

[0087] Step 4:

Chemical formula

[0088] Step 5:

Chemical formula

[0089] Step 6:

Chemical formula

[0090] Synthesis Example 2: Compound IrL a4 (L b1 )2(metal complex 4) synthesis

[0091] Step 1:

Chemical formula

[0092] Step 2:

Chemical formula

[0093] Step 3:

Chemical formula

[0094] Synthesis Example 3: Synthesis of compound IrL a2 (L b1 )2 (metal complex 2)

[0095] Step 1:

Chemical formula

[0096] Step 2:

Chemical formula

[0097] Step 3:

Chemical formula

[0098] Step 4:

Chemical formula

[0099] Step 5:

Chemical formula

[0100] Step 6:

Chemical formula

[0101] Synthesis Example 4: Synthesis of compound IrL a3 (L b1 )2 (metal complex 3)

[0102] Step 1:

Chemical formula

[0103] Step 2:

Chemical formula

[0104] Step 3:

Chemical formula

[0105] Synthesis Example 5: Compound IrL a1 (L b3 )2 (metal complex 67) synthesis

[0106] Step 1:

Chemical formula

[0107] Synthesis Example 6: Compound IrL a1 (L b4 )2 (metal complex 107) synthesis

[0108] Step 1: [Chemical formula] To a dried 500 mL round-bottom flask, intermediate 5 (2.2 g, 8.1 mmol), iridium complex (4.0 g, 5.4 mmol), and ethanol (120 mL) were added in sequence. The flask was purged with N2 three times and protected with N2, and then heated until the reflux reaction was carried out for 24 h. After the reaction was cooled, it was filtered through diatomaceous earth. It was washed twice each with methanol and n-hexane, and the yellow solid on the diatomaceous earth was dissolved in dichloromethane. The organic phase was collected, concentrated under reduced pressure, purified by column chromatography, and the yellow solid compound IrL a1 (L b4 )2 (metal complex 107) (0.8 g, yield 18.6%) was obtained. The product was confirmed as the target product with a molecular weight of 798.

[0109] Synthesis Example 7: Compound IrL a1 (L b8 )2 (metal complex 147) synthesis

[0110] Step 1: [Chemical formula] To a dried 500 mL round-bottom flask, intermediate 5 (2.4 g, 8.9 mmol), iridium complex (3.3 g, 4.4 mmol), and ethanol (250 mL) were added in sequence. The flask was purged with N2 three times and protected with N2, and then heated until the reflux reaction was carried out for 24 h. After the reaction was cooled, it was filtered through diatomaceous earth. It was washed twice each with methanol and n-hexane, and the yellow solid on the diatomaceous earth was dissolved in dichloromethane. The organic phase was collected, concentrated under reduced pressure, purified by column chromatography, and the yellow solid compound IrL a1 (L b8 )2 (metal complex 147) (1.0 g, yield 27.5%) was obtained. The product was confirmed as the target product with a molecular weight of 826.

[0111] Synthesis Example 8: Compound IrL a221 (L b1 )2 (metal complex 17) synthesis

[0112] Step 1:

Chem.

[0113] Step 2:

Chem.

[0114] Synthesis Example 9: Synthesis of compound IrL a962 (L b1 )2 (metal complex 53)

[0115] Step 1:

Chem.

[0116] Synthesis Example 10: Compound IrL a962 (L b3 )2 (metal complex 93) synthesis

[0117] Step 1:

Chemical formula

[0118] Synthesis Example 11: Compound IrL a293 (L b1 )2 (metal complex 19) synthesis

[0119] Step 1: [Chemical formula] To a dried 250 mL round-bottom flask, intermediate 17 (2.6 g, 7.5 mmol), iridium complex (2.2 g, 6.0 mmol), and 150 mL of ethanol were sequentially added. Under the protection of N2, the mixture was heated until the reflux reaction was carried out for 24 h. After the reaction was cooled, it was filtered through diatomaceous earth. It was washed twice with methanol and n-hexane respectively, and the yellow solid on the diatomaceous earth was dissolved in dichloromethane. The organic phase was collected, concentrated under reduced pressure, purified by column chromatography, and the yellow solid compound IrL a293 (L b1 )2(metal complex 19) (0.6 g, yield 12%) was obtained. The product was confirmed as the target product with a molecular weight of 846.

[0120] Synthesis Example 12: Compound IrL a293 (L b3 )2(metal complex 77) synthesis

[0121] Step 1: [Chemical formula] To a dried 250 mL round-bottom flask, intermediate 17 (2.6 g, 7.5 mmol), iridium complex (2.2 g, 6.0 mmol), and 150 mL of ethanol were sequentially added. Under the protection of N2, the mixture was heated until the reflux reaction was carried out for 24 h. After the reaction was cooled, it was filtered through diatomaceous earth. It was washed twice with methanol and n-hexane respectively, and the yellow solid on the diatomaceous earth was dissolved in dichloromethane. The organic phase was collected, concentrated under reduced pressure, purified by column chromatography, and the yellow solid compound IrL a293 (L b3 )2(metal complex 77) (0.6 g, yield 12%) was obtained. The product was confirmed as the target product with a molecular weight of 874.

[0122] Synthesis Example 13: Compound IrL a987 (L b3 )2(metal complex 102) synthesis

[0123] Step 1: [Chemical formula] To a dried 250 mL round-bottom flask, 18 (3.0 g, 8.5 mmol) of intermediate, 4.2 g (5.7 mmol) of iridium complex, 100 mL each of 2-ethoxyethanol and DMF were sequentially added. Under the protection of N2, the mixture was heated and reacted at 85 °C for 96 h. After the reaction was cooled, it was filtered through diatomaceous earth. It was washed twice with methanol and n-hexane respectively, and the yellow solid on the diatomaceous earth was dissolved in dichloromethane. The organic phase was collected, concentrated under reduced pressure, purified by column chromatography, and the yellow solid compound IrL a987 (L b3 )2 (metal complex 102) (0.9 g, yield 18.0%) was obtained. The product was confirmed as the target product with a molecular weight of 879.

[0124] Those skilled in the art should know that the above preparation method is merely exemplary, and other compound structures of the present invention can be obtained by improving it.

[0125] Examples of the device

[0126] Example 1

[0127] First, a glass substrate having an indium tin oxide (ITO) anode with a thickness of 120 nm was cleaned and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glove box to remove water. Then, the substrate was attached to a substrate holder and placed in a vacuum chamber. Subsequently, for the specified organic layers, when the degree of vacuum was 10 -8 torr, evaporation was sequentially performed on the ITO anode by hot vacuum evaporation at a rate of 0.2 - 2 angstroms / second. Compound HI (100 Å) was used as the hole injection layer (HIL). Compound HT (350 Å) was used as the hole transport layer (HTL). Compound H1 (50 Å) was used as the electron blocking layer (EBL). Then, compound IrL in the present invention a1 (Lb1 )2 (Metal complex 1) was doped into host compounds H1 and H2 to form a light-emitting layer (EML, 8:46:46, 400 Å). Compound H2 (100 Å) was used as a hole-blocking layer (HBL). In the HBL, a mixture of compound ET and 8-hydroxyquinoline-lithium (Liq) was deposited as an electron transport layer (ETL, 40:60, 350 Å). Finally, Liq with a thickness of 10 Å was deposited as an electron injection layer, and 1200 Å of Al was deposited as a cathode. Then, the device was transferred to a glove box and encapsulated using a glass cover and a moisture absorbent to complete the device.

[0128] Example 2

[0129] Example 2 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a2 (L b1 )2 (Metal complex 2) in the present invention is used to replace the compound IrL a1 (L b1 )2 (Metal complex 1) in the present invention in Example 1.

[0130] Example 3

[0131] Example 3 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a1 (L b3 )2 (Metal complex 67) in the present invention is used to replace the compound IrL a1 (L b1 )2 (Metal complex 1) in the present invention in Example 1.

[0132] Example 4

[0133] Example 4 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a1 (L b4 )2 (Metal complex 107) in the present invention is used to replace the compound IrL a1 (L b1 )2 (Metal complex 1) in the present invention in Example 1.

[0134] Example 5

[0135] Example 5 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a1 (L b8 )2 (metal complex 147) in the present invention is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0136] Example 6

[0137] Example 6 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a962 (L b1 )2 (metal complex 53) in the present invention is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0138] Example 7

[0139] Example 7 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a962 (L b3 )2 (metal complex 93) in the present invention is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0140] Example 8

[0141] Example 8 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL a293 (L b3 )2 (metal complex 77) in the present invention is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0142] Example 9:

[0143] Example 9 is the same as the embodiment in Example 1, except that in the light-emitting layer, the compound IrL in the present invention, IrL a987 (L b3 )2 (metal complex 102) is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0144] Comparative Example 1

[0145] Comparative Example 1 is the same as the embodiment in Example 1, except that in the light-emitting layer, Comparative Compound 1 is used to replace the compound IrL a1 (L b1 )2 (metal complex 1) in the present invention in Example 1.

[0146] For one or more layers in which the materials used are different, they are obtained by doping compounds in the above weight ratio.

[0147] The layer structure and thickness of some details of the device are shown in Table 1.

Table 7

Table 8

[0148] The structure of the materials used in the device is represented as follows.

Chemical formula

Chemical formula

[0149] The device IVL and service life characteristics were measured at different current densities and voltages. Table 2 shows the measured external quantum efficiency (EQE), λ max , full width at half maximum (FWHM), voltage (V), and CIE data at 1000 nits.

Table 9

[0150] Table 3 shows the external quantum efficiency (EQE), λ max , full width at half maximum (FWHM), voltage (V), and CIE data measured at 1000 nits for Examples 3 to 9 and Comparative Example 1. The lifetime (LT97) data for Examples 3 to 9 and Comparative Example 1 were measured at a constant current of 80 mA / cm 2 .

Table 10

[0151] Summary As can be seen from Table 2, the examples of the devices having the compounds in the present invention exhibit a plurality of advantages over the comparative compounds. Compared with Comparative Compound 1, the compounds in the present invention unexpectedly exhibit many characteristics. For example, in Examples 1 and 2, the EQE reached high efficiencies of 23.62% and 24.81% respectively, and the voltage was 0.2 V or more lower than that of Comparative Example 1 using Comparative Compound 1 without cyano group substitution, and there was no obvious blue shift or red shift in emission. Most unexpectedly, it has a very narrow emission peak width, especially the full width at half maximum in Example 2 is only 42.5 nm, which is unprecedented in green phosphorescent devices. These advantages contribute extremely greatly to the improvement of the level and color saturation of the green light emitting devices.

[0152] As can be seen from Table 3, the examples of the devices having the compounds in the present invention exhibit a plurality of advantages over the comparative compounds. Examples 3 to 7 show higher EQE (23.25% - 24.15% vs. 22.52%) compared to Comparative Example 1, and the lifetime is clearly superior to that of Comparative Example 1 (17.9 h - 23.7 h vs. 15 h). Example 6 has a lifetime approximately 60% higher than that of Comparative Example 1 (23.7 h vs. 15 h), and the voltage is 0.2 V - 0.3 V or more lower than that of Comparative Example 1 without cyano group substitution.

[0153] Examples 8 and 9 show higher EQE (26.23%, 25.93% vs. 22.52%) and a voltage drop of 0.3 V or more (2.64 V to 2.67 V vs. 2.98 V) compared to Comparative Example 1. Example 9 showed a 14.67% improvement in service life (17.2 h vs 15 h) compared to Comparative Example 1. Most surprisingly, it has a very narrow emission peak width, especially the full width at half maximum in Example 8 is only 37.8 nm, which is unprecedented in green phosphorescent devices.

[0154] Examples 8 and 9 are examples corresponding to the substitution positions being hydride and deuteride. Through comparison, since the service life in Example 9 is superior to that in Example 8, the advantages of deuteride in the present invention have been proven.

[0155] It should be understood that the various examples described herein are merely illustrative and not intended to limit the scope of the present invention. Therefore, it is obvious to those skilled in the art that the present invention to be protected includes variations of the specific and preferred examples described herein. Many of the materials and structures described herein can be replaced with other materials and structures on the premise of not departing from the concept of the present invention. It should be understood that the various theories about why the present invention functions are not limiting.

Claims

1. Use in the production of an organic layer of a metal complex containing the ligand L represented by formula 1 ａ ​ 【Chemical 1】 Formula 1 (Cy is 【Chemical 2】 any structure selected from the group consisting of 「#」 represents the position bonded to the metal M, and 「*」 represents the position bonded to X １ , X ２ , X ３ or X ４ represents the position bonded to R may represent mono-substitution, multiple substitutions up to the most possible substitutions, or no substitution. When multiple Rs are present in any structure, the Rs may be the same or different. X １ to X ４ are each independently selected from C, CR ｘ１ or N, and at least one of X １ to X ４ is C and is bonded to the Cy, and when there are a plurality of CR １ in X ４ to X ｘ１ ｘ１ ｘ１ the R may be the same or different X ５ ~X ８ are each independently selected from CR ｘ２ or N, and when there are a plurality of CRs in X ５ ~X ８ the R ｘ２ may be the same or different ｘ２ ​ X is selected from the group consisting of O, S, Se, NR ｘ３ , CR ｘ４ R ｘ５ and SiR ｘ６ R ｘ７ and is selected from the group consisting of R, R ｘ１ , R ｘ２ , R ｘ３ , R ｘ４ , R ｘ５ , R ｘ６ and R ｘ７ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof. Said R ｘ１ and R ｘ２ at least one of which is a cyano group, Two adjacent substituents may combine to form a ring. X １ , X ２ , X ３ or X ４ is bonded to the metal by a metal-carbon bond or a metal-nitrogen bond.)

2. In the metal complex, Cy is 【Chemical Formula 3】 Use in the manufacture of the organic layer of the metal complex according to Claim 1, wherein ("#" represents the position bonded to metal M, and "*" represents the position bonded to X １ , X ２ , X ３ or X ４ represents the position bonded to, R may represent mono-substitution, multiple substitutions up to the most possible substitutions, or no substitution. When multiple Rs are present in any structure, the Rs may be the same or different. Each R is independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine group having 0 to 20 carbon atoms, carboxyl group, cyano group, isocyano group, thioalkyl group, phosphino group, and combinations thereof. Two adjacent substituents may combine to form a ring.)

3. The metal complex has the general formula M(L ａ ), ｍ (L ｂ ), ｎ (L ｃ ) ｑ wherein L ａ is a first ligand that coordinates with the metal M, and L ｂ and L ｃ are a second ligand and a third ligand that coordinate with the metal M, respectively, and L ｂ and L ｃ may be the same or different. Said L ａ , L ｂ and L ｃ may combine to form a polydentate ligand, m is 1, 2 or 3, n is 0, 1 or 2, q is 0, 1 or 2, and m + n + q is equal to the oxidation state of M. The metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt. L ａ is, independently, 【Chemical 4】 【Chemical Formula 5】 【Chemical Formula 6】 【Chemical Formula 7】 selected from the group consisting of X is selected from the group consisting of O, S, Se, NR ｘ３ , CR ｘ４ R ｘ５ and SiR ｘ６ R ｘ７ and is selected from the group consisting of R １ 、 R ２ 、 R ３ and R ４ may represent mono-substitution, di-substitution, tri-substitution, tetra-substitution, or no substitution, R １ 、R ２ 、R ３ 、R ４ 、R ｘ３ 、R ｘ４ 、R ｘ５ 、R ｘ６ and R ｘ７ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof. R ３ and R ４ at least one of which is a cyano group, Two adjacent substituents may combine to form a ring. L ｂ and L ｃ are each independently 【Chemical 8】 selected from the group consisting of R ａ , R ｂ , and R ｃ may represent mono-substituted, di-substituted, tri-substituted, tetra-substituted, or unsubstituted. X ｂ is selected from the group consisting of O, S, Se, NR Ｎ１ , and CR Ｃ１ R Ｃ２ and is selected from the group consisting of R ａ , R ｂ , R ｃ , R Ｎ１ , R Ｃ１ and R Ｃ２ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof. Use in the manufacture of the organic layer of the metal complex according to Claim 1, wherein two adjacent substituents may combine to form a ring.

4. Use in the manufacture of the organic layer of the metal complex according to Claim 3, wherein the metal M is selected from Pt, Os or Ir.

5. Use in the production of an organic layer of the metal complex according to claim 3, wherein the metal complex has a structure represented by any one of Formula 2 to Formula 10. 【Chemical Formula 9】 【Chemical Formula 10】 (m is 1, 2, or 3, X is selected from O, S, or Se, R １ 、R ３ and R ４ may represent mono-substitution, di-substitution, tri-substitution, tetra-substitution, or unsubstitution, R ａ 、 R ｂ 、 and R ｃ may represent mono-substitution, di-substitution, tri-substitution, tetra-substitution, or unsubstitution, R １ , R ３ , R ４ , R ａ , R ｂ and R ｃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof. R ３ and R ４ at least one of which is a cyano group, and two adjacent substituents may be bonded to form a ring.)

6. Use in the production of an organic layer of the metal complex according to claim 5, wherein the metal complex has a structure represented by Formula 2-a. 【Chemical 11】 (m is 1, 2, or 3, X is selected from O, S, or Se, R ３ and R ４ may represent mono-substituted, di-substituted, tri-substituted, tetra-substituted, or unsubstituted, R ａ , R ｂ , and R ｃ may represent mono-substitution, di-substitution, tri-substitution, tetra-substitution, or unsubstitution, R １１ 、R １２ 、R １３ 、R １４ 、R ３ 、R ４ 、R ａ 、and R ｂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof. R ３ 、 R ４ at least one of which is a cyano group, and two adjacent substituents may be bonded to form a ring.)

7. R １１ and R １４ are both hydrogen, R １２ and R １３ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and combinations thereof, and the sum of the number of carbon atoms in １２ R １３ is 1 or less, Alternatively, R １１ and R １４ are not hydrogen, R １２ and R １３ each independently represents hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, a carboxyl group, a cyano group, an isocyano group, a thioalkyl group, a phosphino group, and a combination thereof, and is used in the production of the organic layer of the metal complex according to claim 6.

8. R １１ 、R １２ 、R １３ 、R １４ 、R ａ 、and R ｂ are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and combinations thereof. R ３ and R ４ each independently represents hydrogen, deuterium, a halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a cyano group, and a combination thereof, and is selected from the group consisting of: R ３ 、 R ４ Use in the production of an organic layer of the metal complex according to claim 6, wherein at least one of

9. In the formula 1, X ５ ~X ８ At least one of which is CR ｘ２ And the R ｘ２ Is a cyano group, use in the production of the organic layer of the metal complex according to claim 1.

10. In the formula 1, X ５ ~X ８ are each independently selected from CR ｘ２ , and at least one of the R ｘ２ is a cyano group, use in the production of the organic layer of the metal complex according to claim 1.

11. In the formula 1, X ７ is selected from CR ｘ２ and at least one of the R ｘ２ is a cyano group, or X ８ is selected from CR ｘ２ and at least one of the R ｘ２ is a cyano group, Use in the production of the organic layer of the metal complex according to claim 1.

12. R ４ may represent mono-substitution, di-substitution, tri-substitution or tetra-substitution. When R ４ is plural, they may be the same or different. R ４ is selected from the group consisting of deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a cyano group, and combinations thereof, and at least one of R ４ is a cyano group, use in the production of the organic layer of the metal complex according to claim 5 or 6.

13. R ４ may represent mono-substitution, di-substitution, tri-substitution or tetra-substitution. When R ４ is plural, they may be the same or different. R ４ is selected from the group consisting of deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a cyano group, and combinations thereof, and at least one of R ４ is a cyano group. R ３ may represent monosubstitution, disubstitution, or no substitution, and when ３ there are a plurality of Rs, they may be the same or different. ３ R is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, and combinations thereof, and is used in the production of the organic layer of the metal complex according to claim 5 or 6.

14. Ligand L ａ is 【Chemical 12】 【Chemical 13】 【Chemical 14】 【Chemical Formula 15】 【Chemical 16】 【Chemical 17】 【Chemical 18】 【Chemical 19】 【Chemical 20】 【Chemical 21】 【Chemical 22】 【Chemical 23】 【Chemical 24】 【Chemical Formula 25】 【Chemical 26】 【Chemical 27】 【Chemical 28】 【Chemical 29】 【Chemical Formula 30】 【Chemical 31】 【Chemical 32】 【Chemical 33】 【Chemical 34】 【Chemical 35】 【Chemical 36】 【Chemical 37】 【Chemical 38】 【Chemical Formula 39】 【Chemical Formula 40】 【Chemical Formula 41】 【Chemical 42】 【Chemical 43】 【Chemical 44】 【Chemical 45】 【Chemical 46】 【Chemical 47】 【Chemical 48】 【Chemical 49】 【Chemical Formula 50】 【Chemical Formula 51】 【Chemical 52】 【Chemical Formula 53】 【Chemical 54】 【Chemical 55】 【Chemical 56】 【Chemical 57】 【Chemical 58】 【Chemical Formula 59】 【Chemical Formula 60】 【Chemical Formula 61】 【Chemical Formula 62】 【Chemical Formula 63】 【Chemical Formula 64】 【Chemical Formula 65】 Use in the production of an organic layer of the metal complex according to claim 3, selected from the group consisting of

15. Said L ａ is used in the production of the organic layer of the metal complex according to claim 14, which may be partially or fully deuterated.

16. The hydrogen in the aryl group of the foregoing L ａ may be partially or fully deuterated, Or the hydrogen in the alkyl group of the L ａ may be partially or fully deuterated, and its use in the production of the organic layer of the metal complex according to claim 14.

17. The metal complex has the formula IrL ａ (L ｂ ) ２ or Ir(L ａ ) ２ L ｂ and has, L ａ is L ａ１ to L ａ３９２ and L ａ４０８ to L ａ１０１９ is one or two selected from L ｂ is 【Chemical Formula 66】 【Chemical Formula 67】 【Chemical Formula 68】 Use in the production of an organic layer of the metal complex according to claim 14, which is one or two selected from the group consisting of

18. The metal complex has the formula Ir(L ａ ), ２ L ｃ or IrL ａ (L ｃ ), ２ and has L ａ is L ａ１ to L ａ３９２ and L ａ４０８ to L ａ１０１９ is one or two selected from L ｃ is 【Chemical Formula 69】 【Chemical 70】 【Chemical 71】 【Chemical 72】 【Chemical Formula 73】 【Chemical 74】 【Chemical 75】 【Chemical 76】 【Chemical 77】 【Chemical 78】 【Chemical Formula 79】 【Chemical 80】 【Chemical 81】 【Chemical 82】 【Chemical 83】 Use in the production of an organic layer of the metal complex according to claim 17, which is one or two selected from

19. The metal complex is selected from the structures represented by any one of Metal Complex 1 to Metal Complex 316, Metal complexes 1 to 226 have the structure of IrL ａ (L ｂ ) ２ and two L ｂ are the same, and L ａ and L ｂ respectively correspond to the structures shown in the following table. 【Table 1】 【Table 2】 【Table 3】 【Table 4】 Metal complexes 227 to 274 have the structure of Ir(L ａ ), ２ L ｃ wherein two L ａ are identical, and L ａ and L ｃ correspond to the structures shown in the following table, respectively. 【Table 5】 Metal complexes 275 to 316 have the structure of Ir(L ａ ), ３ wherein the three L ａ are identical, and L ａ is used in the production of the organic layer of the metal complex according to claim 18, corresponding to the structure shown in the following table. 【Table 6】

20. Use in the production of an electro-luminescent element of the metal complex, wherein the electro-luminescent element includes an anode, a cathode, and an organic layer provided between the anode and the cathode, and the organic layer includes an organic layer obtained by use in the production of an organic layer of the metal complex according to any one of claims 1 to 19.

21. Use in the production of an electro-luminescent element of the metal complex according to claim 20, wherein the electro-luminescent element is incorporated into an element in the group consisting of consumer products, electronic element modules, organic light-emitting elements, and lighting panels.

Images