CN113087745B

CN113087745B - Metal complex containing silicon substituent

Info

Publication number: CN113087745B
Application number: CN202010011458.2A
Authority: CN
Inventors: 王珍; 桑明; 王涛; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2020-01-08
Filing date: 2020-01-08
Publication date: 2023-04-18
Anticipated expiration: 2040-01-08
Also published as: CN113087745A

Abstract

A silicon-containing substituted metal complex is disclosed. The novel silicon-containing substituted metal complexes have M (L) _a ) _m (L _b ) _n (L _c ) _q In which the ligand L _a Is a ligand with silicon base substitution, and can be used as a luminescent material in an electroluminescent device. The novel metal complexes have the advantages of remarkably improving the quantum efficiency of the material, effectively controlling the light-emitting wavelength and the light-emitting color, reducing the driving voltage and providing better device performance. An electroluminescent device and compound formulation are also disclosed.

Description

Metal complex containing silicon substituent

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 silicon-containing substituted metal complex, and an organic electroluminescent device and a compound formulation including 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, ismann 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 capable of generating 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.

In J.Mater.Chem.2009, 19,8347-8359, a structure of Ir (ppyTPS) is reported ₃ Metal complexes of (2)

Complexes with different ligand structures are not disclosed and taught therein.

Having the formula disclosed in KR1020120032054A

An iridium complex of the structure. In the numerous iridium complexes disclosed therein reference is made to->

However, the synthesis and further study of these two compounds were not carried out. It focuses primarily on the specific properties of iridium complexes with substituted diphenylpyridine ligands and does not disclose and teach the introduction of specific aryl substituents with silyl substituents at specific positions of phenylpyridine ligands and the effect of variations in substituents on the silyl substituents on metal complexes.

In US20160141526A1Is disclosed to have

Structural iridium complexes, a specific example being ` H `>

It notes the change in properties brought about by the introduction of a silyl substituent on a 2, 5-disubstituted pyridine ligand, but where the silyl phenyl substituent must be located at the pyridine position 5, it does not disclose or teach the use of the silyl phenyl substituent substituted elsewhere in the pyridine ring in metal complexes.

In US2010102710A1, a composition having the structure is disclosed

In particular examples of iridium complexes which are->

However, the synthesis and further study of this compound were not carried out. It is primarily concerned with having->

The iridium complexes of the particular framework ligands of the substituted azaanthracene structure do not disclose and teach the effect of ligands of the aryl pyridine structure with silicon-based substituents on metal complexes.

The phosphorescent iridium complex can be used as a phosphorescent doping material of a luminescent layer and applied to the field of organic electroluminescence or display. Existing phosphorescent iridium complexes, for example Ir (ppy) ₃ The material can be used as a green phosphorescent doped material, but the performance of the material needs to be further improved to meet the increasing performance requirements, and particularly, a more effective means for controlling the light-emitting wavelength, reducing the driving voltage and improving the quantum efficiency of the material is provided. Compared with the reported phosphorescent metal complex, the novel silicon-containing phosphorescent metal complex has the advantages of remarkably improving the quantum efficiency of the material, effectively controlling the light-emitting wavelength and reducing the driving voltage.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of silicon-containing substituted metal complexes. The metal complex can be used as a light-emitting material in an organic electroluminescent device. Compared with the reported phosphorescent metal complex, the novel silicon-containing substituted metal complex has the advantages of remarkably improving the quantum efficiency of the material, effectively controlling the light-emitting wavelength and the light-emitting color, reducing the driving voltage and providing better device performance.

According to one embodiment of the present invention, a metal complex is disclosed having M (L) _a ) _m (L _b ) _n (L _c ) _q Wherein M is selected from metals having a relative atomic mass greater than 60; wherein said L _a ，L _b And L _c Respectively a first ligand, a second ligand and a third ligand coordinated to the metal M, a first ligand L _a Is different in structure from the second ligand L _b Or a third ligand L _c A second ligand L _b And a third ligand L _c Have the same or different structures;

m is selected from 1 or 2, n is selected from 0,1 or 2, q is selected from 0,1 or 2, and M + n + q is equal to the oxidation state of metal M; when m is 2, L _a May be the same or different; when n is 2, L _b May be the same or different; when q is 2, L _c May be the same or different;

L _a ，L _b and L _c Can optionally be linked to form a tetradentate or hexadentate ligand;

said L _a Each occurrence, the same or different, has a structure represented by formula 1:

wherein Cy1 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;

wherein Cy2 is a substituted or unsubstituted heteroaryl group having 6 ring atoms;

wherein Y is ₁ ，Y ₂ And Y ₃ Each independently selected from CR _y Or N;

wherein R is _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 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 thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein Q is ₁ To Q ₃ Each occurrence, the same or different, is selected from the group consisting of: 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 aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

wherein adjacent substituents Q ₁ ,Q ₂ And Q ₃ Can optionally be linked to form a ring;

wherein, each occurrence of L is selected, identically or differently, from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

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 May represent mono-, poly-, or unsubstituted;

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 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, 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 thio group, a sulfinyl group, a sulfonyl group, a phosphino group, 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;

wherein the third ligand L _c Are monoanionic bidentate ligands.

According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprisingA metal complex having M (L) _a ) _m (L _b ) _n (L _c ) _q Wherein M is selected from metals having a relative atomic mass greater than 60; wherein said L _a ，L _b And L _c Respectively a first ligand, a second ligand and a third ligand coordinated to the metal M, a first ligand L _a Is different in structure from the second ligand L _b Or a third ligand L _c A second ligand L _b And a third ligand L _c Have the same or different structures;

L _a ，L _b and L _c Optionally linked to form a tetradentate or hexadentate ligand;

wherein, Y ₁ ，Y ₂ And Y ₃ Each independently selected from CR _y Or N;

wherein R is _y 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 atomsA group, 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 thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein Q ₁ To Q ₃ Each occurrence, the same or different, is selected from the group consisting of: 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 aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

wherein, for each occurrence, L is selected, identically or differently, from a substituted or unsubstituted arylene having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms, or a combination thereof;

wherein R is _a ,R _b And R _c May represent mono-, poly-, or unsubstituted;

X _c And X _d Selected from the group consisting of: o, S, se and NR _N2 ；

wherein the third ligand L _c Are monoanionic bidentate ligands.

According to another embodiment of the invention, a compound formulation is also disclosed, which comprises the above-described metal complex.

The novel silicon-containing substituted metal complex disclosed by the invention can be used as a luminescent material in an electroluminescent device. Compared with the reported phosphorescent metal complex, the novel silicon-containing substituted metal complex has the advantages of remarkably improving the quantum efficiency of the material, effectively controlling the light-emitting wavelength and the light-emitting color, reducing the driving voltage and providing 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 complex 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 nature and function of the various layers and exemplary materials are described in more detail in U.S. Pat. No. 7,279,704B2 at columns 6-10, which is incorporated herein by reference in its entirety.

There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. 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 (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. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: ag and an overlying layer of transparent, conductive, sputter-deposited ITO. 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. May be incorporated in its entiretyA description of protective layers is found in U.S. patent application publication No. 2004/0174116, which is incorporated by way of illustration.

The above-described hierarchical structure is provided via a non-limiting embodiment. 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. Pat. No. 7,968,146b2, 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. In the case where the first layer is described as being "disposed on" the second layer, the first layer is disposed farther from the substrate. Unless it is specified that a first layer is "in contact with" a second layer, there may be other layers between the first and second layers. 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 that 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 generally be divided 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%, far exceeding 25% of the spin statistics of the electrogenerated excitons.

The E-type delayed fluorescence characteristic can be seen in the excitation complex systemIn a system or a single compound. 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 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 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 the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 3-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group and a 3-phenyl-1-butenyl group. 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 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 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, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, quinoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, benzothienobipyridine, cinnoline, selenobenzene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, azaborizole and 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 the aryl and heteroaryl groups 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.

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, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives may be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed within the terms 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 alkynyl, 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 groups selected from deuterium, halogen, unsubstituted alkyl groups 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 alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, thio, sulfinyl, sulfonyl, phosphino 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 optionally be linked to form a ring, both in the case where adjacent substituents may be linked to form a ring and in 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 exemplified by the following equation:

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said L is _a Each occurrence, the same or different, has a structure represented by formula 1:

wherein R is _y 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 alkyl havingA 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

wherein R is _a ,R _b And R _c May represent mono-, poly-, or unsubstituted;

X _c And X _d Selected from the group consisting of: o, S, se and NR _N2 ；

wherein the third ligand L _c Are monoanionic bidentate ligands.

In this example, adjacent substituents Q ₁ ,Q ₂ And Q ₃ Can optionally be linked to form a ring, intended to denote adjacent substituents Q ₁ And Q ₂ Q of ₁ And Q ₃ And/or Q ₂ And Q ₃ The two or more may be connected to form a ring, or may not be connected to form a ring.

In this example, 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, intended to denote adjacent substituents R _a And R _b R is _b And R _c R is _a And R _c R is _C1 And R _C2 R is _a And R _N1 R is _b And R _N1 R is _c And R _N1 R is _a And R _N2 R is _b And R _N2 R is _a And R _C1 R is _b And R _C1 R is _c And R _C1 R is _c And R _C2 R is _a And R _C2 R is _b And R _C2 Between two R _a Between two R _b One or more of these substituent groups may be linked to form a ring, and it is obvious to those skilled in the art that none of these substituent groups may be linked to form a ring.

According to one embodiment of the invention, wherein the metal M is selected from the group consisting of Cu, ag, au, ru, rh, pd, os, ir, and Pt.

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

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

According to one embodiment of the invention, wherein said Cy1, on each occurrence, is selected, identically or differently, from the group consisting of:

wherein denotes the position of linkage to Cy2 and # denotes the position of linkage to M;

wherein Z is selected from the group consisting of: o, S, se, NR _N3 ,CR _C3 R _C4 And SiR _Si1 R _Si2 ；

Wherein R is ₁ To R ₆ ，R _N3 ，R _C3 ，R _C4 ，R _Si1 And R _Si2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted orAn 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

According to an embodiment of the present invention, wherein in the formula 1, L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

According to one embodiment of the present invention, wherein in said formula 1, L is a substituted or unsubstituted phenylene group.

According to one embodiment of the present invention, wherein in said formula 1, L is 1, 4-phenylene.

According to an embodiment of the present invention, wherein said L _a Each occurrence, identically or differently, is selected from the group consisting of:

/>

wherein R is _x ，R _y May be mono-, poly-or unsubstituted;

wherein R is ₁ To R ₆ ，R _x And R _y Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted withAn alkyl group of 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 carboxylic acid group, an ester group, a cyano group, an isocyano group, a thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

Q ₁ to Q ₃ Each occurrence, the same or different, is selected from the group consisting of: 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 aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

According to an embodiment of the present invention, wherein in said formula 1, Q ₁ To Q ₃ Each occurrence, identically or differently, is selected from the group consisting of:

in this embodiment, "-" indicates a position where the substituent is attached to the silicon atom in formula 1.

According to an embodiment of the present invention, wherein said L _b And L _c Identical or different on each occurrence is:

wherein R is _a1 And R _b1 Watch capable of showingMono-, poly-, or unsubstituted;

wherein R is _a1 And R _b1 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, 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 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, cyano groups, isocyano groups, and combinations thereof;

adjacent substituents are optionally linked to form a ring.

In this example, adjacent substituents are optionally linked to form a ring, intended to mean adjacent substituents R _a1 And R _b1 Between two R _a1 And/or two R _b1 May be linked to form a ring, and it is obvious to those skilled in the art that these substituent groups may not be linked to form a ring.

According to one embodiment of the invention, wherein said ligand L _a Each occurrence, identically or differently, of a group selected from L _a1 To L _a591 Group of wherein L _a1 To L _a591 See claim 8 for specific structure of (a).

According to an embodiment of the present invention, wherein said L _b And L _c Each occurrence, the same or different, is selected from the group consisting of:

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in this embodiment, L _b And L _c Each occurrence being selected identically or differently from L _b1 To L _b63 Group of ligands, i.e. in the metal complexes disclosed in the present invention, if ligands L are present _b Then ligand L _b Is selected from L _b1 To L _b63 Any one or any two of, if present, ligands L _c Then ligand L _c May also be selected from L _b1 To L _b63 Any one or any two of; if there are two L _b Two of L _b May be the same or different; if there are two L _c Two of L _c May be the same or different; if there is one L at the same time _b And one L _c L being present simultaneously _b And L _c May be the same or different.

According to an embodiment of the present invention, wherein said L _a1 To L _a591 And L is _b1 To L _b63 The hydrogens in the structure may be partially or fully substituted with deuterium.

According to one embodiment of the present invention, wherein the metal complex is selected from the group consisting of metal complex 1 to metal complex 1344; wherein the metal complexes 1 to 1104 have Ir (L) _a )(L _b ) ₂ Of structure (2), two of which L _b The same; wherein the metal complexes 1105 to 1216 have Ir (L) _a )(L _b )(L _c ) The structure of (1); wherein metal complexes 1217 to 1344 have Ir (L) _a ) ₂ (L _b ) Of structure (2), two of which L _a The same; the specific structures of metal complexes 1 to 1344 are shown in claim 11.

In the present embodiment, the metal complex 1105 to the metal complex 1216 therein have Ir (L) _a )(L _b )(L _c ) Structure of (1), wherein L _b And L _c Are all selected from L _b1 To L _b66 Groups of, for example, metal complexes 1105, three ligands L _a ,L _b And L _c Are each L _a1 ,L _b28 And L _b30 Due to the factThe structure of the metal complex 1105 is

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 metal complex having M (L) _a ) _m (L _b ) _n (L _c ) _q Wherein M is selected from metals having a relative atomic mass greater than 60; wherein said L _a ，L _b And L _c Respectively a first ligand, a second ligand and a third ligand coordinated to the metal M, a first ligand L _a Is different from the second ligand L _b Or a third ligand L _c A second ligand L _b And a third ligand L _c Have the same or different structures;

wherein, Y ₁ ，Y ₂ And Y ₃ Each independently selected from CR _y Or N;

wherein R is _a ,R _b And R _c May represent mono-, poly-, or unsubstituted;

X _c And X _d Selected from the group consisting of: o, S, se and NR _N2 ；

wherein the third ligand L _c Are monoanionic bidentate ligands.

According to one embodiment of the present invention, in the 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 device emits yellow light.

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

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

According to one embodiment of the invention, in the device, the organic layer is a light emitting layer, which further comprises a host material.

According to one embodiment of the invention, in the device, the organic layer is a light emitting layer, which further comprises at least two host materials.

According to one embodiment of the invention, the organic layer is a light emitting layer, the light emitting layer further comprising a 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 another embodiment of the invention, a compound formulation comprising a compound having M (L) is also disclosed _a ) _m (L _b ) _n (L _c ) _q A metal complex of the general formula (II). The specific structure of the metal complex is shown in any one of the 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 US2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that can 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 can 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, the entire contents of which are incorporated herein by reference. 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 is subjected to structural validation and characterization using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai prism-based fluorescence spectrophotometer, wuhan Corset's electrochemical workstation, anhui Beidek's sublimator, etc.) in a manner well known to those skilled 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 Anttrom 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 to, and the synthetic route and the preparation method thereof are as follows:

synthesis example 1: synthesis of Metal Complex 1

The method comprises the following steps:

a dry 250mL round-bottomed flask was charged with 4-chloro-2-phenylpyridine (4.3g, 23.0mmol) and pinacol diboron ester (B) ₂ Pin ₂ ) (6.1g, 24.0mmol), X-Phos (0.6g, 1.4mmol), palladium acetate (0.2g, 0.9mmol), potassium acetate (3.4g, 34.5mmol) and dioxane 100mL, N ₂ Substituted three times and in N ₂ Heat to reflux under protection and stir overnight. After the reaction was completed, it was filtered through celite, anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to give intermediate 1 (crude product) which was used directly in the next step.

Step two:

a dry 250mL round bottom flask was charged with intermediate 1 (crude), 1-bromo-4-trimethylsilylbenzene (6.7 g, 29.2mmol), pd (dppf) Cl in that order ₂ (0.4 g,0.5 mmol), potassium carbonate (4.8 g,34.5 mmol), dioxane 90mL and water 30mL in N ₂ Heating to reflux reaction for 12h under protection. After completion of the reaction, extraction was performed with ethyl acetate, the mixture was washed three times with saturated brine, and the organic phases were combined and dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to afford intermediate 2 as a white solid (4.7 g, 67% yield), the intermediate structure of which was confirmed by NMR.

Step three:

a dry 500mL round-bottom flask was charged with intermediate 2 (3.0 g,9.9 mmol), iridium complex (3.5 g,4.9 mmol), 290mL of ethanol in turn in N ₂ Heating to reflux reaction for 36h under protection. After the reaction was cooled, the celite was filtered. Washing with methanol and n-hexane for 2 times, dissolving yellow solid above diatomaceous earth with dichloromethane, collecting organic phase, and reducing pressureConcentrated under reduced pressure, and purified by column chromatography to give metal complex 1 (1.3 g, yield 33%) as a yellow solid. The product structure was confirmed by NMR and LCMS and was identified as the target product, molecular weight 803.

Synthesis example 2: synthesis of Metal complexes 57

The method comprises the following steps:

p-bromoiodobenzene (28.3g, 100.0 mmol) was dissolved in 200mL of tetrahydrofuran, n-butyllithium (40mL, 100.0 mmol) was slowly added dropwise at-78 deg.C, and after reaction at-78 deg.C for half an hour, a solution of dimethylphenylchlorosilane (17.0 g,100.0 mmol) in tetrahydrofuran was slowly added dropwise over half an hour, keeping the addition at a slow rate. After keeping the reaction at low temperature for one hour, the temperature was slowly raised to room temperature for overnight reaction. After completion of the reaction, 200mL of a saturated aqueous ammonium chloride solution was added to quench, the aqueous phase was extracted three times with dichloromethane, and the organic phases were combined and washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to give intermediate 3 as a colourless oil (23.2 g, yield 80%) whose structure was confirmed by NMR.

Step two:

2-chloro-4-iodopyridine (23.9g, 100.0 mmol) is dissolved in 200mL tetrahydrofuran, isopropyl magnesium chloride lithium chloride solution (84.6mL, 110.0 mmol) is slowly dropped at 0 ℃, after reaction at 0 ℃ for half an hour, zinc chloride tetrahydrofuran solution (70mL, 70.0 mmol) is slowly dropped, half an hour of addition is completed, the temperature is slowly raised to room temperature, after 1 hour, intermediate 3 (23.3g, 80.0 mmol), palladium acetate (0.4g, 2.0 mmol) and S-Phos (1.6g, 4.0 mmol) are sequentially added, and the mixture is stirred at room temperature overnight. After completion of the reaction, 200mL of a saturated aqueous ammonium chloride solution was added to quench, the aqueous phase was extracted three times with dichloromethane, and the organic phases were combined and washed with a saturated brine and dried over anhydrous sodium sulfate. Concentrating under reduced pressure. The crude product was purified by column chromatography to afford intermediate 4 (24.2 g, 75% yield) as a white solid, the intermediate structure of which was confirmed by NMR.

Step three:

intermediate 4 (16.3g, 50.5mmol), phenylboronic acid (7.3g, 60.6 mmol), tetrakis (triphenylphosphine) palladium (2.2g, 2.0 mmol) and sodium carbonate (10.6 g,100.0 mmol) were placed in a reaction flask, and 150mL of dioxane and 50mL of water were added, and the mixture was heated to 90 ℃ to react overnight. After completion of the reaction, 200mL of a saturated aqueous ammonium chloride solution was added to quench, the aqueous phase was extracted three times with dichloromethane, and the organic phases were combined and washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to afford intermediate 5 (15.2 g, 85% yield) as a white solid, the intermediate structure being confirmed by NMR.

Step four:

a dry 500mL round-bottomed flask was charged with intermediate 5 (3.0 g, 8.2mmol), iridium complex (4.4 g, 6.2mmol), ethanol 200mL, and N in that order ₂ Heating to reflux reaction for 36h under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 57 (1.9 g, yield 36%) as a yellow solid. The product structure was confirmed by NMR and LCMS and was identified as the target product, with a molecular weight of 865.

Synthetic example 3: synthesis of Metal Complex 73

The method comprises the following steps:

dried 500mL round bottom flask was charged with para-bromoiodobenzene (10.1g, 35.7 mmol) and tetrahydrofuran 150mL in sequence, cooled to-78 deg.C, N ₂ Under protection, n-BuLi (14.2mL, 35.7 mmol) is slowly dropped into the mixture, the mixture is kept at low temperature for reaction for 0.5h, then diphenylmethylchlorosilane is added into the mixture at one time, the reaction is continued for 0.5h, and the temperature is raised to room temperature for reaction overnight. After the reaction was completed, ethyl acetate and water were added, liquid separation was performed, the combined organic layers were dried over anhydrous sodium sulfate, and after evaporation to dryness under reduced pressure, column chromatography was performed to obtain intermediate 6 (8.1 g, yield 64%) as a white solid, the structure of which was confirmed by NMR characterization.

Step two:

a dry 250mL round-bottomed flask was charged with 4-chloro-2-phenylpyridine (4.3g, 23.0mmol) and pinacol diboron ester (B) ₂ Pin ₂ ) (6.1g, 24.0mmol), X-Phos (0.6g, 1.4mmol), palladium acetate (0.2g, 0.9mmol), potassium acetate (3.4g, 34.5mmol) and dioxane 100mL ₂ Substituted three times and in N ₂ Heat to reflux under protection and stir overnight. After the reaction was completed, it was filtered through celite, anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to give intermediate 1 (crude product) which was used directly in the next step.

Step three:

a dry 500mL round bottom flask was charged with intermediate 1, intermediate 6 (8.1g, 23.0 mmol), pd (dppf) Cl in that order ₂ (0.5g, 0.7mmol), potassium carbonate (4.8g, 34.5mmol), dioxane 90mL and water 30mL, N ₂ Heating to reflux reaction for 12h under protection. After completion of the reaction, the mixture was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to afford intermediate 7 (8.0 g, 81% yield) as a colorless oil, the intermediate structure of which was confirmed by NMR.

Step four:

a dry 500mL round-bottom flask was charged with intermediate 7 (4.8g, 11.2mmol), iridium complex (3.2g, 4.5mmol), ethanol 100mL, and N in that order ₂ Heating to reflux reaction for 36h under protection. After the reaction was cooled, the celite was filtered. After washing with methanol and n-hexane 2 times, respectively, the yellow solid on the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to obtain metal complex 73 (1.4 g, yield 33%) as a yellow solid. The product structure was confirmed by NMR and LCMS and was identified as the desired product, molecular weight 927.

Synthetic example 4: synthesis of metal complex 121:

the method comprises the following steps:

a dry 500mL round-bottom flask was charged with p-dibromobenzene (8.9 g,37.6 mmol) and THF 200mL in sequence, cooled to-78 deg.C, N ₂ Under protection, n-BuLi (16.0 mL,39.6 mmol) is slowly dropped, after 0.5h, triphenyl chlorosilane is slowly dropped, after 0.5h of reaction, the temperature is raised to room temperature for reaction overnight. After completion of the reaction, the white precipitate was removed by filtration, extracted with ethyl acetate, washed with saturated aqueous sodium chloride solution, the combined organic layers were dried over anhydrous sodium sulfate, evaporated to dryness under reduced pressure, and subjected to column chromatography to obtain intermediate 8 (7.8 g, yield 50%) as a white solid, the structure of which was confirmed by NMR characterization.

Step two:

a dry 250mL round-bottomed flask was charged with 4-chloro-2-phenylpyridine (2.6 g,13.7 mmol) and pinacol ester diboron (B) ₂ Pin ₂ ) (4.5g, 17.7mmol), palladium acetate (0.2g, 0.9mmol), X-Phos (0.7g, 1.5mmol), potassium acetate (4.0g, 40.5mmol) and Dioxane 150mL, N ₂ Heat to reflux with protection and stir overnight. After the reaction is finished, diatomite and anhydrous sulfuric acidMagnesium filtration, ethyl acetate washing twice, organic phase collection under reduced pressure concentration to give intermediate 1 (crude product) for the next step.

Step three:

a dry 500mL round-bottom flask was charged with intermediate 1 obtained in the previous step, intermediate 8 (7.8g, 18.8mmol), palladium acetate (0.2g, 0.9mmol), X-Phos (0.7g, 1.5mmol), potassium phosphate (8.6g, 40.5mmol), 1, 4-dioxane 100mL and water 30mL, N ₂ Heating to reflux reaction for 12h under protection. After completion of the reaction, the mixture was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to afford intermediate 9 (4.5 g, 67% yield) as a white solid, the intermediate structure of which was confirmed by NMR.

Step four:

a dry 500mL round-bottom flask was charged with intermediate 9 (2.2g, 4.5mmol), iridium complex (2.7g, 3.7mmol), ethanol 125mL, N ₂ Heating to reflux reaction for 36h under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 121 (1.2 g, yield 33%) as a yellow solid. The product structure was confirmed by NMR and LCMS and was identified as the target product, molecular weight 989.

It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other structures of the compounds of the present invention.

Device embodiments

Example 1:

first, a glass substrate having an Indium Tin Oxide (ITO) anode 80nm thick was cleaned, and thenFollowed by treatment 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. The organic layer specified below was 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 was used as a Hole Injection Layer (HIL) with a thickness of

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

The compound H1 is used as an Electron Blocking Layer (EBL) with a thickness of

Then, the metal complex 1 (Ir (L) of the present invention _a1 )(L _b28 ) ₂ ) Doped in a host compound H1 and a compound H2 as a light-emitting layer (10: 45:45, EML), thickness is>

Compound H2 as Hole Blocking Layer (HBL) in thickness->

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

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.

Example 2:

the preparation method of example 2 is the same as that of example 1 except that the metal complex 57 of the present invention is used in the light-emitting layer instead of the metal complex 1 of the present invention.

Example 3:

the production method of example 3 is the same as in example 1 except that the metal complex 121 of the present invention is used in the light-emitting layer instead of the metal complex 1 of the present invention.

Comparative example 1:

comparative example 1 was prepared in the same manner as in example 1 except that the compound a was used in the light-emitting layer instead of the metal complex 1 of the present invention.

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

TABLE 1 device structures of device examples and comparative examples

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The material structure used in the device is as follows:

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the IVL characteristics of the device were measured. Table 2 is the measured External Quantum Efficiency (EQE), λ max, voltage (V), current Efficiency (CE) and CIE data at 1000 nits.

TABLE 2 device data

Discussion:

as can be seen from table 2, device examples using the metal complexes of the present invention show several advantages over the comparative compounds. Compared to comparative example 1 (compound a), the CE and EQE of examples 1,2 and 3 are significantly higher than comparative example 1, with voltages 0.26v,0.11v and 0.13V, respectively, lower than with comparative compound a without silicon-based substitution. Meanwhile, the lambda max and the CIE data show that the introduction of the silicon-based substitution can also finely regulate and control the light-emitting wavelength and color. In conclusion, the silicon-group-substituted metal complex disclosed by the invention has the advantages of remarkably improving the efficiency of a device, reducing the driving voltage, regulating and controlling the light-emitting wavelength and the like, and is an OLED material with a good application prospect.

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 invention works are not intended to be limiting.

Claims

1. A metal complex having M (L) _a )(L _b ) ₂ Wherein M is selected from Ir; said L _a ，L _b Respectively a first ligand, a second ligand, a first ligand L coordinated to the metal M _a Is different in structure from the second ligand L _b ；

L _a And L _b Optionally linked to form a tetradentate or hexadentate ligand;

wherein Cy1 is a substituted or unsubstituted aryl group having 6 carbon atoms;

wherein, Y ₁ ，Y ₂ And Y ₃ Each independently selected from CR _y ；

Wherein R is _y Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, in generalSubstituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

wherein Q is ₁ To Q ₃ Each occurrence, the same or different, is selected from the group consisting of: substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and combinations thereof;

wherein L is a substituted or unsubstituted phenylene group;

L _b the same or different at each occurrence is:

wherein R is _a1 And R _b1 May represent mono-, poly-, or no substitution;

wherein R is _a1 And R _b1 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. The metal complex of claim 1, wherein Cy1, identically or differently at each occurrence, is selected from the group consisting of:

wherein # indicates the position of linkage to Cy2, # indicates the position of linkage to M;

wherein R is ₁ To R ₄ Each occurrence, which may be 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.

3. A metal complex according to claim 1, wherein L is 1, 4-phenylene.

4. Gold according to claim 3A complex of the genus, wherein L _a Selected from the group consisting of:

wherein R is _x ，R _y May be mono-, poly-or unsubstituted;

wherein R is ₁ To R ₄ ，R _x And R _y 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.

5. A metal complex according to claim 1, wherein Q is ₁ To Q ₃ Each occurrence, identically or differently, is selected from the group consisting of:

6. the metal complex of claim 1, wherein L _b The same or different at each occurrence is:

wherein R is _a1 And R _b1 May represent mono-, poly-, or no substitution;

wherein R is _a1 And R _b1 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof.

7. The metal complex as claimed in any of claims 1 to 6, wherein the ligand L _a Each occurrence, the same or different, is selected from the group consisting of:

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8. a metal complex according to claim 7, wherein L _b Each occurrence, the same or different, is selected from the group consisting of:

9. the method of claim 8A metal complex of which L _a ，L _b The hydrogens in the structure may be partially or fully substituted with deuterium.

10. The metal complex of claim 8, wherein metal complex 1 to metal complex 368 have Ir (L) _a )(L _b ) ₂ Of structure (2), two of which L _b Same, L _a And L _b Corresponding to a structure selected from those shown in the following table:

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11. 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 1-10.

12. The device of claim 11, wherein the organic layer is an emissive layer and the metal complex is a light emitting material.

13. The device of claim 11, wherein the device emits yellow, green, or white light.

14. The device of claim 12, wherein the light emitting layer further comprises a host material.

15. The device of claim 12, the light emitting layer comprising at least two host materials.

16. The device of claim 14, wherein 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.

17. A composition for an organic electroluminescent device comprising the metal complex of any one of claims 1 to 10.