CN113387983B

CN113387983B - Metal complex of ligand with polysubstituted biaryl structure

Info

Publication number: CN113387983B
Application number: CN202010165068.0A
Authority: CN
Inventors: 张翠芳; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2020-03-11
Filing date: 2020-03-11
Publication date: 2023-04-18
Anticipated expiration: 2040-03-11
Also published as: CN113387983A

Abstract

Disclosed is a metal complex having a ligand of a polysubstituted biaryl structure. The metal complex has M (L) _a ) _m (L _b ) _n Wherein the first ligand L _a Selected from ligands having a polysubstituted biaryl structure. The metal complexes can be used as light-emitting materials in electroluminescent devices. The novel metal complexes can improve the melting point under the condition of keeping the sublimation temperature unchanged, are beneficial to sublimation, prepare devices by an evaporation method, can greatly prolong the service life of the devices while improving the external quantum efficiency, and can provide better device performance. An electroluminescent device and compound formulation are also disclosed.

Description

Metal complex of ligand with polysubstituted biaryl structure

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. And more particularly, to a metal complex containing a ligand of a polysubstituted biaryl structure, and an organic electroluminescent device and a compound formulation comprising the same.

Background

Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic Light Emitting Transistors (OLETs), organic Photovoltaics (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic plasma light emitting devices.

In 1987, tang and Van Slyke, by Isman Kodak, reported a two-layer organic electroluminescent device comprising 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). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). State-of-the-art OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Since OLEDs are a self-emissive solid state device, it offers great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in the fabrication of flexible substrates.

OLEDs can be classified into three different types according to their light emitting mechanisms. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes 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, making it possible to return excitons from the triplet state to the singlet state. In TADF devices, triplet excitons are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymer OLED comprises a conjugated polymer and a non-conjugated polymer having pendant light-emitting groups. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.

Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.

The light emitting color of the OLED can be realized by the structural design of the light emitting material. An OLED may comprise one light emitting layer or a plurality of light emitting layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have the problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full-color OLED displays typically employ a hybrid strategy, using either blue fluorescence and phosphorescent yellow, or red and green. At present, the rapid decrease in efficiency of phosphorescent OLEDs at high luminance is still a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.

Has been disclosed in US20050164030A1

A metal complex of the structure wherein R ₃ ' must be selected from the group consisting of alkyl, heteroalkyl, aryl, heteroaryl and aralkyl, with a specific example being ` X `>

It is noted that the use of biphenyl structural segments in carbon-nitrogen ligands is contemplated, but there is no disclosure of continued introduction of substituents on the biphenyl segments, nor is there any improvement in performance that can be achieved thereby.

JP2011105676A discloses a liquid crystal display device

Structural metal complexes, a specific example being ` er `>

The inventors have noted that long-chain alkyl substitution can enhance the solubility of the light-emitting material, thereby facilitating wet film formation, and that such compounds have good stability in solution and in light-emitting devices. However, the disclosed compounds must have three identical ligands and do not disclose or teach the performance enhancements that result when different ligands are coordinated to the metal.

The small molecule phosphorescent doped material is an important part of phosphorescent luminescent materials, and although the small molecule phosphorescent luminescent materials have been widely researched, the performance of the small molecule phosphorescent luminescent materials still has a space for further improvement so as to meet the requirements on device preparation, device performance and the like. In addition, the evaporation method is a method for manufacturing a device commonly used for a small molecule phosphorescent light-emitting material, and the preparation of the device is not facilitated by too high sublimation temperature or too low melting point.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of novel metal complexes having ligands of polysubstituted biaryl structures. The compounds are useful as light-emitting materials in organic electroluminescent devices. Compared with the reported phosphorescent metal complexes, the novel metal complexes with the ligands of the polysubstituted biaryl structures can improve the melting point under the condition of keeping the sublimation temperature unchanged, are beneficial to sublimation, can prepare devices by an evaporation method, can greatly prolong the service life of the devices while improving the external quantum efficiency, and can provide better device performance.

According to one embodiment of the present invention, a method of manufacturing a semiconductor device having M (L) _a ) _m (L _b ) _n Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, L _a And L _b First and second ligands, respectively, of said complex;

wherein M is 1,2 or 3,n is 0,1 or 2,m + n equals the oxidation state of metal M; when m =2, two L _a The same or different; when m =3, there are at least two different L _a (ii) a When n =2, two L _b The same or different;

wherein the first ligand L _a Has a structure represented by formula 1 or 2:

wherein, in formula 1, X ₁ -X ₃ Selected from CR, identically or differently at each occurrence _x Or N, adjacent substituents R, R _x Can optionally be linked to form a ring;

wherein, in formula 2, X ₄ -X ₈ Selected from CR, identically or differently at each occurrence _x N, C or NR _x Adjacent substituents R _x Can optionally be linked to form a ring;

in formula 1 and formula 2, Y ₁ -Y ₅ Selected from CR, identically or differently at each occurrence _y Or N, and Y ₁ -Y ₅ At least one of them is selected from CR _y And said R is _y At least one substituent selected from the group consisting of a substituent having one or more carbon atoms;

wherein R, R ₁ 、R ₂ 、R _x And R _y Each occurrence, the same or different, 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 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein R is ₃ Each occurrence, the same or different, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atomsUnsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

wherein the adjacent substituents R _y Can optionally be linked to form a ring;

wherein L is _b Each occurrence, the same or different, is selected from the group consisting of:

wherein R is _a 、R _b And R _c Represents mono-, poly-, or no substitution;

X _b each occurrence, the same or different, is selected from the group consisting of: o, S, se, NR _N1 And CR _C1 R _C2 ；

X _c And X _d Each occurrence, the same or different, is selected from the group consisting of: o, S, se and NR _N2 ；

R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, orSubstituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

wherein the adjacent substituents R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Can optionally be linked to form a ring.

According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having M (L) _a ) _m (L _b ) _n Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, L _a And L _b First and second ligands, respectively, of said complex;

wherein the first ligand L _a Has a structure represented by formula 1 or 2:

wherein R is ₃ Each occurrence, the same or different, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

wherein the adjacent substituents R _y Can optionally be linked to form a ring;

wherein R is _a 、R _b And R _c Represents mono-, poly-, or unsubstituted;

R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Each occurrence, the same or different, 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 arylalkyl 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

According to another embodiment of the invention, a compound formulation comprising a compound having M (L) is also disclosed _a ) _m (L _b ) _n The metal complex of the general formula (1).

The novel metal complex of the ligand with the polysubstituted biaryl structure can be used as a luminescent material in an electroluminescent device. Compared with the reported phosphorescent metal complexes, the novel metal complexes with ligands of polysubstituted biaryl structures can improve the melting point under the condition of keeping the sublimation temperature unchanged, are beneficial to sublimation, can prepare devices by an evaporation method, and can greatly prolong the service life of the devices while improving the external quantum efficiency. These novel compounds provide better device performance.

Drawings

FIG. 1 is a schematic representation of an organic light emitting device that may contain the metal complexes and compound formulations disclosed herein.

FIG. 2 is a schematic representation of another organic light emitting device that may contain the metal complexes and compound formulations disclosed herein.

Detailed Description

OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. 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, an emissive 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 fabricated by sequentially depositing the described layers. The properties and functions of the various layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.

There are more instances of each of these layers. For example, flexible and transparent are disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entiretyA substrate-anode combination. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50 ₄ m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which 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 U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including a composite cathode having a thin layer of a metal such as Mg: ag with an overlying transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of a protective layer can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.

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

The OLED also requires an encapsulation layer, as shown in fig. 2, which is an exemplary, non-limiting illustration of an organic light emitting device 200, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.

Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.

The materials and structures described herein may also be used in other organic electronic devices as previously listed.

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.

As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.

A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.

It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).

On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch between energy states. Thermal energy can activate a transition from a triplet state back to a singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the retardation component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, then the fraction of backfill singlet excited states may reach 75%. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrogenerated excitons.

The delayed fluorescence characteristic of type E can be found in excited complex systems or in single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small singlet-triplet energy gap (Δ Ε) _S-T ). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ E _S-T . These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).

Definitions for substituent terms

Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.

Alkyl-comprises both straight and branched chain 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, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbons in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferable.

Cycloalkyl-as used herein, comprises a cyclic alkyl group. Preferred cycloalkyl groups are those containing from 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, the cycloalkyl group may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.

Alkenyl-as used herein, encompasses both straight and branched chain olefinic groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl and 3-phenyl-1-butenyl. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, straight and branched alkynyl groups are contemplated. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,

perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylphenyl and m-quaterphenyl.

Heterocyclyl or heterocyclic-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing from 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms are contemplated. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, quinoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, benzothiophenecopyridine, selenophene bipyridine, selenobenzene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 3236 zxzborane, 5262-azaborine, 3763-oxaborone, 3763-aza-oxazaft analogs thereof. In addition, the heteroaryl group may be optionally substituted.

Alkoxy-is represented by-O-alkyl. Examples and preferred examples of the alkyl group are the same as those described above. Examples of the alkoxy group 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.

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

Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally 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 -naphthylethyl, 2- β -naphthylethyl, 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-nitrobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenyl-isopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable.

The term "aza" in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylene includes dibenzo [ f, h ] quinoxaline, dibenzo [ f, h ] quinoline and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the aza derivatives described above will be readily apparent to one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as described herein.

In this disclosure, unless otherwise defined, when any one of the terms in the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino, any of which groups may be substituted with one or more moieties selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkenyl having 6 to 30 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, substituted silyl, substituted aryl, substituted carbonyl, substituted sulfonyl, and combinations thereof.

It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.

In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because it enhances the efficiency and stability of the device.

In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.

In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.

The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

the expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

further, the expression that adjacent substituents can be optionally connected to form a ring is also intended to be taken to mean that, in the case where one of two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at a position to which the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following equation:

according to one embodiment of the present invention, a method is disclosed having M (L) _a ) _m (L _b ) _n Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, L _a And L _b First and second ligands, respectively, of said complex;

wherein the first ligand L _a Has a structure represented by formula 1 or 2:

wherein, in formula 1, X ₁ -X ₃ Is selected, identically or differently on each occurrence, from CR _x Or N, adjacent substituents R, R _x Can optionally be linked to form a ring;

in formula 1 and formula 2, Y ₁ -Y ₅ Is selected, identically or differently on each occurrence, from CR _y Or N, and Y ₁ -Y ₅ At least one of them is selected from CR _y And said R is _y At least one substituent selected from the group consisting of a substituent having one or more carbon atoms;

of these, R, R ₁ 、R ₂ 、R _x And R _y Each occurrence, the same or different, 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 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein R is ₃ Each occurrence, the same or different, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atomsA group, 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein the adjacent substituents R _y Can optionally be linked to form a ring;

wherein R is _a 、R _b And R _c Represents mono-, poly-, or no substitution;

R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 6 to 30 carbon atomsAryloxy, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

Here, the adjacent substituent R, R _x Can optionally be linked to form a ring, intended to denote an adjacent group of substituents, such as substituents R and R _x In between, two substituents R _x Can be connected to form a ring. Obviously, these substituent groups may not be connected to form a ring.

In this context, adjacent substituents R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Can optionally be linked to form a ring, is intended to mean a group in which adjacent substituents are present, for example two substituents R _a In between, two substituents R _b In between, two substituents R _c Of R is a substituent _a And R _b Of R is a substituent _a And R _c Of R is a substituent _b And R _c Of R is a substituent _a And R _N1 Of a substituent R _b And R _N1 Of a substituent R _a And R _C1 Of a substituent R _a And R _C2 Of R is a substituent _b And R _C1 Of R is a substituent _b And R _C2 Of a substituent R _a And R _N2 And a substituent R _b And R _N2 And any one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be connected to each other to form a ring.

According to one embodiment of the invention, wherein the metal M is selected from Ir, rh, re, os, pt, au or Cu.

According to one embodiment of the invention, wherein the metal M is selected from Ir or Pt.

According to one embodiment of the present invention, wherein the metal M is Ir.

According to one embodiment of the invention, wherein the ligand L _a Each occurrence, the same or different, is selected from the group consisting of structures represented by formulas 1-1, 1-2, or 1-3:

wherein ring B is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;

R _B represents mono-, poly-or unsubstituted;

X ₁ -X ₃ selected from CR, identically or differently at each occurrence _x Or N; y is ₁ -Y ₅ Selected from CR, identically or differently at each occurrence _y Or N, and, Y ₁ -Y ₅ At least one of them is selected from CR _y And said R is _y At least one substituent selected from the group consisting of a substituent having one or more carbon atoms;

wherein R, R ₁ 、R ₂ 、R _x 、R _y And R _B Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atomsOr unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

adjacent substituents R _B Can optionally be linked to form a ring.

In this example, the adjacent substituents R _B Can optionally be linked to form a ring, intended to mean if more substituents R are present _B Then two adjacent R _B Can be linked to form a ring. Obviously, when a plurality of substituents R are present _B When adjacent to R _B Or may be both unconnected to form a ring.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ At least one of them is selected from CR _y And said R is _y Each occurrence, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ At least two of which are selected from CR _y And said R is _y Each occurrence, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ At least three of which are selected from CR _y And said R is _y Each occurrence, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ Each independently selected from CR _y And wherein at least one of said R _y Each occurrence, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ Each independently selected from CR _y And wherein there are at least two of said R _y Each occurrence, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to one embodiment of the present invention, wherein Y ₁ -Y ₅ Each independently selected from CR _y And wherein at least one of said R _y Selected, identically or differently on each occurrence, from methyl, ethyl or isopropyl.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ Each independently selected from CR _y And in Y ₁ 、Y ₃ And Y ₅ In which at least one of said R _y Selected, identically or differently on each occurrence, from methyl, ethyl or isopropyl.

According to an embodiment of the invention, wherein Y ₁ -Y ₅ Each independently selected from CR _y And in Y ₁ 、Y ₃ And Y ₅ In which at least two of said R _y Selected, identically or differently on each occurrence, from methyl, ethyl or isopropyl.

According to one embodiment of the invention, wherein R ₁ And R ₂ Each occurrence being the same or different and selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted having 1 to 20 carbon atomsA substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, and combinations thereof; r ₃ Selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms.

According to one embodiment of the invention, wherein R ₁ And R ₂ Each occurrence being the same or different and selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms; r is ₃ Selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

According to one embodiment of the invention, wherein R ₁ And R ₂ Selected from hydrogen; r ₃ Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclohexyl, and combinations thereof.

According to an embodiment of the invention, wherein X ₁ -X ₃ Each independently selected from CR _x 。

According to an embodiment of the invention, wherein X ₁ -X ₃ At least one of which is selected from N.

According to an embodiment of the invention, wherein X ₁ -X ₃ One of which is selected from N.

According to an embodiment of the invention, wherein X ₂ Is N.

According to an embodiment of the present invention, wherein, in formula 1-1, formula 1-2 or formula 1-3, ring B is a benzene ring.

According to an embodiment of the present invention, wherein, in formula 1-1, formula 1-2 or formula 1-3, ring B is a benzene ring, and R is _B Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkyl having 6 to 20 carbon atomsArylsilyl groups, and combinations thereof.

According to an embodiment of the present invention, wherein, in formula 1-1, formula 1-2 or formula 1-3, ring B is a benzene ring, and R is _B Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, and combinations thereof.

According to one embodiment of the invention, wherein the ligand L _a Each occurrence being selected identically or differently from L _a1 To L _a1086 Group (d) of (a). Said L _a1 To L _a1086 See claim 11 for a specific structure of (a).

According to one embodiment of the invention, wherein the ligand L _b Each occurrence being selected identically or differently from L _b1 To L _b444 Group (iii) of (iv). Said L _b1 To L _b444 See claim 12 for a specific structure of (a).

According to an embodiment of the present invention, wherein the metal complex is selected from the group consisting of compounds 1 to 238, and the specific structures of the compounds 1 to 238 are shown in claim 13.

According to an embodiment of the present invention, there is also disclosed an electroluminescent device, including:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, the organic layer comprising a material having M (L) _a ) _m (L _b ) _n Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, L _a And L _b First and second ligands, respectively, of said complex;

wherein the first ligand L _a Has a structure represented by formula 1 or 2:

wherein R is ₃ Identical in each occurrence orVariously selected from the group consisting of: halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

wherein the adjacent substituents R _y Can optionally be linked to form a ring;

wherein R is _a 、R _b And R _c Represents mono-, poly-, or no substitution;

R _a 、R _b 、R _c 、R _N1 、R _N2 、R _C1 And R _C2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstitutedUnsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

According to an 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.

According to one embodiment of the invention, the electroluminescent device emits red light.

According to one embodiment of the invention, the electroluminescent device emits white light.

According to one embodiment of the invention, the light emitting layer further comprises at least one host material.

According to one embodiment of the invention, the light emitting layer further comprises at least one host material comprising at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

According to the inventionAlso disclosed is a compound formulation comprising a compound having M (L) _a ) _m (L _b ) _n A metal complex of the general formula (II). The specific structure of the metal complex is as shown in any one of the preceding embodiments.

In combination with other materials

The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application Ser. No. 0132-0161, paragraphs 2016/0359122A1, which is hereby incorporated by reference in its entirety. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application US2015/0349273A1, paragraphs 0080-0101, which is incorporated herein by reference in its entirety. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

In the examples of material synthesis, all reactions were carried out under nitrogen unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product was structurally identified and characterized using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai prism technique fluorescence spectrophotometer, electrochemical workstation of wuhan koste, bei Yi g sublimator of ann hui, etc.) in a manner well known to those of skill in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.

Materials synthesis example:

the preparation method of the compound of the present invention is not limited, and the following compounds are typically but not limited, and the synthetic route and preparation method thereof are as follows:

synthesis example 1: synthesis of Compound 45

Step 1: synthesis of intermediate 3

6g (1.2eq, 24.19mmol) of intermediate 1,4.14g of intermediate 2 (1eq, 20.16mmol) and 92mg of Pd ₂ (dba) ₃ (0.05eq, 0.1mmol), 133mg of L,6.4g of potassium phosphate (1.5eq, 30.24mmol) were dissolved in 60mL of toluene, heated to 100 ℃, stirred overnight, GC-MS showed complete disappearance of intermediate 2, cooled to room temperature, diluted with water, extracted three times with EA, the organic phases washed with saturated brine, combined and dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and column chromatography (PE) was purified to give 7.83g of intermediate 3 in 98% yield.

Step 2: synthesis of intermediate 4

7.83g (1eq, 23.8mmol) of intermediate 3,7.25g of B ₂ Pin ₂ (pinacol diboron) (1.2eq, 28.57mmol), 0.267g Pd (OAc)) ₂ (0.05eq, 1.19mmol), 0.98g of S-Phos (0.1eq, 2.38mmol), 3.5g of potassium acetate (1.5eq, 35.7mmol) were dissolved in 80mL dioxane, heated to 110 ℃, stirred overnight, TLC showed completion of the starting material reaction, cooled to room temperature, diluted with water, extracted three times with EA, the organic phases washed with saturated brine, combined and dried over anhydrous magnesium sulfate, the solvent removed under reduced pressure, column chromatography (PE: EA = 30).

And step 3: synthesis of intermediate 6

10.1g (1eq, 24.02mmol) of intermediate 4,5.23g of intermediate 5 (1.1eq, 26.42mmol), 0.98g of tetratriphenylphosphine palladium (0.05eq, 1.2mmol), 3.82g of sodium carbonate (1.5eq, 36.03mmol) were dissolved in 90mL of tetrahydrofuran and 30mL of water, heated to 100 ℃ and stirred overnight, TLC showed complete disappearance of intermediate 4, cooled to room temperature, diluted with water, extracted three times with EA, the organic phases washed with saturated brine, combined and dried over anhydrous magnesium sulfate, the solvent removed under reduced pressure, and column chromatography (PE: EA = 20.

And 4, step 4: synthesis of intermediate 8

5.8g (1eq, 12.72mmol) of intermediate 6,2.59g of intermediate 7 (2eq, 25.43mmol), 143mg of palladium acetate (0.05eq, 0.64mmol), 525mg of S-phos (0.1eq, 1.28mmol), 8.1g of tripotassium phosphate trihydrate (3eq, 38.11mmol) were dissolved in 60mL of toluene, heated to 100 ℃, stirred overnight, TLC showed complete disappearance of intermediate 6, diluted with water, extracted three times with EA, the organic phases washed with saturated brine, combined and dried over anhydrous magnesium sulfate, the solvent removed under reduced pressure, and column chromatography (PE: EA = EA 20) afforded 5.8g of intermediate 8 in 95% yield. Then, the n-hexane was recrystallized four times, and the purity was 99.9%.

And 5: synthesis of Iridium dimers

1.91g (3eq, 4 mmol) of intermediate 8 are dissolved in 20mL of 2-ethoxyethanol and 7mL of water at room temperature, and 0.47g of IrCl is added ₃ ·3H ₂ O (1eq, 1.33mmol) was replaced with nitrogen three times, heated to 130 ℃ under reflux for 24 hours, and cooled to room temperature. And filtering, and washing the solid with methanol until the washing liquid is colorless to obtain a red solid which is directly used for the next reaction without further purification.

Step 6: synthesis of Compound 45

1.5g (1eq, 1.43mmol) of iridium dimer was charged to a 100mL round bottom flask, and 1.97g of K was added ₂ CO ₃ (10eq, 14.3mmol), 1.42g of 3,7-diethyl-3-methylnonane-4,6-dione (4eq, 5.72mmol) and 48mL of ethoxyethanol were replaced with nitrogen at room temperature three times, heated to 50 ℃ and stirred under nitrogen for 24 hours, filtered through celite, the solid washed with methanol until the washing was colorless, the red solid above the celite was dissolved in 200mL of dichloromethane, and the resulting dichloromethane solution was placed in a flask, after which 20mL of methanol was added to the flask, dichloromethane was removed under reduced pressure, the solid precipitated in the remaining methanol, and the solid was collected by filtration. Column chromatography with eluent (PE: DCM =50 1) gave a red solid. The red solid was dissolved in 200mL of dichloromethane and filtered through celite, 20mL of methanol was added to the filtrate, dichloromethane was removed under reduced pressure, the solid was precipitated in the remaining methanol, the resulting red solid was collected on a filter paper, and a total of 0.85g of Compound 45 was collected, and the yields in steps 5 and 6 were calculated as 46.6%. The product was identified as the target product, molecular weight 1370.8.

Device embodiments

Device example 1

First, a glass substrate having a thickness of 120nm was cleanedIndium Tin Oxide (ITO) anode, then treated with oxygen plasma and UV ozone. After treatment, the substrate was dried in a glove box to remove moisture. The substrate is then mounted on a substrate holder and loaded into a vacuum chamber. Organic layers specified below, in a vacuum of about 10 degrees ^-8 In the case of torr, the evaporation was carried out on the ITO anode in turn by thermal vacuum evaporation at a rate of 0.2-2 a/s. Compound HI as Hole Injection Layer (HIL) in thickness

Compound HT is used as Hole Transport Layer (HTL) in thickness->

Compound EB as an Electron Blocking Layer (EBL), thickness->

Then, the compounds 45 according to the invention are doped in the host compound RH and serve as light-emitting layer (EML), thickness +>

Compound HB serves as hole-blocking layer (HBL), thickness->

On HBL, a mixture of compound ET and 8-hydroxyquinoline-lithium (Liq) is deposited as an Electron Transport Layer (ETL), thickness->

Finally, liq with a thickness of 1nm was deposited as an electron injection layer, and Al with a thickness of 120nm was deposited as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device comparative example 1

Device comparative example 1 was prepared in the same manner as in device example 1 except that the compound RD was used in place of the compound 45 of the present invention in the light-emitting layer.

The partial layer structure and thickness of the device are shown in the table below. Wherein more than one of the materials used is obtained by doping different compounds in the recited weight ratios.

TABLE 1 partial device structures of device examples and comparative examples

The material structure used in the device is as follows:

the IVL and lifetime characteristics of the devices were measured at different current densities and voltages. Table 2 shows the CIE data measured at 1000 nits, the maximum emission wavelength (. Lamda.) _max ) External Quantum Efficiency (EQE) and full width at half maximum (FWHM), and at 80mA/cm ² Lifetime at constant current (LT 95). Sublimation temperature (T) of Compound 45 and Compound RD of the present invention _sub ) And melting point data (T) _m ) Was also measured and is shown in table 3.

TABLE 2 device data

As can be seen from the data in Table 2, by adding substituents on the biphenyl structure of the ligand, the lambda of the compound can be maintained _max And half-peak width is unchanged, the External Quantum Efficiency (EQE) of the device example 1 is slightly improved to 22.55% of that of the device comparative example 1, and reaches an industry higher level of 22.85%; meanwhile, compared with 46 hours of the device comparative example 1, the service life of the device example 1 is greatly prolonged to 96 hours, which is 2.09 times of that of the device comparative example 1.

TABLE 3 sublimation temperature and melting point data

Compound number	T _sub (℃)	T _m (℃)
			Compound 45	280	299
Compound RD	280	284

As can be seen from the data in Table 3, the sublimation temperature of the compound RD is 280 ℃, the melting point of the compound RD is 284 ℃, the melting point of the compound RD is only 4 ℃ higher than the sublimation temperature, the small temperature difference makes the compound RD easy to melt during sublimation, and the sublimation temperature of the compound 45 is also kept at 280 ℃, but the melting point is increased to 299 ℃, and the difference between the melting point and the sublimation temperature reaches 19 ℃, so that the possibility of melting during sublimation of the compound is greatly reduced. Sublimation is a necessary purification means before the OLED material is used as a device, when a melting phenomenon occurs in the sublimation process of the red light emitting material, the material is decomposed, the purity of the material is greatly reduced, even the light emitting material is completely decomposed, the device performance of the low-purity red light emitting material is greatly reduced, and the commercial demand cannot be met. Increasing the melting point of the material is a necessary prerequisite for commercial production of the luminescent material.

In conclusion, the compound disclosed by the invention introduces a specific substituent group on a biphenyl structure in a ligand of a metal complex, so that the compound disclosed by the invention can greatly prolong the service life of a device while obtaining high device efficiency, can effectively regulate and control the temperature difference between sublimation temperature and melting point, is beneficial to sublimation, and is used for preparing the device in an evaporation mode, and the uniqueness and the importance of the compound disclosed by the invention are highlighted.

It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. Thus, the invention as claimed may include variations from the specific embodiments and preferred embodiments described herein, as will be apparent to those skilled in the art. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present invention. It should be understood that various theories as to why the present invention works are not intended to be limiting.

Claims

1. A metal complex having M (L) _a ) ₂ (L _b ) Wherein the metal M is selected from Ir metal, L _a And L _b First and second ligands, respectively, of said metal complex;

first ligand L _a Each occurrence, the same or different, is selected from the structures represented by formulas 1-1:

wherein, ring B is selected from benzene ring;

R _B represents mono-, poly-or unsubstituted;

wherein R is _B Each occurrence being the same or different and selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

wherein, X ₁ -X ₂ Selected from CR, identically or differently at each occurrence _x ；

Y ₂ 、Y ₄ Selected from CR, identically or differently at each occurrence _y (ii) a Wherein R is _y Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen; y is ₁ 、Y ₃ And Y ₅ The R in (1) _y Selected from the same or different at each occurrenceMethyl, ethyl or isopropyl;

R ₁ 、R ₂ 、R _x each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

wherein R is ₃ Each occurrence, the same or different, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

wherein L is _b Each occurrence, identically or differently, is selected from:

X _c and X _d Selected from O, identically or differently at each occurrence;

R _a 、R _b 、R _c each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof.

2. A metal complex as claimed in claim 1, R ₁ And R ₂ Selected from hydrogen; r ₃ Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, and combinations thereof.

3. A metal complex according to claim 1, wherein X ₁ -X ₂ Each independently selected from CR _x 。

4. A metal complex as claimed in claim 1, R _B Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, isobutyl, trifluoromethyl, and combinations thereof.

5. The metal complex of claim 1, wherein L _a Each occurrence, the same or different, is selected from the group consisting of:

6. the metal complex of claim 1 or 5, wherein the L _b Each occurrence, the same or different, is selected from the group consisting of:

7. the metal complex of claim 6, wherein the metal complex is selected from the group consisting of compounds 29-31, 38-39, 42-45, 52, 55, 151-152, 154-160;

wherein, the compounds 29-31, 38-39, 42-45, 52, 55, 151-152, 154-160 have Ir (L) _a ) ₂ (L _b ) Wherein two L are _a Same, L _a And L _b Each corresponding to a structure selected from those listed in the following table:

wherein the compounds 225-226, 229, 231, 233, 236, 238 have Ir (L) _a ) ₂ (L _b ) Wherein two L are _a Different, L _a And L _b Respectively corresponding to the structures listed in the following table:

compound (I) L _a L _a L _b Compound (I) L _a L _a L _b 225 L _a1042 L _a913 L _b85 226 L _a1056 L _a913 L _b85 229 L _a1070 L _a913 L _b121 231 L _a1070 L _a913 L _b368 233 L _a1070 L _a913 L _b85 236 L _a921 L _a1078 L _b31 238 L _a870 L _a1082 L _b101

。

8. An electroluminescent device, comprising:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex of any one of claims 1 to 7.

9. The electroluminescent device of claim 8, wherein the organic layer is a light-emitting layer and the metal complex is a light-emitting material; the electroluminescent device emits red or white light.

10. The electroluminescent device of claim 9 wherein said light emitting layer further comprises at least one host material;

the host material comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

11. A composition for an organic electroluminescent device comprising the metal complex of any one of claims 1 to 7.