CN114907413A - Organic electroluminescent material and device thereof - Google Patents

Organic electroluminescent material and device thereof Download PDF

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CN114907413A
CN114907413A CN202110165117.5A CN202110165117A CN114907413A CN 114907413 A CN114907413 A CN 114907413A CN 202110165117 A CN202110165117 A CN 202110165117A CN 114907413 A CN114907413 A CN 114907413A
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蔡维
桑明
王珍
李宏博
邝志远
夏传军
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Beijing Summer Sprout Technology Co Ltd
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Abstract

Organic electroluminescent materials and devices thereof are disclosed. The organic electroluminescent material is a material comprising L having the structure of formula 1 a Metal complexes of ligands, which are useful as light-emitting materials in electroluminescent devices. The novel compounds can be applied to electroluminescent devices to show more excellent performance, can reduce driving voltage, improve device efficiency, especially improve EQE, and finally can obviously improve the comprehensive performance of the devices. Also disclosed are an electroluminescent device comprising the metal complex and a compound combination comprising the metal complex.

Description

Organic electroluminescent material and device thereof
Technical Field
The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. More particularly, it relates to a composition comprising L having the structure of formula 1 a Metal complexes of ligands, and electroluminescent devices and compound combinations comprising the metal complexes.
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 of Islamic 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). The most advanced OLEDs may comprise 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 achieved high efficiency through Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return 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 fabrication 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.
The applicant previously disclosed in US20200251666a1 ligands having the structure shown below
Figure BDA0002937504240000011
Wherein X 1 -X 8 At least one of which is selected from C-CN, further discloses iridium complexes having the structure
Figure BDA0002937504240000021
The organic electroluminescent device can improve the performance and color saturation of the device when being applied to the organic electroluminescent device, and although the organic electroluminescent device reaches the higher level in the industry, the organic electroluminescent device still has room for improvement. In this application only R is disclosed 4 Metal complexes of aryl substituents being phenyl groups and their use in devices, the introduction of (hetero) aryl groups having the effect as specified herein at specific positions in the metal complexes on device performance is not disclosed and taught.
In our previous US20200091442a1, the applicant disclosed ligand structures having the following structure
Figure BDA0002937504240000022
Further disclosed are iridium complexes having the structure
Figure BDA0002937504240000023
In the application, fluorine at a specific position of the ligand can improve the performance of the material, including improving the service life of the device, increasing the thermal stability and the like, and still has room for improvement. In this application only R is disclosed 4 Metal complexes of aryl substituents being phenyl groups and their use in devices, the introduction of (hetero) aryl groups having the effect as specified herein at specific positions in the metal complexes on device performance is not disclosed and taught.
US2013119354a1 discloses a metal complex having the general structure:
Figure BDA0002937504240000024
wherein R is 1 -R 4 Selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In this application only R is disclosed 1 Metal complexes of aryl substituents being phenyl groups and their use in devices, the introduction of (hetero) aryl groups having the effect as specified herein at specific positions in the metal complexes on device performance is not disclosed and taught.
U.S. Pat. No. 3, 20200287144, 1 discloses a metal complex comprising a ligand structure having the structure shown below
Figure BDA0002937504240000031
And
Figure BDA0002937504240000032
wherein X 1 Selected from silicon and germanium, further discloses an iridium complex having the following general structure:
Figure BDA0002937504240000033
the application is primarily concerned with the effect of introducing silicon or germanium groups into the metal complex on device performance, and does not disclose or teach the effect of introducing (hetero) aryl groups at specific positions in the metal complex as specified herein on device performance.
Disclosure of Invention
The present invention is directed to a series of L's comprising a structure having formula 1 a Metal complexes of ligands solve at least part of the above problems.
According to one embodiment of the present invention, a metal complex is disclosed comprising a metal M, and a ligand L coordinated to the metal M a Wherein L is a Has a structure represented by formula 1:
Figure BDA0002937504240000034
in the case of the formula 1, the compound,
the metal M is selected from metals having a relative atomic mass greater than 40;
each occurrence of Cy is the same or different and is selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms, or a combination thereof;
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R' are the same or different;
X 1 -X 5 selected from CR, identically or differently at each occurrence x Or N;
ar has a structure represented by formula 2:
Figure BDA0002937504240000035
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence denotes mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is 8 or more;
R’，R x ，R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"" indicates the attachment position of formula 2;
adjacent substituents R', R x ，R a1 ，R a2 Can optionally be linked to form a ring.
According to another 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 the metal complex of the previous embodiment.
According to another embodiment of the present invention, a combination of compounds is also disclosed, which comprises the metal complex of the previous embodiment.
The invention discloses a series of L containing structures with formula 1 a Metal complexes of ligands, which are useful as light-emitting materials in electroluminescent devices. The novel compounds can be applied to electroluminescent devices to show more excellent performance, can reduce driving voltage, improve device efficiency, especially improve EQE, and finally can obviously improve comprehensive performance of the devices.
Drawings
FIG. 1 is a schematic representation of an organic light emitting device that can contain the metal complexes and compound combinations disclosed herein.
FIG. 2 is a schematic representation of another organic light emitting device that may contain combinations of the metal complexes and compounds 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 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, the entire disclosure is incorporated by referenceA flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:1 4 -TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, 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 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 injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer may 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 the other organic electronic devices listed previously.
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. 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 may be described as "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 a fluorescent OLED can be statistically limited by delaying fluorescence by more than 25% spin. 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 the transition from the triplet state back to the 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. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state. The total singlet fraction may be 100%, far exceeding 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 typically 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-as used herein, includes both straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 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. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.
Cycloalkyl-as used herein, comprises a cyclic alkyl group. The cycloalkyl group may be a cycloalkyl group having 3 to 20 ring carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Among the above, preferred are cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl. In addition, cycloalkyl groups may be optionally substituted.
Heteroalkyl-as used herein, heteroalkyl comprises a alkyl chain wherein one or more carbons are substituted with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium and boron atoms. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxyethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, trimethylgermylisopropyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, tert-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. In addition, heteroalkyl groups may be optionally substituted.
Alkenyl-as used herein, encompasses straight chain, branched chain, and cyclic olefin groups. The alkenyl group may be an alkenyl group containing 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2, 2-diphenylvinyl, 1-methylallyl, 1, 1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight chain alkynyl groups are contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, and the like. Of the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, phenylethynyl. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene,the reaction product of fluorene, pyrene,
Figure BDA0002937504240000061
perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-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-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, mesityl and m-quaterphenyl. In addition, the aryl group may be optionally substituted.
Heterocyclyl or heterocyclic-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. In addition, the heterocyclic group may be optionally substituted.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom and a boron atom. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, and more preferably a heteroaryl group having 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, benzoselenophenepyridyl, selenophene bipyridine, selenobenzodipyridine, selenium benzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.
Alkoxy-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as those described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, alkoxy groups may be optionally substituted.
Aryloxy-as used herein, 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. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the aryloxy group include a phenoxy group and a biphenyloxy group. In addition, the aryloxy group may be optionally substituted.
Aralkyl-as used herein, encompasses aryl substituted alkyl. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. 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-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable. In addition, the aralkyl group may be optionally substituted.
Alkylsilyl-as used herein, alkyl substituted silyl is contemplated. The alkylsilyl group may be an alkylsilyl group having 3 to 20 carbon atoms, preferably an alkylsilyl group having 3 to 10 carbon atoms. Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, methyldiethylsilyl group, ethyldimethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, methyldiisopropylsilyl group, dimethylisopropylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, dimethyl-tert-butylsilyl group, and methyl-di-tert-butylsilyl group. Additionally, the alkylsilyl group may be optionally substituted.
Arylsilyl-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of the arylsilyl group include triphenylsilyl group, phenylbiphenylsilyl group, diphenylbiphenylsilyl group, phenyldiethylsilyl group, diphenylethylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, phenyldiisopropylsilyl group, diphenylisopropylsilyl group, diphenylbutylsilyl group, diphenylisobutylsilyl group, and diphenyltert-butylsilyl group. In addition, the arylsilyl group may be optionally substituted.
Alkylgermyl-as used herein, alkyl-substituted germyl is contemplated. The alkylgermyl group may be an alkylgermyl group having 3 to 20 carbon atoms, preferably an alkylgermyl group having 3 to 10 carbon atoms. Examples of the alkylgermyl group include a trimethylgermyl group, a triethylgermyl group, a methyldiethylgermyl group, an ethyldimethylgermyl group, a tripropyl-germyl group, a tributyl-germyl group, a triisopropylgermyl group, a methyldiisopropylgermyl group, a dimethylisopropyl-germyl group, a tri-tert-butylgermyl group, a triisobutylgermyl group, a dimethyl-tert-butylgermyl group, and a methyl-di-tert-butylgermyl group. In addition, the alkylgermyl group may be optionally substituted.
Arylgermyl-as used herein, encompasses at least one aryl or heteroaryl substituted germyl. The arylgermanium group may be an arylgermanium group having 6 to 30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of the arylgermanium group include a triphenylgermanium group, a phenylbiphenylgermanium group, a diphenylbiphenylgermanium group, a phenyldiethylgermanium group, a diphenylethylgermanium group, a phenyldimethylgermanium group, a diphenylmethylgermanium group, a phenyldiisopropylgermanium group, a diphenylisopropylgermanium group, a diphenylbutylgermanium group, a diphenylisobutylgermanium group, a diphenyltert-butylgermanium group. In addition, the arylgermyl group may be optionally substituted.
The term "aza" in azabenzofuran, azabenzothiophene, etc., means that one or more of the 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 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 heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermyl, substituted arylgermyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, meaning alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, alkylgermyl, arylgermyl, amino, 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 heterocyclyl having 3 to 20 ring 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 alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, mercapto, 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 compound 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 (including spiro, bridged, fused, etc.), 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:
Figure BDA0002937504240000091
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:
Figure BDA0002937504240000092
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 further away are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
Figure BDA0002937504240000093
further, the expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following equation:
Figure BDA0002937504240000094
according to one embodiment of the present invention, a metal complex is disclosed comprising a metal M, and a ligand L coordinated to the metal M a Wherein L is a Has a structure represented by formula 1:
Figure BDA0002937504240000095
in the case of the formula 1, the compound,
the metal M is selected from metals having a relative atomic mass greater than 40;
each occurrence of Cy is the same or different and is selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms, or a combination thereof;
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R' are the same or different;
X 1 -X 5 selected from CR, identically or differently at each occurrence x Or N;
ar has a structure represented by formula 2:
Figure BDA0002937504240000101
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence indicates mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
R’，R x ，R a1 and R a2 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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 toolsAn alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl 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 hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
"Tuo" indicates the attachment position of formula 2;
adjacent substituents R', R x ，R a1 ，R a2 Can optionally be linked to form a ring.
As used herein, the "adjacent substituents R', R x ，R a1 ，R a2 Can optionally be linked to form a ring ", is intended to mean a group in which adjacent substituents are present, for example, between two substituents R', two substituents R x In between, two substituents R a1 In between, two substituents R a2 In between, two substituents R a1 And R a2 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.
As used herein, "ring atom" in the aromatic ring and the heteroaromatic ring means an atom constituting the ring itself in a cyclic structure having aromaticity (for example, a monocyclic (hetero) aromatic ring, a condensed (hetero) aromatic ring). Both the carbon and heteroatoms in the ring (including but not limited to O, S, N, Se or Si, etc.) are counted as being within the number of ring atoms. When the ring is substituted with a substituent, the atoms included in the substituent are not included in the number of ring atoms. For example, the number of ring atoms of phenyl, pyridyl and triazinyl is 6; the ring atom number of the bithiophene and the bitofuran is 8; the ring atoms of the benzothiophenyl and the benzofuranyl are both 9; the number of ring atoms of naphthyl, quinolyl, isoquinolyl, quinazolinyl and quinoxalinyl is 10; the number of ring atoms of dibenzothiophene, dibenzofuran, fluorene, azadibenzothiophene, azadibenzofuran and azafluorene are all 13; the various examples described herein are by way of example only, and so forth. When a in formula 2 is 0, i.e.Represents Ar has
Figure BDA0002937504240000102
Structure of (1), at this time "Ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) being 8 or more represents ring Ar 1 Is an aromatic or heteroaromatic ring having a total number of ring atoms of 8 or more; when a in formula 2 is 1, it means that Ar has a formula
Figure BDA0002937504240000103
The structure shown; for example when ring Ar 1 And ring Ar 2 Are each phenyl, R a1 And R a2 When both are hydrogen, ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is equal to 12; and e.g. then ring Ar 1 And ring Ar 2 Are each phenyl, R a1 Are each hydrogen, R a2 When it is monosubstituted and phenyl, ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is equal to 12. And so on for other cases.
According to an embodiment of the invention, wherein Cy is selected from any of the structures in the group consisting of:
Figure BDA0002937504240000111
wherein, the first and the second end of the pipe are connected with each other,
r represents, identically or differently on each occurrence, mono-, polysubstituted or unsubstituted; when multiple R are present in any structure, the R are the same or different;
r is selected, identically or differently on each occurrence, 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amine group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R can optionally be linked to form a ring;
wherein, '#' indicates a position to which the metal M is connected,
Figure BDA0002937504240000112
is represented by X 1 ，X 2 ，X 3 Or X 4 The location of the connection.
Herein, "adjacent substituents R can be optionally linked to form a ring", is intended to mean a group of substituents wherein any two adjacent substituents R may be linked to form a ring. Obviously, none of these substituents may be linked to each other to form a ring.
According to an embodiment of the present invention, wherein L a Each occurrence, the same or different, is selected from the group consisting of:
Figure BDA0002937504240000113
Figure BDA0002937504240000121
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R's are the same or different;
ar has a structure represented by formula 2:
Figure BDA0002937504240000131
a is selected from 0, 1,2, 3,4 or 5;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
R，R x ，R a1 and R a2 The same or different at each occurrence represents mono-, poly-, or no substitution;
R，R’，R x ，R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R, R', R x ，R a1 And R a2 Can optionally be linked to form a ring;
"Twining" indicates the attachment position of formula 2.
As used herein, the "adjacent substituents R, R', R x ，R a1 And R a2 Can optionally be linked to form a ring ", is intended to denote a group in which adjacent substituents are present, for example, between two substituents R', two substituents R x In between, two substituents R a1 In between, two substituents R a2 In between, two substituents R a1 And R a2 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 complex has M (L) a ) m (L b ) n (L c ) q A general formula (II) of (I);
wherein, the first and the second end of the pipe are connected with each other,
m is selected, identically or differently on each occurrence, from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; preferably, M is selected, identically or differently on each occurrence, from Pt or Ir;
L a 、L b and L c Respectively a first, a second and a third ligand coordinated to the metal M, and L c And said L a Or L b Are the same or different; wherein L is a 、L b And L c Optionally linked to form a multidentate ligand;
m is selected from 1,2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, M + n + q is equal to the oxidation state of the metal M; when m is 2 or more, a plurality of L a The same or different; when n is equal to 2, two L b The same or different; when q is equal to 2, two of L c The same or different;
L b and L c A structure, which is the same or different at each occurrence, selected from any one of the group consisting of:
Figure BDA0002937504240000132
Figure BDA0002937504240000141
wherein the content of the first and second substances,
R a ，R b the same or different at each occurrence 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 ，CR C1 R C2 ；
R a ，R b ，R c ，R N1 ，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 heterocyclyl having 3 to 20 ring 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 alkynyl 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, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amine group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R a ，R b ，R c ，R N1 ，R C1 And R C2 Can optionally be linked to form a ring.
In this context, it is intended that,"Adjacent substituents R a ，R b ，R c ，R N1 ，R C1 And R C2 Can optionally be linked to form a ring ", is intended to denote a group of adjacent substituents therein, e.g. two substituents R a In between, two substituents R b In between, two substituents R c Of a substituent R a And R b Of a substituent R a And R c Of a substituent R b And R c Of a substituent R a And R N1 Of a substituent R b And R N1 Of R is a substituent a And R C1 Of a substituent R a And R C2 Of a substituent R b And R C1 Of R is a substituent b And R C2 And R is C1 And R C2 And any one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be linked to each other to form a ring.
According to one embodiment of the invention, wherein the metal M is selected, identically or differently at each occurrence, 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, identically or differently on each occurrence.
According to one embodiment of the invention, the metal complex Ir (L) is a ) m (L b ) 3-m Has a structure represented by formula 3:
Figure BDA0002937504240000142
wherein, the first and the second end of the pipe are connected with each other,
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R's are the same or different;
m is selected from 1,2 or 3; when m is selected from 1, two of L b The same or different; when m is selected from 2 or 3, a plurality of L a The same or different;
Y 1 -Y 4 selected from CR, identically or differently at each occurrence y Or N;
X 1 -X 5 selected from CR, identically or differently at each occurrence x Or N;
ar has a structure represented by formula 2:
Figure BDA0002937504240000151
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence represents mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
"Tuo" indicates the attachment position of formula 2;
R’，R x ，R y ，R 1 -R 8 、R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl group having 3 to 20 carbon atoms, substituted or unsubstitutedSubstituted arylgermanyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents R', R x ，R y ，R a1 ，R a2 Can optionally be linked to form a ring;
adjacent substituents R 1 -R 8 Can optionally be linked to form a ring.
As used herein, the "adjacent substituents R', R x ，R y ，R a1 ，R a2 Can optionally be linked to form a ring ", is intended to mean a group in which adjacent substituents are present, for example, between two substituents R', two substituents R x In between, two substituents R y In between, two substituents R a1 In between, two substituents R a2 In between, two substituents R a1 And R a2 In the presence of two substituents R' and R x 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. "Adjacent substituents R 1 -R 8 Can optionally be linked to form a ring ", is intended to mean a group in which adjacent substituents are present, for example, adjacent substituents R 1 And R 2 Between, adjacent substituents R 3 And R 2 Between, adjacent substituents R 3 And R 4 Adjacent substituents R 5 And R 4 Adjacent substituents R 5 And R 6 Between, adjacent substituents R 7 And R 6 Between, adjacent substituents R 7 And R 8 And any one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be linked to each other to form a ring.
According to one embodiment of the invention, among others, the metal complex Ir (L) a ) m (L b ) 3-m Has a structure represented by formula 3A:
Figure BDA0002937504240000161
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R's are the same or different;
m is selected from 1,2 or 3; when m is selected from 1, two of L b The same or different; when m is selected from 2 or 3, a plurality of L a The same or different;
R x and R y The same or different at each occurrence represents mono-, poly-or no-substitution;
ar has a structure represented by formula 2:
Figure BDA0002937504240000162
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence represents mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
the "denotes the attachment position of formula 2;
R’，R x ，R y ，R 1 -R 8 、R a1 and R a2 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 heterocyclyl having 3 to 20 ring 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 aryloxy having 2 to 2 carbon atoms0 carbon atom alkenyl group, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine group having 0 to 20 carbon atoms, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, hydroxyl group, mercapto group, sulfinyl group, sulfonyl group, phosphino group, and combinations thereof;
adjacent substituents R', R x ，R y ，R a1 ，R a2 Can optionally be linked to form a ring;
adjacent substituents R 1 -R 8 Can optionally be linked to form a ring.
According to one embodiment of the present invention, wherein X 1 -X 5 Is the same or different at each occurrence and is selected from CR x 。
According to an embodiment of the invention, wherein Y 1 -Y 4 Identical or different at each occurrence and selected from CR y 。
According to one embodiment of the present invention, wherein X 1 -X 5 In which at least one is N, e.g. X 1 -X 8 One of which is N or two of which are N.
According to an embodiment of the invention, wherein Y 1 -Y 4 At least one of them being N, e.g. Y 1 -Y 4 One of which is N or two of which are N.
According to one embodiment of the invention, wherein X is selected from O or S.
According to one embodiment of the invention, wherein X is selected from O.
According to an embodiment of the invention, wherein a is selected from 0, 1,2 or 3.
According to one embodiment of the invention, wherein a is selected from 1.
According to the inventionAn embodiment of the invention, wherein R a1 And R a2 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 aralkyl groups having 7 to 30 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, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof.
According to one embodiment of the invention, wherein R a1 And R a2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 15 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein R a1 And R a2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, and combinations thereof.
According to one embodiment of the invention, wherein, in Ar, ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 18 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is not less than 8 and not more than 30.
According to one embodiment of the invention, among Ar, ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is not less than 8 and not more than 24.
According to one embodiment of the invention, in Ar, ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is not less than 8 and not more than 18.
According to one embodiment of the invention, in Ar, ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 ring atoms, or a heteroaromatic ring having 5 or 6 ring atoms, or a combination thereof.
According to one embodiment of the invention, in Ar, ring Ar 1 And ring Ar 2 Selected, identically or differently on each occurrence, from aromatic or heteroaromatic rings having 6 ring atoms.
According to one embodiment of the invention, among Ar, ring Ar 1 And ring Ar 2 Selected from aromatic rings having 6 ring atoms, identically or differently on each occurrence.
According to one embodiment of the invention, among Ar, ring Ar 1 And ring Ar 2 Each occurrence, the same or different, is selected from the group consisting of: a benzene ring, a pyridine ring, a pyrimidine ring, a naphthalene ring, a triazine ring, a phenanthrene ring, an anthracene ring, a silafluorene ring, a quinoline ring, an isoquinoline ring, a benzofuran ring, a bithiophene ring, a benzothiophene ring, an indene ring, a dibenzofuran ring, a dibenzothiophene ring, a triphenylene ring, a carbazole ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, an azasilafluorene ring, and combinations thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is not less than 8 and not more than 30.
According to one embodiment of the invention, wherein Ar, on each occurrence, is selected, identically or differently, from the group consisting of:
Figure BDA0002937504240000171
Figure BDA0002937504240000172
Figure BDA0002937504240000181
Figure BDA0002937504240000191
Figure BDA0002937504240000192
and combinations thereof;
optionally, the above groups may be partially or fully deuterated; wherein ". sup." represents the bonding position of Ar.
According to one embodiment of the invention, wherein 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, 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, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein R x Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 11 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to an embodiment of the invention, wherein R is x At least one selected from the group consisting of: 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 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, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein R x At least one ofSelected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein R x At least one selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, cyano groups, and combinations thereof.
According to an embodiment of the invention, wherein X 1 -X 5 At least one of them is selected from CR x And said R is x Is cyano or fluorine.
According to an embodiment of the invention, wherein X 3 -X 5 At least one of them is selected from CR x And said R is x Is cyano or fluorine.
According to an embodiment of the invention, wherein X 5 Is CR x And said R is x Is cyano or fluorine.
According to one embodiment of the invention, wherein 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, 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, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein R y Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, or a pharmaceutically acceptable salt thereofSubstituted or unsubstituted alkylsilyl groups of 3-15 carbon atoms, and combinations thereof.
According to an embodiment of the invention, wherein at least one R y Selected from the group consisting of: 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 aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all selected from the group consisting of: deuterium, 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 one embodiment of the invention, wherein R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all selected from the group consisting of: deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, neopentyl, tert-pentyl, and combinations thereof; optionally, the hydrogens in the above groups are partially or fully deuterated.
According to one embodiment of the invention, wherein R' is 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' is methyl or deuterated methyl.
According to one embodiment of the invention, wherein R 7 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 heterocyclyl having 3 to 20 ring 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 amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof.
According to one embodiment of the present invention, wherein L a Each occurrence being selected identically or differently from L a1 To L a1177 Group of wherein L a1 To L a1177 The specific structure of (a) is as defined in claim 16.
According to an embodiment of the invention, wherein L b Each occurrence, identically or differently, of a group selected from L b1 To L b128 Group of wherein L b1 To L b128 The concrete structure of (3) is as described in claim 17.
According to an embodiment of the invention, wherein L c Each occurrence being selected identically or differently from L c1 To L c360 Group of wherein L c1 To L c360 The specific structure of (a) is as described in claim 18.
According to one embodiment of the invention, wherein the metal complex has Ir (L) a ) 2 (L b ) Structure of (1), L a Each occurrence being selected identically or differently from L a1 To L a1177 Any one or any two of the group consisting of, L b Is selected from the group consisting of L b1 To L b128 Any one of the group consisting of wherein L a1 To L a1177 According to claim 16, L b1 To L b128 The concrete structure of (3) is as described in claim 17.
According to one embodiment of the invention, wherein the metal complex has Ir (L) a )(L b ) 2 Structure of (1), L a Each occurrence being selected identically or differently from L a1 To L a1177 Any one of the group consisting of L b Is selected from the group consisting of L b1 To L b128 Any one or any two of the group consisting of, wherein L a1 To L a1177 According to claim 16, L b1 To L b128 The specific structure of (A) is as described in claim 17.
According to one embodiment of the invention, wherein the metal complex has Ir (L) a ) 3 Structure of (1), L a Each occurrence, identically or differently, of a group selected from L a1 To L a1177 Any one or any two or any three of the group consisting of wherein L a1 To L a1177 See claim 16 for details of the structure.
According to one embodiment of the invention, wherein the metal complex has Ir (L) a ) 2 (L c ) Structure of (1), L a Each occurrence being selected identically or differently from L a1 To L a1177 Any one or any two of the group consisting of, L c Is selected from the group consisting of L c1 To L c360 Any one of the group consisting of wherein L a1 To L a1177 According to claim 16, L c1 To L c360 The specific structure of (a) is as described in claim 18.
According to one embodiment of the invention, wherein the metal complex has Ir (L) a )(L c ) 2 Structure of (1), L a Each occurrence being selected identically or differently from L a1 To L a1177 Any one of the group consisting of L c Is selected from the group consisting of L c1 To L c360 Any one or any two of the group consisting of, wherein L a1 To L a1177 According to claim 16, L c1 To L c360 According to claim 18.
According to one embodiment of the invention, the metal complex has Ir (L) a )(L b )(L c ) Structure of (1), wherein L a Each occurrence being selected identically or differently from L a1 To L a1177 Any one of the group consisting of L b Is selected from the group consisting of L b1 To L b128 Any one of the group consisting of L c Is selected from the group consisting of L c1 To L c360 Any one of the group consisting of; wherein L is a1 To L a1177 According to claim 16, L b1 To L b128 According to claim 17, L c1 To L c360 According to claim 18.
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 1008, and the specific structures of metal complex 1 to metal complex 1008 are described in claim 19.
According to one embodiment of the present invention, there is 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 the metal complex of any of the preceding embodiments.
According to an embodiment of the present invention, wherein the organic layer including the metal complex in the electroluminescent device is a light-emitting layer.
According to an embodiment of the invention, wherein said light emitting layer of said electroluminescent device is emitting green light.
According to an embodiment of the invention, wherein the light emitting layer of the electroluminescent device is emitting white light.
According to one embodiment of the present invention, wherein the light emitting layer of the electroluminescent device comprises a first host compound therein.
According to one embodiment of the present invention, wherein the light-emitting layer of the electroluminescent device comprises a first host compound and a second host compound.
According to an embodiment of the invention, wherein at least one of the host compounds in the electroluminescent device 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.
According to one embodiment of the present invention, wherein the first host compound has a structure represented by formula 4:
Figure BDA0002937504240000211
wherein, the first and the second end of the pipe are connected with each other,
E 1 -E 6 is selected, identically or differently on each occurrence, from C, CR e Or N, and E 1 -E 6 At least two of which are N, E 1 -E 6 At least one of which is C and is connected with the formula A;
Figure BDA0002937504240000221
wherein the content of the first and second substances,
q is the same or different at each occurrence and is selected from the group consisting of O, S, Se, N, NR ", CR" R ", SiR" R ", GeR" R "and R" C ═ CR "; when two R 'are present at the same time, the two R' may be the same or different;
p is 0 or 1; r is 0 or 1;
when Q is selected from N, p is 0 and r is 1;
when Q is selected from the group consisting of O, S, Se, NR ", CR" R ", SiR" R ", GeR" R "and R" C ═ CR ", p is 1 and R is 0;
l is selected, identically or differently on each occurrence, from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;
Q 1 -Q 8 selected, identically or differently at each occurrence, from C, CR q Or N;
R e r' and R q Each occurrence, identically or differently, 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"" represents the connection position of formula a and formula 4;
adjacent substituents R e ，R”，R q Can optionally be joined to form a ring.
As used herein, the "adjacent substituents R e ，R”，R q Can optionally be linked to form a ring ", is intended to mean a group in which adjacent substituents are present, e.g. two substitutionsRadical R e Between two substituents R', two substituents R q In between, two substituents R' and R q 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 an embodiment of the invention, wherein E 1 -E 6 Is selected, identically or differently on each occurrence, from C, CR e Or N, and E 1 -E 6 Three of them are N, E 1 -E 6 At least one is CR e And said R is e Each occurrence, the same or different, is selected from the group consisting of: 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 invention, wherein E 1 -E 6 Selected, identically or differently at each occurrence, from C, CR e Or N, and E 1 -E 6 Three of them are N, E 1 -E 6 At least one is CR e And said R is e Each occurrence, the same or different, is selected from the group consisting of: substituted or unsubstituted phenyl, substituted or substituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, and combinations thereof.
According to one embodiment of the invention, wherein Q is selected, identically or differently on each occurrence, from O, S, N or NR ".
According to an embodiment of the present invention, wherein Q 1 -Q 8 At least one or at least two of them are selected from CR q And said R is q Selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5 to 30 carbon atoms, or combinations thereof.
According to an embodiment of the invention, wherein Q 1 -Q 8 At least one or at least two of them are selected from CR q And said R is q Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted pyridyl, or combinations thereof.
According to one embodiment of the invention, wherein each occurrence of L, which is the same or different, is selected from a single bond, a substituted or unsubstituted arylene having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein L is selected, identically or differently on each occurrence, from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted fluorenylene group.
According to one embodiment of the invention, wherein L is selected, identically or differently on each occurrence, from the group consisting of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group.
According to one embodiment of the present invention, wherein the first host compound is selected from the group consisting of H-1 to H-243, wherein the specific structures of H-1 to H-243 are as defined in claim 26.
According to an embodiment of the present invention, wherein the second host compound in the electroluminescent device has a structure represented by formula 5:
Figure BDA0002937504240000231
wherein the content of the first and second substances,
L x each occurrence identically or differently selected from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;
v is selected, identically or differently on each occurrence, from C, CR v Or N, and at least one of V is C, and with L x Connecting;
u is selected, identically or differently on each occurrence, from C, CR u Or N, and at least one of U is C, and with L x Connecting;
R v and R u Each occurrence, identically or differently, 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
Ar 6 each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a combination thereof;
adjacent substituents R v And R u Can optionally be linked to form a ring;
in this embodiment, the "adjacent substituents R v And R u Can optionally be linked to form a ring ", is intended to denote a group of adjacent substituents therein, e.g. two substituents R v BetweenTwo substituents R u In between, two substituents R v And R u 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 present invention, wherein the second host compound in the electroluminescent device has a structure represented by formula 5-a to
A structure represented by one of formulas 5-j:
Figure BDA0002937504240000241
wherein, the first and the second end of the pipe are connected with each other,
L x each occurrence identically or differently selected from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;
v is selected, identically or differently on each occurrence, from C, CR v Or N, and at least one of V is C, and with L x Connecting;
u is selected, identically or differently on each occurrence, from C, CR u Or N, and at least one of U is C, and with L x Connecting;
R v and R u Each occurrence, identically or differently, 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 heterocyclic group having 3 to 20 ring 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 alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atomsA group, 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 alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl 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 hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
Ar 6 each occurrence, identically or differently, is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a combination thereof;
adjacent substituents R v And R u Can optionally be linked to form a ring;
according to one embodiment of the present invention, wherein the second host compound is selected from the group consisting of compounds X-1 to X-128, wherein the specific structures of compounds X-1 to X-128 are defined in claim 28.
According to one embodiment of the present invention, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% to 30% of the total weight of the light-emitting layer.
According to one embodiment of the invention, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% -13% of the total weight of the light-emitting layer.
According to another embodiment of the present invention, a combination of compounds is disclosed, the combination of compounds comprising a metal complex according to 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 of U.S. 2016/0359122A1, 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.
Materials described herein as useful for particular layers in organic light emitting devices 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, paragraph 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 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 to, and the synthetic route and the preparation method thereof are as follows:
synthesis example 1: synthesis of Metal Complex 127
Step 1:
Figure BDA0002937504240000261
a dry 500mL round bottom flask was charged with 5-methyl-2-phenylpyridine (10.0g, 59.2mmol), iridium trichloride trihydrate (5.0g, 14.2mmol), 300mL 2-ethoxyethanol, 100mL water, three times with nitrogen displacement and nitrogen blanket, heated at 130 ℃ and stirred for 24 h. After cooling, filtration, washing with methanol and n-hexane three times respectively, and suction drying gave 7.5g of intermediate 1 as a yellow solid (97% yield).
Step 2:
Figure BDA0002937504240000262
a500 mL dry round bottom flask was charged with intermediate 1(7.5g, 6.8mmol), dry dichloromethane 250mL, methanol 10mL, silver triflate (3.8g, 14.8mmol) sequentially, replaced with nitrogen three times and stirred at room temperature overnight. Filtration through celite, 2-fold rinsing with dichloromethane, the lower organic phase collected and concentrated under reduced pressure to give 9.2g of intermediate 2 (93% yield).
And step 3:
Figure BDA0002937504240000263
a dry 500mL round bottom flask was charged with intermediate 2(1.3g, 1.7mmol), intermediate 3(0.9g, 2.3mmol), 250mL of ethanol, three times replaced with nitrogen and the reaction was heated at 100 ℃ for 18h under nitrogen. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 127(0.75g, 47.7% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 925.3.
Synthesis example 2: synthesis of Metal Complex 505
Step 1:
Figure BDA0002937504240000271
a dry 500mL round bottom flask was charged with 5-tert-butyl-2-phenylpyridine (13.2g, 62.9mmol), iridium trichloride trihydrate (5.5g, 15.7mmol), 300mL 2-ethoxyethanol, 100mL water, three times with nitrogen displacement and nitrogen blanket, and stirred at 130 ℃ for 24 h. After cooling, filtration, three washes with methanol and n-hexane respectively, and pump dried to give 9.7g of intermediate 4 (97% yield).
And 2, step:
Figure BDA0002937504240000272
a500 mL dry round bottom flask was charged with intermediate 4(9.7g, 7.7mmol), dry dichloromethane 250mL, methanol 10mL, silver triflate (4.3g, 16.7mmol) in that order, replaced with nitrogen three times and stirred at room temperature overnight. Celite was filtered, washing 2 times with dichloromethane, the lower organic phase was collected and concentrated under reduced pressure to give 13.2g of intermediate 5 as a yellow solid (93% yield).
And step 3:
Figure BDA0002937504240000273
a dry 500mL round bottom flask was charged with intermediate 5(1.4g, 1.8mmol), intermediate 3(0.9g, 2.2mmol), 300mL ethanol, three times with nitrogen substitution and nitrogen blanket, and heated at 100 ℃ for 24 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 505(0.75g, 41.3% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 1009.4.
Synthetic example 3: synthesis of Metal Complex 520
Step 1:
Figure BDA0002937504240000281
a dry 250mL round bottom flask was charged with intermediate 6(2.0g, 4.9mmol), intermediate 5(2.7g, 3.3mmol), 2-ethoxyethanol and N, N-dimethylformamide each 50mL in sequence, replaced with nitrogen three times and reacted under nitrogen with heating at 100 ℃ for 96 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 520(1.74g, 51.5% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 1023.4.
Synthetic example 4: synthesis of Metal Complex 532
Step 1:
Figure BDA0002937504240000282
a dry 500mL round bottom flask was charged with intermediate 7(1.8g, 4.5mmol), intermediate 5(2.5g, 3.0mmol), 300mL of ethanol, three times replaced with nitrogen and the reaction was heated at 100 ℃ for 24h under nitrogen. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 532(0.55g, 18.2% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 1009.4.
Synthetic example 5: synthesis of Metal Complex 181
Step 1:
Figure BDA0002937504240000283
a dry 500mL round bottom flask was charged with intermediate 2(2.6g, 3.5mmol), intermediate 8(2.2g, 5.3mmol), 250mL of ethanol, replaced with nitrogen three times and the reaction was heated at 100 ℃ for 18h under nitrogen. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 181(1.1g, 33.3% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 943.2.
Synthetic example 6: synthesis of Metal Complex 559
Step 1:
Figure BDA0002937504240000291
a dry 500mL round bottom flask was charged with intermediate 5(2.1g, 2.6mmol), intermediate 8(1.5g, 3.6mmol), 300mL of ethanol, three times with nitrogen substitution and nitrogen blanket, and the reaction was heated at 100 ℃ for 24 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 559(1.30g, 48.7% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 1027.3.
Synthetic example 7: synthesis of Metal Complex 197
Step 1:
Figure BDA0002937504240000292
a dry 250mL round bottom flask was charged with intermediate 2(2.0g, 2.8mmol), intermediate 9(1.8g, 3.9mmol), 2-ethoxyethanol and N, N-dimethylformamide each 50mL in sequence, replaced with nitrogen three times and reacted under nitrogen with heating at 100 ℃ for 72 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 197(1.2g, 43.4% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 1006.3.
Synthesis example 8: synthesis of Metal Complex 460
Step 1:
Figure BDA0002937504240000293
a dry 250mL round bottom flask was charged with 4- (methyl-d) in sequence 3 ) -2-phenylpyridine-5-d (5.0g, 28.9mmol), iridium trichloride (2.6g, 7.4mmol), 2-ethoxyethanol (60mL) and water (20mL), heated to reflux under nitrogen and stirred for 24 h. After cooling, suction filtration under reduced pressure, methanol and n-hexane were washed three times, respectively, to give 4.0g of yellow solid intermediate 10 (94.8% yield).
Step 2:
Figure BDA0002937504240000301
a500 mL dry round bottom flask was charged with intermediate 10(4.0g, 3.5mmol), dry dichloromethane (250mL), methanol (10mL), silver triflate (1.9g, 7.6mmol) sequentially, replaced with nitrogen three times and stirred at room temperature overnight. Filtration through celite, washing 2 times with dichloromethane, the lower organic phase was collected and concentrated under reduced pressure to give 5.1g of intermediate 11 (97.4% yield).
And step 3:
Figure BDA0002937504240000302
a dry 250mL round bottom flask was charged with intermediate 12(1.5g, 3.7mmol), intermediate 11(2.1g, 2.2mmol), N, N-dimethylformylAmine 50mL, 2-Ethoxyethanol 50mL, N 2 And (4) protecting, heating to reflux, and reacting for 96 hours. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 460(0.82g, 40.0% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 932.3.
Synthetic example 9: synthesis of Metal Complex 571
Step 1:
Figure BDA0002937504240000303
a dry 250mL round bottom flask was charged with intermediate 13(1.4g, 1.7mmol), intermediate 5(1.0g, 2.4mmol), 2-ethoxyethanol and N, N-dimethylformamide each 50mL in sequence, replaced with nitrogen three times and reacted under nitrogen with heating at 100 ℃ for 72 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 571(0.5g, 28.4% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 1034.3.
Synthesis example 10: synthesis of Metal Complex 572
Step 1:
Figure BDA0002937504240000311
a dry 250mL round bottom flask was charged with intermediate 5(2.4g, 2.9mmol), intermediate 14(1.5g, 3.4mmol), 2-ethoxyethanol and N, N-dimethylformamide in 50mL each, displaced with nitrogen three times and protected with nitrogen, and heated at 100 ℃ for 72 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 572(0.7g, 23.0% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 1048.4.
Synthetic example 11: synthesis of Metal Complex 579
Step 1:
Figure BDA0002937504240000312
a dry 250mL round bottom flask was charged with intermediate 5(2.2g, 2.7mmol), intermediate 15(1.5g, 3.6mmol), 2-ethoxyethanol and N, N-dimethylformamide in 50mL each, displaced with nitrogen three times and protected with nitrogen, and heated at 100 ℃ for 72 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid on top of the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the product metal complex 579(0.8g, 30.7% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 1034.3.
Synthetic example 12: synthesis of Metal Complex 697
Step 1:
Figure BDA0002937504240000313
a dry 500mL round bottom flask was charged with 5-neopentyl-2-phenylpyridine (13.4g, 59.1mmol), iridium trichloride trihydrate (5.2g, 14.8mmol), 300mL 2-ethoxyethanol, 100mL water, three times with nitrogen displacement and nitrogen blanket, heated at 130 ℃ and stirred for 24 h. After cooling, filtration, three washes with methanol and n-hexane respectively, and suction dried to give 8.5g of intermediate 16 (88% yield).
Step 2:
Figure BDA0002937504240000321
a500 mL dry round bottom flask was charged with intermediate 16(9.7g, 7.7mmol), dry dichloromethane 250mL, methanol 10mL, silver triflate (4.3g, 16.7mmol) sequentially, replaced with nitrogen three times and stirred at room temperature overnight. Celite was filtered and the lower organic phase was collected by washing 2 times with dichloromethane and concentrated under reduced pressure to give 11.8g of intermediate 17 as a yellow solid (100% yield).
And step 3:
Figure BDA0002937504240000322
a dry 250mL round bottom flask was charged with intermediate 17(2.0g, 2.3mmol), intermediate 13(1.4g, 3.2mmol), 2-ethoxyethanol and N, N-dimethylformamide each 50mL in sequence, replaced with nitrogen three times and reacted under nitrogen with heating at 100 ℃ for 72 h. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above the celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the metal complex 697(0.8g, 32.7% yield) as a yellow solid product. The product was identified as the target product and had a molecular weight of 1062.4.
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 examples 1-1
First, a glass substrate, having an Indium Tin Oxide (ITO) anode 80nm thick, was cleaned and 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. 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 Hole Injection Layer (HIL). The compound HT is used as a Hole Transport Layer (HTL). The compound X-4 was used as an Electron Blocking Layer (EBL). The metal complex 127 of the present invention is then doped in the compound X-4 and the compound H-91 to co-deposit as an emitting layer (EML). On the EML, compound H-1 acts as a Hole Blocking Layer (HBL). On HBL, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-deposited as an electrodepositA sub transport layer (ETL). Finally, 8-hydroxyquinoline-lithium (Liq) was evaporated to a thickness of 1nm as an electron injection layer, and 120nm of aluminum as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorbent to complete the device.
Device example 2-1
Device example 2-1 was carried out in the same manner as device example 1-1 except that the metal complex 505 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device example 2-2
Device example 2-2 was implemented in the same manner as device example 1-1 except that the present metal complex 520 was used in the light-emitting layer in place of the present metal complex 127.
Device examples 2 to 3
Device example 2-3 was carried out in the same manner as device example 1-1 except that the metal complex 532 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device comparative example 1-1
Device comparative example 1-1 was conducted in the same manner as in device example 1-1 except that the compound GD1 was used in place of the metal complex 127 of the present invention in the light-emitting layer (EML).
Device comparative example 2-1
Device comparative example 2-1 was conducted in the same manner as in device example 1-1 except that the compound GD2 was used in place of the metal complex 127 of the present invention in the light-emitting layer (EML).
Device comparative examples 2-2
Device comparative example 2-2 was implemented in the same manner as in device example 1-1 except that the compound GD3 was used in the light-emitting layer (EML) instead of the metal complex 127 of the present invention.
Comparative device examples 2 to 3
Device comparative example 2-3 was conducted in the same manner as in device example 1-1 except that the compound GD4 was used in place of the metal complex 127 of the present invention in the light-emitting layer (EML).
Device comparative examples 2 to 4
Device comparative examples 2 to 4 were carried out in the same manner as in device example 1 to 1 except that the compound GD5 was used in place of the metal complex 127 of the present invention in the light-emitting layer (EML).
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 examples 1-1, 2-1 to 2-3 and comparative examples 1-1, 2-1 to 2-4
Figure BDA0002937504240000331
Figure BDA0002937504240000341
The material structure used in the device is as follows:
Figure BDA0002937504240000342
Figure BDA0002937504240000351
the IVL characteristics of the device were measured. At 1000cd/m 2 The CIE data of the devices, the maximum emission wavelength lambda, were measured max Full width at half maximum (FWHM), voltage (V), Current Efficiency (CE), Power Efficiency (PE). External Quantum Efficiency (EQE) data was at 15mA/cm 2 The test was performed at constant current. These data are recorded and presented in table 2.
TABLE 2 device data for examples 1-1, 2-1 to 2-3 and comparative examples 1-1, 2-1 to 2-4
Figure BDA0002937504240000352
Discussion:
table 2 shows device properties of examples and comparative examples. Example 1-1 compared with comparative example 1-1, and examples 2-1 to 2-3 compared with comparative example 2-1, the difference is that the specific Ar substituent of the metal complex is replaced by phenyl, and the CE, PE and EQE of the device are obviously improved under the conditions that the half-peak width is equivalent to the maximum emission wavelength and the driving voltage is slightly reduced. Example 1-1 compared to comparative example 1-1, EQE was improved by about 8.3%, PE was improved by about 8.6%, and CE was improved by about 7.4%. Examples 2-1 to 2-3 showed about 10.2%, 8.2%, 6.7% improvement in EQE, 14.7%, 16.8%, and 10.5% improvement in PE, and 9.6%, 7.4%, and 5.3% improvement in CE, respectively, compared to comparative example 2-1. The metal complex provided by the invention has the advantages that the specific Ar substituent group substituted phenyl group is superior to the comparative example in multiple properties of the device, and the comprehensive performance of the device can be obviously improved.
Metal complexes GD3, GD4, and GD5 having specific Ar substitutions at other positions were synthesized for comparison, i.e., comparative examples 2-2 to 2-4. Example 2-1 is different from comparative examples 2-2 to 2-4 in L of the metal complex a The biphenyl of the ligand is at different substitution sites, and under the condition of equivalent driving voltage, the CE, PE and EQE of the device are greatly improved. Example 2-1 the EQE was increased by 12.5%, 29.7% and 21.7% respectively compared to comparative examples 2-2 to 2-4; PE is respectively improved by 10.1%, 37.9% and 23.8%; CE increased by 7.2%, 32% and 22.6%, respectively. This indicates that L of the present invention having a specific Ar substituent at a specific position a The metal complex of the ligand is superior to the complex of the comparative example in multiple properties of the device, and the comprehensive performance of the device can be obviously improved. The advantages observed with the compounds of the present invention of introducing specific substituents at specific positions are completely unexpected. Even for the person skilled in the art, it is not possible to predict this.
Device example 3-1
Device example 3-1 was carried out in the same manner as in device example 1-1 except that the metal complex 181 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device example 3-2
Device example 3-2 was implemented in the same manner as device example 1-1 except that the metal complex 559 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device example 4-1
Device example 4-1 was carried out in the same manner as in device example 1-1 except that the metal complex 197 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device example 4-2
Device example 4-2 was implemented in the same manner as device example 1-1 except that the metal complex 460 of the present invention was used in the light-emitting layer instead of the metal complex 127 of the present invention.
Device examples 4 to 3
Device example 4-3 was carried out in the same manner as device example 1-1 except that the metal complex 571 of the present invention was used in the light-emitting layer in place of the metal complex 127 of the present invention.
Device examples 4 to 4
Device example 4-4 was carried out in the same manner as in device example 1-1 except that the present metal complex 572 was used in place of the present metal complex 127 in the light-emitting layer.
Device examples 4 to 5
Device examples 4 to 5 were carried out in the same manner as device example 1 to 1 except that the metal complex 579 of the present invention was used in place of the metal complex 127 of the present invention in the light-emitting layer.
Device examples 4 to 6
Device examples 4-6 were carried out in the same manner as device example 1-1 except that the metal complex 127 of the present invention was replaced with the metal complex 697 of the present invention in the light-emitting layer.
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 3 device structures of examples 3-1 to 3-2 and 4-1 to 4-6
Figure BDA0002937504240000361
Figure BDA0002937504240000371
The structure of the material used in the device is as follows:
Figure BDA0002937504240000372
Figure BDA0002937504240000381
the IVL characteristics of the device were measured. At 1000cd/m 2 The CIE data of the devices, the maximum emission wavelength lambda, were measured max Full width at half maximum (FWHM), voltage (V), Current Efficiency (CE), Power Efficiency (PE). External Quantum Efficiency (EQE) data was at 15mA/cm 2 The test was performed at constant current. These data are recorded and presented in table 4.
TABLE 4 device data for examples 3-1 to 3-2 and 4-1 to 4-6
Figure BDA0002937504240000382
Discussion:
table 4 shows the device properties of inventive examples 3-1 to 3-2 and 4-1 to 4-6. Metal complexes of examples 3-1 to 3-2 except at L a The ligand has a fluorine substitution in addition to the specific Ar substitution at specific positions, and the EQE, CE and PE are slightly improved compared with examples 1-1 and 2-1 without fluorine substitution.
Meanwhile, the metal complexes of examples 4-1 to 4-6 were prepared except that a The specific position of the ligand has specific Ar substituent and also further comprises cyano group substitution, and compared with examples 1-1 and 2-1 to 2-3 without cyano group substitution, the ligand has the advantages that the driving voltage is obviously reduced, the half-peak width is narrowed to be within 21.7nm to 26.9nm, and the maximum emission wavelength lambda is increased max In the equivalent case, narrowing of the half-width is advantageous for obtaining more saturated luminescence. The EQE reached levels greater than 24%, especially 26.35% for example 4-1.
The above results indicate that the L of the present invention comprising a specific Ar substitution at a specific position a Metal complex of ligand, further in L a The ligand has at least one substituent group, such as fluorine or cyano group substitution, and the complex is superior to the complex of the comparative example in multiple properties of the device, so that the comprehensive properties of the device can be obviously improved, and the device properties can be further improved compared with the metal complex only containing specific Ar substitution.
Meanwhile, the metal complex 505 of the present invention is used as a light emitting dopant, and is applied to a light emitting layer of an organic electroluminescent device in cooperation with first host compounds of different structures to prepare devices of device examples 5-1 to 5-5, and the properties thereof are characterized.
Device example 5-1
Device example 5-1 was implemented in the same manner as device example 2-1 except that the ratio of the compound X-4, the compound H-91, and the metal complex 505 in the light-emitting layer was 66:28: 6.
Device example 5-2
Device example 5-2 was carried out in the same manner as in device example 5-1 except that the compound H-1 was used in place of H-91 in the light-emitting layer.
Device examples 5 to 3
Device example 5-3 was carried out in the same manner as in device example 5-1 except that the compound H-141 was used in place of H-91 in the light-emitting layer.
Device examples 5 to 4
Device example 5-4 was implemented in the same manner as device example 5-1 except that the compound H-171 was used in place of H-91 in the light-emitting layer.
Device examples 5 to 5
Device example 5-5 was carried out in the same manner as in device example 5-1 except that the compound H-172 was used in place of H-91 in the light-emitting layer.
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 5 device example 5-1 to device example 5-5 device structures
Figure BDA0002937504240000391
The structure of the material used in the device is as follows:
Figure BDA0002937504240000401
the IVL characteristics of the device were measured. At 1000cd/m 2 The CIE data of the device is measured, the maximum emission wavelength lambda max Full width at half maximum (FWHM), voltage (V), Current Efficiency (CE), Power Efficiency (PE). External Quantum Efficiency (EQE) data was at 15mA/cm 2 The test was performed at constant current. These data are recorded and presented in table 6.
TABLE 6 device data for device examples 5-1 through 5-5
Figure BDA0002937504240000402
From the above data, it can be seen that examples 5-1 to 5-5 are comparable to example 2-1 in performance, with the EQE also being around 24%, especially the EQE of example 5-2 reaching 25.03%. As explained above, the invention is directed to L substituted at a particular Ar a The metal complex of the ligand can be used as a light-emitting material in a light-emitting layer of an electroluminescent device, and when the metal complex is used in combination with host materials of different structures, excellent device performance can be achieved.
In summary, the invention includes L having a particular Ar substitution at a particular position a Compared with the existing metal complex with Ar substituent groups at other substitution positions in La ligand, the metal complex of the ligand in the device has more excellent performance, can reduce driving voltage, improves device efficiency, especially improves EQE, and finally can obviously improve the comprehensive performance of the device. The advantages observed with the compounds of the invention are completely unexpected, even if it is predicted for the person skilled in the art that this is the caseIt is not possible.
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 (30)

1. A metal complex comprising a metal M, and a ligand L coordinated to the metal M a Wherein L is a Has a structure represented by formula 1:
Figure FDA0002937504230000011
in the case of the formula 1, the compound,
the metal M is selected from metals having a relative atomic mass greater than 40;
cy, the same or different at each occurrence, is selected from a substituted or unsubstituted aromatic ring having 6 to 24 ring atoms, a substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms, or a combination thereof;
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R' are the same or different;
X 1 -X 5 selected from CR, identically or differently at each occurrence x Or N;
ar has a structure represented by formula 2:
Figure FDA0002937504230000012
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence indicates mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
R’，R x ，R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"Tuo" indicates the attachment position of formula 2;
adjacent substituents R', R x ，R a1 ，R a2 Can optionally be linked to form a ring.
2. The metal complex according to claim 1, wherein Cy is any one structure selected from the group consisting of:
Figure FDA0002937504230000013
Figure FDA0002937504230000021
wherein the content of the first and second substances,
r represents, identically or differently on each occurrence, mono-, polysubstituted or unsubstituted; when multiple R are present in any structure, the R are the same or different;
r is selected, identically or differently on each occurrence, 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 heterocyclyl having 3 to 20 ring 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 alkynyl 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, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermyl group having 3-20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6-20 carbon atoms, a substituted or unsubstituted amine group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R can optionally be linked to form a ring;
wherein, '#' indicates the position where the metal M is connected,
Figure FDA0002937504230000022
is represented by the formula X 1 ，X 2 ，X 3 Or X 4 Connection ofThe position of (a).
3. The metal complex of claim 1 or 2, wherein the metal complex has M (L) a ) m (L b ) n (L c ) q A general formula (II) of (I);
wherein the content of the first and second substances,
each occurrence of M is selected, identically or differently, from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; preferably, M is selected, identically or differently on each occurrence, from Pt or Ir;
L a 、L b and L c Are respectively a first, a second and a third ligand coordinated to the metal M, and L c And said L a Or L b Are the same or different; wherein L is a 、L b And L c Optionally linked to form a multidentate ligand;
m is selected from 1,2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, M + n + q is equal to the oxidation state of the metal M; when m is 2 or more, a plurality of L a The same or different; when n is equal to 2, two L b The same or different; when q is equal to 2, two L c The same or different;
L a each occurrence, the same or different, is selected from the group consisting of:
Figure FDA0002937504230000023
Figure FDA0002937504230000031
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R's are the same or different;
ar has a structure represented by formula 2:
Figure FDA0002937504230000041
a is selected from 0, 1,2, 3,4 or 5;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
"" indicates the attachment position of formula 2;
R，R x ，R a1 and R a2 The same or different at each occurrence indicates mono-, poly-, or no substitution;
L b and L c A structure, which is the same or different at each occurrence, selected from any one of the group consisting of:
Figure FDA0002937504230000042
wherein the content of the first and second substances,
X b each occurrence, the same or different, is selected from the group consisting of: o, S, Se, NR N1 ，CR C1 R C2 ；
R a And R b The same or different at each occurrence indicates mono-, poly-, or no substitution;
R，R’，R x ，R a ，R b ，R c ，R N1 ，R C1 ，R C2 ，R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkene having 2 to 20 carbon atomsA group, a substituted or unsubstituted alkynyl 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 alkylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl 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 hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents R, R', R x ，R a1 And R a2 Can optionally be linked to form a ring;
adjacent substituents R a ，R b ，R c ，R N1 ，R C1 ，R C2 Can optionally be linked to form a ring.
4. The metal complex of claim 1, wherein the metal complex Ir (L) a ) m (L b ) 3-m Has a structure represented by formula 3:
Figure FDA0002937504230000051
wherein the content of the first and second substances,
x is selected from the group consisting of O, S, Se, NR ', SiR ' R ' and GeR ' R '; when two R 'are present at the same time, the two R's are the same or different;
m is selected from 1,2 or 3; when m is selected from 1, two of L b The same or different; when m is selected from 2 or 3, a plurality of L a The same or different;
Y 1 -Y 4 selected from CR, identically or differently at each occurrence y Or N;
X 1 -X 5 is selected, identically or differently on each occurrence, from CR x Or N;
ar has a structure represented by formula 2:
Figure FDA0002937504230000052
a is selected from 0, 1,2, 3,4 or 5;
R a1 and R a2 The same or different at each occurrence indicates mono-, poly-or no-substitution;
ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (a) is not less than 8;
R’，R x ，R y ，R 1 -R 8 、R a1 and R a2 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"Tuo" indicates the attachment position of formula 2;
adjacent substituents R', R x ，R y ，R a1 ，R a2 Can optionally be linked to form a ring;
adjacent substituents R 1 -R 8 Can optionally be linked to form a ring.
5. The metal complex of claim 1 or 4, wherein X 1 -X 5 Identical or different at each occurrence and selected from CR x And/or Y 1 -Y 4 Identical or different at each occurrence and selected from CR y 。
6. The metal complex of claim 1 or 4, wherein X 1 -X 5 At least one of which is N, and/or Y 1 -Y 4 At least one of which is N.
7. The metal complex of any one of claims 1 to 6, wherein X is selected from O or S, a is selected from 0, 1,2 or 3; preferably, a is 1.
8. A metal complex as claimed in any one of claims 1 to 7, wherein R a1 And R a2 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 aralkyl groups having 7 to 30 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, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof;
preferably, R a1 And R a2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 18 carbon atomsAn aryl group of carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 15 carbon atoms, and combinations thereof;
more preferably, R a1 And R a2 Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, and combinations thereof.
9. The metal complex of any one of claims 1 to 8, in Ar, ring Ar 1 And ring Ar 2 Each occurrence, the same or different, is selected from an aromatic ring having 6 to 18 ring atoms, a heteroaromatic ring having 5 to 18 ring atoms, or a combination thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (B) is not less than 8 and not more than 30;
preferably, among Ar, ring Ar 1 And ring Ar 2 Each occurrence, the same or different, is selected from the group consisting of: a benzene ring, a pyridine ring, a pyrimidine ring, a naphthalene ring, a triazine ring, a phenanthrene ring, an anthracene ring, a silafluorene ring, a quinoline ring, an isoquinoline ring, a benzofuran ring, a bithiophene ring, a benzothiophene ring, an indene ring, a dibenzofuran ring, a dibenzothiophene ring, a triphenylene ring, a carbazole ring, an azacarbazole ring, an azadibenzofuran ring, an azadibenzothiophene ring, an azasilafluorene ring, and combinations thereof; and ring Ar 1 And ring Ar 2 The total number of ring atoms of (2) is not less than 8 and not more than 30.
10. The metal complex of any one of claims 1 to 8, in Ar, ring Ar 1 And ring Ar 2 Each occurrence, identically or differently, is selected from an aromatic ring having 6 ring atoms, a heteroaromatic ring having 5 or 6 ring atoms, or a combination thereof;
preferably, ring Ar 1 And ring Ar 2 Each occurrence of the same orVariously selected from aromatic or heteroaromatic rings having 6 ring atoms;
more preferably, ring Ar 1 And ring Ar 2 Selected from aromatic rings having 6 ring atoms, identically or differently on each occurrence.
11. The metal complex of any one of claims 1 to 8, wherein Ar, on each occurrence, is selected, identically or differently, from the group consisting of:
Figure FDA0002937504230000061
Figure FDA0002937504230000071
Figure FDA0002937504230000081
Figure FDA0002937504230000082
and combinations thereof;
optionally, the above groups may be partially or fully deuterated; wherein ". sup." represents the bonding position of Ar.
12. The metal complex of any one of claims 1 to 11, wherein 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, 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, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof;
preferably, R x At least one selected from the group consisting of: deuterium, fluoro, substituted or unsubstituted, having 1-6 carbon atomsA substituted or unsubstituted cycloalkyl group having from 3 to 6 ring carbon atoms, a substituted or unsubstituted aryl group having from 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having from 3 to 12 carbon atoms, a substituted or unsubstituted alkylsilyl group having from 3 to 6 carbon atoms, a cyano group, and combinations thereof;
more preferably, R x At least one selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, cyano groups, and combinations thereof.
13. A metal complex according to any one of claims 1 to 12, wherein X 1 -X 5 At least one of them is selected from CR x And said R is x Is cyano or fluorine;
preferably, X 3 -X 5 At least one of them is selected from CR x And said R is x Is cyano or fluorine;
more preferably, X 5 Is CR x And said R is x Is cyano or fluorine.
14. A metal complex as claimed in claim 4, wherein 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, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 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, and combinations thereof;
preferably, at least one R y Selected from the group consisting of: 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted alkyl having 3 to 30 carbon atomsAn atomic heteroaryl group, and combinations thereof.
15. A metal complex according to claim 4, wherein R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, 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;
preferably, R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, and combinations thereof;
more preferably, R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, neopentyl, tert-pentyl, and combinations thereof; optionally, the hydrogens in the above groups can be partially or fully deuterated.
16. The metal complex of claim 1, wherein L a Each occurrence, identically or differently, is selected from any one of the group consisting of:
Figure FDA0002937504230000091
Figure FDA0002937504230000101
Figure FDA0002937504230000111
Figure FDA0002937504230000121
Figure FDA0002937504230000131
Figure FDA0002937504230000141
Figure FDA0002937504230000151
Figure FDA0002937504230000161
Figure FDA0002937504230000171
Figure FDA0002937504230000181
Figure FDA0002937504230000191
Figure FDA0002937504230000201
Figure FDA0002937504230000211
Figure FDA0002937504230000221
Figure FDA0002937504230000231
Figure FDA0002937504230000241
Figure FDA0002937504230000251
Figure FDA0002937504230000261
Figure FDA0002937504230000271
Figure FDA0002937504230000281
Figure FDA0002937504230000291
Figure FDA0002937504230000301
Figure FDA0002937504230000311
Figure FDA0002937504230000321
Figure FDA0002937504230000331
Figure FDA0002937504230000341
Figure FDA0002937504230000351
Figure FDA0002937504230000361
Figure FDA0002937504230000371
Figure FDA0002937504230000381
Figure FDA0002937504230000391
Figure FDA0002937504230000401
Figure FDA0002937504230000411
Figure FDA0002937504230000421
Figure FDA0002937504230000431
Figure FDA0002937504230000441
Figure FDA0002937504230000451
Figure FDA0002937504230000461
Figure FDA0002937504230000471
Figure FDA0002937504230000481
Figure FDA0002937504230000491
Figure FDA0002937504230000501
Figure FDA0002937504230000511
Figure FDA0002937504230000521
Figure FDA0002937504230000531
Figure FDA0002937504230000541
Figure FDA0002937504230000551
Figure FDA0002937504230000561
Figure FDA0002937504230000571
Figure FDA0002937504230000581
Figure FDA0002937504230000591
Figure FDA0002937504230000601
Figure FDA0002937504230000611
17. a metal complex according to claim 3 or 16, wherein L b Each occurrence, the same or different, is selected from the group consisting of:
Figure FDA0002937504230000612
Figure FDA0002937504230000621
Figure FDA0002937504230000631
Figure FDA0002937504230000641
18. a metal complex according to claim 3 or 17, wherein L c Each occurrence, the same or different, is selected from the group consisting of:
Figure FDA0002937504230000642
Figure FDA0002937504230000651
Figure FDA0002937504230000661
Figure FDA0002937504230000671
Figure FDA0002937504230000681
Figure FDA0002937504230000691
Figure FDA0002937504230000701
Figure FDA0002937504230000711
19. the metal complex of claim 18, wherein the metal complex has Ir (L) a ) 2 (L b ) Or Ir (L) a )(L b ) 2 Or Ir (L) a ) 3 In which L is a Each occurrence being selected identically or differently from L a1 To L a1177 Any one or any two or any three of the group consisting of, L b Is selected from the group consisting of L b1 To L b128 Any one or two of the group consisting of;
or the metal complex has Ir (L) a ) 2 (L c ) Or Ir (L) a )(L c ) 2 In which L is a Each occurrence being selected identically or differently from L a1 To L a1177 Any one or any two of the group consisting of, L c Is selected from the group consisting of L c1 To L c360 Any one or two of the group consisting of;
or the metal complex has Ir (L) a )(L b )(L c ) In which L is a Each occurrence being selected identically or differently from L a1 To L a1177 Any one of the group consisting of L b Is selected from the group consisting of L b1 To L b128 Any one of the group consisting of L c Is selected from the group consisting of L c1 To L c360 Any one of the group consisting of;
preferably, among these, the metal complex is selected from the group consisting of metal complex 1 to metal complex 1008, wherein metal complex 1 to metal complex 1008 have IrL a (L b ) 2 Of structure (2), two of which L b Same wherein L a And L b Respectively corresponding to the structures indicated in the following table:
Figure FDA0002937504230000712
Figure FDA0002937504230000721
Figure FDA0002937504230000731
Figure FDA0002937504230000741
Figure FDA0002937504230000751
Figure FDA0002937504230000761
Figure FDA0002937504230000771
Figure FDA0002937504230000781
Figure FDA0002937504230000791
Figure FDA0002937504230000801
Figure FDA0002937504230000811
Figure FDA0002937504230000821
Figure FDA0002937504230000831
Figure FDA0002937504230000841
。
20. an electroluminescent device, comprising:
an anode, a cathode, an 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 1-19.
21. The electroluminescent device of claim 20, wherein the organic layer comprising the metal complex is a light emitting layer.
22. The electroluminescent device of claim 20 wherein the electroluminescent device emits green or white light.
23. The electroluminescent device of claim 21 wherein the light-emitting layer comprises a first host compound;
preferably, the light-emitting layer further comprises a second host compound;
more preferably, the first and/or second host compound 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.
24. The electroluminescent device of claim 23, wherein the first host compound has a structure represented by formula 4:
Figure FDA0002937504230000851
wherein, the first and the second end of the pipe are connected with each other,
E 1 -E 6 is selected, identically or differently on each occurrence, from C, CR e Or N, and E 1 -E 6 At least two of which are N, E 1 -E 6 At least one of which is C and is linked to formula A;
Figure FDA0002937504230000852
wherein the content of the first and second substances,
q, identical or different at each occurrence, is selected from the group consisting of O, S, Se, N, NR ", CR" R ", SiR" R ", GeR" R "and R" C ═ CR "; when two R 'are present at the same time, the two R' may be the same or different;
p is 0 or 1; r is 0 or 1;
when Q is selected from N, p is 0 and r is 1;
when Q is selected from the group consisting of O, S, Se, NR ", CR" R ", SiR" R ", GeR" R "and R" C ═ CR ", p is 1 and R is 0;
l is selected, identically or differently on each occurrence, from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;
Q 1 -Q 8 is selected, identically or differently on each occurrence, from C, CR q Or N;
R e r' and R q Each occurrence, identically or differently, 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 group with 3-20 carbon atoms, substituted or unsubstituted arylsilyl group with 6-20 carbon atoms, substituted or unsubstituted alkylgermyl group with 3-20 carbon atoms, substituted or unsubstituted aryl group with 6-20 carbon atomsGermanyl, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"" represents the connection position of formula a and formula 4;
adjacent substituents R e ，R”，R q Can optionally be joined to form a ring.
25. The electroluminescent device of claim 24, wherein E 1 -E 6 Selected, identically or differently at each occurrence, from C, CR e Or N, and E 1 -E 6 Three of them are N, E 1 -E 6 At least one is CR e And said R is e Each occurrence, the same or different, is selected from the group consisting of: 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;
and/or Q is selected, identically or differently on each occurrence, from O, S, N or NR ";
and/or Q 1 -Q 8 At least one or at least two of them are selected from CR q And said R is q Selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 5 to 30 carbon atoms, or combinations thereof;
and/or L is selected, identically or differently on each occurrence, from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof.
26. The electroluminescent device of claim 24, wherein the first host compound is selected from the group consisting of:
Figure FDA0002937504230000861
Figure FDA0002937504230000871
Figure FDA0002937504230000881
Figure FDA0002937504230000891
Figure FDA0002937504230000901
Figure FDA0002937504230000911
Figure FDA0002937504230000921
Figure FDA0002937504230000931
Figure FDA0002937504230000941
Figure FDA0002937504230000951
Figure FDA0002937504230000961
Figure FDA0002937504230000971
Figure FDA0002937504230000981
Figure FDA0002937504230000991
Figure FDA0002937504230001001
Figure FDA0002937504230001011
Figure FDA0002937504230001021
Figure FDA0002937504230001031
Figure FDA0002937504230001041
27. the electroluminescent device of claim 23, wherein the second host compound has a structure represented by formula 5:
Figure FDA0002937504230001042
wherein, the first and the second end of the pipe are connected with each other,
L x each occurrence, which is the same or different, is selected from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;
v is selected, identically or differently on each occurrence, from C, CR v Or N, and at least one of V is C, and with L x Connecting;
u is selected, identically or differently on each occurrence, from C, CR u Or N, and at least one of U is C, and with L x Connecting;
R v and R u Each occurrence, identically or differently, 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl 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, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
Ar 6 each occurrence being the same or different and is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atomsOr a combination thereof;
adjacent substituents R v And R u Can optionally be linked to form a ring;
preferably, wherein the second host compound has a structure represented by one of formulae 5-a to 5-j:
Figure FDA0002937504230001051
Figure FDA0002937504230001061
28. the electroluminescent device of claim 27, wherein the second host compound is selected from the group consisting of:
Figure FDA0002937504230001062
Figure FDA0002937504230001071
Figure FDA0002937504230001081
Figure FDA0002937504230001091
Figure FDA0002937504230001101
Figure FDA0002937504230001111
Figure FDA0002937504230001121
Figure FDA0002937504230001131
Figure FDA0002937504230001141
Figure FDA0002937504230001151
Figure FDA0002937504230001161
29. the electroluminescent device as claimed in claim 23, wherein a metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1-30% of the total weight of the light-emitting layer;
preferably, the weight of the metal complex accounts for 3% -13% of the total weight of the light-emitting layer.
30. A combination of compounds comprising the metal complex of any one of claims 1-19.
CN202110165117.5A 2021-02-06 2021-02-06 Organic electroluminescent material and device thereof Pending CN114907413A (en)

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