CN114516890A

CN114516890A - Organic electroluminescent material and device thereof

Info

Publication number: CN114516890A
Application number: CN202111011390.9A
Authority: CN
Inventors: 桑明; 王珍; 李宏博; 蔡维; 刘艳华; 汤斌; 张玄; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2020-11-18
Filing date: 2021-09-02
Publication date: 2022-05-20

Abstract

Disclosed are an organic electroluminescent material and a device thereof. The organic electroluminescent material is L containing a structure of formula 1A_aLigands and L of formula 1B_bMetal complexes of ligands, which can give higher sublimation yields upon sublimation, have lower evaporation temperatures. The application of the organic electroluminescent material in an electroluminescent device can provide better device performance, such as the improvement of the service life of the device and narrower half-peak width. Also disclosed are an electroluminescent device comprising the metal complex and a compound composition 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 L comprising the structure of formula 1A_aLigands and L of formula 1B_bMetal complexes of ligands, and organic 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 has 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 polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.

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

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

Cyano substitution is not often introduced into phosphorescent metal complexes, such as iridium complexes. US20140252333a1 discloses a series of cyano-phenyl substituted iridium complexes and the results do not clearly show the effect brought by the cyano group. In addition, since cyano is a substituent of very electron withdrawing, it is also used as an emission spectrum of a blue-shifted phosphorescent metal complex, as in US20040121184a 1. The application US20200251666a1, which was filed earlier by the applicant of the present application, discloses metal complexes with cyano-substituted ligands, which can be applied to organic electroluminescent devices to improve device performance and color saturation, although reaching the higher level in the industry, there is still room for improvement.

Alkyl substitution is often introduced into phosphorescent metal complexes, such as iridium complexes, to produce red emission colors. In US2014231755a1 it was found that the 5-deuterated methyl group in 2-phenylpyridine can improve the lifetime of the device.

Disclosure of Invention

The present invention is directed to a series of L's comprising the structure of formula 1A_aLigands and L of formula 1B_bMetal complexes of ligands solve at least part of the above problems. The metal complexes can be used as light-emitting materials in electroluminescent devices. The novel compounds can obtain higher sublimation yield and lower evaporation temperature during sublimation. The application of the organic electroluminescent material in an electroluminescent device can provide better device performance, such as the improvement of the service life of the device and narrower half-peak width.

According to one embodiment of the present invention, a metal complex is disclosed having M (L)_a)_m(L_b)_n(L_c)_qIn the general formula (I) of (A),

wherein the content of the first and second substances,

L_a、L_band L_cRespectively a first, a second and a third ligand coordinated to the metal M, and L_cAnd said L_aOr L_bAre the same or different; wherein L is_a、L_bAnd L_cOptionally linked to form a multidentate ligand;

the metal M is selected from metals having a relative atomic mass greater than 40; preferably, the metal M, equal or different at each occurrence, is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; more preferably, M is selected, identically or differently on each occurrence, from Pt or Ir;

m is 1 or 2, n is 1 or 2, q is 0 or 1, M + n + q is equal to the oxidation state of M; when m is 2, two L_aAre the same or different; when n is 2, two L_bAre the same or different;

L_aeach occurrence, the same or different, having a structure represented by formula 1A; l is_bEach occurrence, the same or different, having a structure represented by formula 1B;

wherein the content of the first and second substances,

z is selected from the group consisting of O, S, Se, NR, CRR and SiRR; when both R are present, both R are the same or different;

X₁-X₈selected from C or CR, identically or differently at each occurrence_x；

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

U₁-U₄selected from CR, identically or differently at each occurrence_uOr N;

W₁-W₄selected from CR, identically or differently at each occurrence_wOr N;

R，R_x，R_y，R_u，R_weach occurrence being the same or different and selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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;

U₁–U₄at least one or more selected from CR_uAnd said R is_uIs a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 ring carbon atoms, or a combination thereof, and all of said R' s_uThe sum of the number of carbon atoms of (a) is at least 4;

R_xat least one of which is cyano;

adjacent substituents R, R_x，R_y，R_u，R_wCan optionally be linked to form a ring;

wherein L is_cA structure, which is the same or different at each occurrence, selected from any one of the group consisting of:

wherein the content of the first and second substances,

R_a，R_band R_cThe same or different at each occurrence represents mono-, poly-, or no substitution;

X_beach occurrence, the same or different, is selected from the group consisting of: o, S, Se, NR_N1，CR_C1R_C2；

R_a，R_b，R_c，R_N1，R_C1And R_C2Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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_a，R_b，R_c，R_N1，R_C1And R_C2Can 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, at least one of the organic layers comprising the metal complex of the above embodiments.

According to another embodiment of the present invention, there is also disclosed a combination of compounds comprising the metal complex of the above embodiment.

The invention discloses a series of L containing a structure of formula 1A_aLigandsAnd L of the structure of formula 1B_bMetal complexes of ligands by reacting at L_aIntroduction of specific substituents into the ligands and in L_bThe cyano group is introduced into the ligand, and the novel compounds can obtain higher sublimation yield in sublimation and have lower evaporation temperature. These metal complexes are useful as light-emitting materials in electroluminescent devices. The application of the organic electroluminescent material in an electroluminescent device can provide better device performance, such as the improvement of the service life of the device and narrower half-peak width.

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, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:1₄TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. N-doped electron transportAn example of a 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 a non-limiting embodiment. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.

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

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

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

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

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

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

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

It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can 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. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, then the fraction of backfill singlet excited states may reach 75%. The total singlet fraction may be 100%, far exceeding 25% of the spin statistics of the electrogenerated excitons.

The 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 mono-triplet energy gap (Δ Ε)_S-T). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ E_S-T. These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).

Definitions for substituent terms

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

Alkyl-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. In addition, the alkyl group may be optionally substituted. 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, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl are preferable. In addition, the cycloalkyl group 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, and 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, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, tert-butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl. 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 the alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 3-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group, a 3-phenyl-1-butenyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cycloheptenyl group, a cycloheptatrienyl group, a cyclooctenyl group, a cyclooctatetraenyl group and a norbornenyl group. 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. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and 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, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,

perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-terphenyl-4-yl-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, 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, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, cinnolino, benzoselenophenopyridine, selenobenzene, 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 aryl and heteroaryl groups are the same as 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 groups. 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, diphenyltert-butylsilyl group, tri-tert-butylsilyl group, dimethyl-tert-butylsilyl group, and methyl-di-tert-butylsilyl group. In addition, the arylsilyl 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, azatriphenylene includes dibenzo [ f, h ] quinoxaline, dibenzo [ f, h ] quinoline and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives may be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed within the terms described herein.

In this disclosure, unless otherwise defined, when any one of the terms in the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino, any of which may be substituted by one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted heterocyclic group having 3 to 20 ring atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted alkynyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino 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, hydroxy, 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 compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.

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

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

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

wherein the content of the first and second substances,

L_a、L_band L_cAre respectively a first, a second and a third ligand coordinated to the metal M, and L_cAnd said L_aOr L_bAre the same or different; wherein L is_a、L_bAnd L_cOptionally linked to form a multidentate ligand; for example, L_a、L_bAnd L_cAny two of which may be linked to form a tetradentate ligand; also for example, L_a、L_bAnd L_cCan be combined withAre connected to form a hexadentate ligand; or also for example L_a、L_b、L_cAre not linked so as not to form a multidentate ligand;

wherein the content of the first and second substances,

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

U₁-U₄selected from CR, identically or differently at each occurrence_uOr N;

W₁-W₄selected from CR, identically or differently at each occurrence_wOr N;

R，R_x，R_y，R_u，R_weach 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 cycloalkyl having 1 to 20 carbon atomsA heterocyclic group of 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino 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;

R_xat least one of which is cyano;

wherein the content of the first and second substances,

In this context, "all of said R_uThe sum of the number of carbon atoms of (a) is at least 4 "means that the following condition" U "is satisfied₁–U₄One or more of them being selected from CR_uAnd said R is_uAll R's are substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 ring carbon atoms, or combinations thereof_uThe total number of carbon atoms of (2) is not less than 4. When U is formed₁–U₄When one of the above conditions is satisfied, the carbon atom of the substituent is 4 or more; when U is turned₁–U₄When two of them satisfy the above conditions, the sum of the number of carbon atoms of the substituents of the two is 4 or more; when U is formed₁–U₄When three of the above conditions are satisfied, the total number of carbon atoms of the three substituents is 4 or more; when U is turned₁–U₄Four of them satisfy the aboveProvided that the total number of carbon atoms of the four substituents is 4 or more. For example when U₂Selected from the group consisting of CR_uAnd the above conditions are satisfied, then U₂Substituent R of_uThe number of carbon atoms of (a) is greater than or equal to 4; when U is turned₃Selected from the group consisting of CR_uAnd the above conditions are satisfied, then U₃Substituent R of_uThe number of carbon atoms of (a) is greater than or equal to 4; and so on for other cases.

In this example, the "adjacent substituents R, R_x，R_y，R_u，R_wCan 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_xIn between, two substituents R_yIn between, two substituents R_uIn between, two substituents R_wIn between, two substituents R_wAnd R_uIn between, two substituents R_yAnd R_xAnd 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, the "adjacent substituent R_a，R_b，R_c，R_N1，R_C1And R_C2Can optionally be linked to form a ring ", is intended to denote a group of adjacent substituents therein, e.g. two substituents R_aIn between, two substituents R_bIn between, two substituents R_cOf a substituent R_aAnd R_bOf a substituent R_aAnd R_cOf a substituent R_bAnd R_cOf a substituent R_aAnd R_N1Of R is a substituent_bAnd R_N1Of R is a substituent_aAnd R_C1Of a substituent R_aAnd R_C2Of R is a substituent_bAnd R_C1Of a substituent R_bAnd R_C2And R is_C1And R_C2And 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 the inventionAn embodiment wherein L_bHas a structure represented by formula 1Ba-1 Bd:

in formula 1Ba, X₃-X₈Selected from CR, identically or differently at each occurrence_x；

In formula 1Bb, X₁And X₄-X₈Selected from CR, identically or differently at each occurrence_x；

In formula 1Bc and formula 1Bd, X₁-X₂And X₅-X₈Selected from CR, identically or differently at each occurrence_x；

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

R，R_x，R_yeach occurrence, which may be 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 alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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_x，R_yCan optionally be linked to form a ring.

In this example, the "adjacent substituents R, R_x，R_yCan 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_xIn between, two substituents R_yIn between, two substituents R_yAnd R_xAnd 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 present invention, wherein the metal complex has a structure represented by formula 2:

wherein the content of the first and second substances,

m is selected from 1 or 2; when m is 1, two L_bAre the same or different; when m is 2, two L_aAre the same or different;

X₃-X₈selected from CR, identically or differently at each occurrence_x；

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

U₁-U₄selected from CR, identically or differently at each occurrence_uOr N;

W₁-W₄selected from CR, identically or differently at each occurrence_wOr N;

R，R_x，R_y，R_u，R_weach 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 unsubstitutedSubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, an ester group, a cyano group, an isocyano group, a hydroxy group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

substituted or unsubstituted heterocyclic radical having 3 to 20 ring atoms, R_uIs a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 ring carbon atoms, or a combination thereof, and all of said R' s_uThe sum of the number of carbon atoms is at least 4;

R_xat least one of which is cyano;

adjacent substituents R, R_x，R_y，R_uCan optionally be linked to form a ring.

In this example, the "adjacent substituents R, R_x，R_y，R_uCan 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_xIn between, two substituents R_yIn between, two substituents R_uIn between, two substituents R_yAnd R_xAnd 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 Z is selected from O and S.

According to one embodiment of the invention, wherein Z is O.

In accordance with one embodiment of the present invention,wherein, R is_xOne of which is cyano and at least one other R_xSelected from the group consisting of: deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof having from 0 to 20 carbon atoms.

According to an embodiment of the invention, wherein R is_xOne of which is cyano and at least one further R_xSelected 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, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, cyano groups, hydroxyl groups, mercapto groups, and combinations thereof.

According to an embodiment of the invention, wherein R is_xOne of which is cyano and at least one further R_xSelected 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 unsubstitutedSubstituted heteroaryl groups having 3-30 carbon atoms, and combinations thereof.

According to an embodiment of the invention, wherein R is_xOne of which is cyano and at least one further R_xSelected from the group consisting of: substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 15 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R_xOne of which is cyano and at least one further R_xSelected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms.

According to an embodiment of the invention, wherein R is_xOne of which is cyano and at least one further R_xSelected from the group consisting of: fluorine, deuterium, methyl, deuterated isopropyl, cyclohexyl, deuterated cyclohexyl, phenyl, deuterated phenyl, methylphenyl, deuterated methylphenyl.

According to an embodiment of the invention, wherein X₅-X₈CR of_xIn (1), at least one is CR_xAnd said R is_xIs cyano.

According to one embodiment of the invention, X₇-X₈CR of_xAt least one of which is CR_xAnd said R is_xIs cyano;

according to one embodiment of the invention, X₇Is CR_xAnd said R is_xIs cyano.

According to one embodiment of the invention, X₈Is CR_xAnd said R is_xIs cyano.

According to an embodiment of the invention, wherein U₁-U₄Identical or different at each occurrence is CR_u，R_uAt least one of which is selected from substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 ring carbon atoms, or combinations thereof, and all of said R' s_uThe sum of the number of carbon atoms is at least 4.

In accordance with one embodiment of the present invention,wherein, U₁-U₄Selected from N or CR, identically or differently at each occurrence_uAnd at least one is CR_uAnd at least one is CR_u，R_uIs a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 ring carbon atoms, or a combination thereof, and said R_uThe sum of the number of carbon atoms is at least 4.

According to one embodiment of the invention, wherein R_uAt least one is selected from substituted or unsubstituted alkyl groups having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the invention, R_uAt least one of which is selected from the group consisting of substituted or unsubstituted substituents as follows:

and combinations thereof; optionally, the hydrogens in the above groups are partially or fully deuterated;

wherein "-" denotes the position of the attachment of the substituent to carbon.

According to one embodiment of the invention, wherein R_uAt least one is selected from substituted or unsubstituted alkyl groups having 4 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 6 carbon atoms, or combinations thereof.

According to an embodiment of the invention, wherein U₂Or U₃Is CR_uAnd said R is_uSelected from substituted or unsubstituted alkyl groups having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 20 carbon atoms, or combinations thereof.

According to an embodiment of the invention, wherein U₂Or U₃Is CR_u，R_uEach occurrence of which may be the same or different, said R_uSelected from substituted or unsubstituted alkyl groups having 4 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 6 carbon atoms, or combinations thereofAnd (4) combining.

According to an embodiment of the invention, wherein U₂And U₃Is CR_uAnd said R is_uEach occurrence identically or differently selected from substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 ring carbon atoms, or combinations thereof, and wherein at least one R is_uThe number of carbon atoms of the substituent is 4 or more.

According to an embodiment of the present invention, wherein U₁And U₄Is CR_u，R_uSelected from hydrogen, deuterium, methyl and deuterated methyl.

According to an embodiment of the invention, wherein W₁-W₄Each occurrence, identically or differently, being CR_w，Y₁-Y₄Each occurrence, identically or differently, being CR_y，R_wAnd R_yEach 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, and combinations thereof.

According to one embodiment of the invention, R_wAnd R_yEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, and combinations thereof.

According to one embodiment of the invention, R_wAnd R_yEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, and combinations thereof.

According to an embodiment of the invention, wherein W₁-W₄Identical or different at each occurrence is CR_wAt least one Rw is selected from the group consisting of: deuteriumHalogen, 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; and/or Y₁-Y₄Each occurrence, identically or differently, being CR_yAt least one R_yIs 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 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms.

According to one embodiment of the invention, wherein R is selected from methyl or deuterated methyl.

According to an embodiment of the invention, wherein L_aEach occurrence being selected identically or differently from L_a1-L_a206Group of wherein L_a1-L_a206The concrete structure of (3) is shown in claim 17.

According to one embodiment of the present invention, wherein L_bEach occurrence, identically or differently, of a group selected from L_b1-L_b972Group of wherein L_b1-L_b972The specific structure of (a) is shown in claim 18.

According to one embodiment of the invention, wherein the metal complex has Ir (L)_a)₂L_bStructure of (1), two L_aThe same; l is_aIs selected from L_a1-L_a206Group of wherein L_a1-L_a206The concrete structure of (A) is shown in claim 17; l is_bIs selected from L_b1-L_b972Group of wherein L_b1-L_b972The concrete structure of (b) is shown in 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 448, wherein the specific structures of metal complex 1 to metal complex 448 are shown in claim 19.

There is also disclosed, in accordance with an embodiment of the present invention, an electroluminescent device, including: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising a 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 one embodiment of the present invention, wherein the light emitting layer in the electroluminescent device emits green light.

According to one embodiment of the present invention, wherein the light emitting layer of the electroluminescent device further comprises at least one first host compound.

According to an embodiment of the present invention, wherein the light emitting layer of the electroluminescent device further comprises at least one first host compound and at least one 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 3:

wherein the content of the first and second substances,

L_xeach occurrence of the same orDifferently 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_vOr N, and at least one of V is C, and with L_xConnecting;

t is selected, identically or differently on each occurrence, from C, CR_tOr N, and at least one of T is C, and with L_xConnecting;

R_vand R_tEach occurrence, identically or differently, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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;

Ar₁each 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_vAnd R_tCan optionally be linked to form a ring.

In this example, "adjacent substituents R_vAnd R_tCan optionally be linked to form a ring ", is intended to denote a group of adjacent substituents therein, e.g. two substituents R_vIn between, two substituents R_tIn between, two substituents R_vAnd R_tAnd 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 present invention, wherein the second host compound has a structure represented by one of formula 3-a to formula 3-j:

wherein the content of the first and second substances,

L_xeach 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 CR_vOr N, and at least one of V is C, and with L_xConnecting;

t is selected, identically or differently on each occurrence, from CR_tOr N, and at least one of T is C, and with L_xConnecting;

R_vand R_tEach 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted aryl having 2 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heteroaryl having two or more substituents, and optionally substituted aryl having two or more substituentsUnsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof;

adjacent substituents R_vAnd R_tCan optionally be linked to form a ring.

According to one embodiment of the invention, the metal complex in the electroluminescent device 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.

According to one embodiment of the invention, the metal complex in the electroluminescent device 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 invention, the invention also discloses a compound combination which comprises a metal complex, wherein the specific structure of the metal complex is shown in any one of the embodiments.

In combination with other materials

The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application 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 being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 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 can be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that can be used in combination.

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 person skilled in the art knows the relevant contents of the above-mentioned device usage, testing method, etc., and can obtain the intrinsic data of the sample with certainty and without influence, the above-mentioned relevant contents are not repeated 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 13

A dry 250mL round bottom flask was charged with intermediate 1(1.6g, 4.6mmol), iridium complex 1(3.18g, 3.8mmol), 2-ethoxyethanol (30mL) and DMF (30mL), N in that order₂The reaction is heated for 144h at 90 ℃ under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above 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 13(0.82g, 22.3% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 958.3.

Synthesis example 2: synthesis of Metal Complex 7

A dry 250mL round bottom flask was charged with intermediate 2(1.0g, 2.9mmol), iridium complex 1(2.2g, 2.6mmol), 2-ethoxyethanol (40mL) and DMF (40mL), N in that order₂And heating to react for 120h at 100 ℃ under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above 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 7(0.45g, 18.1% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 958.3.

Synthetic example 3: synthesis of Metal Complex 17

A dry 250mL round bottom flask was charged with intermediate 2(1.2g, 4.5mmol), iridium complex 1(2.5g, 3.0mmol), 2-ethoxyethanol (30mL) and DMF (30mL), N in that order₂The reaction is heated for 144h at 90 ℃ under protection. After the reaction was cooled, the celite was filtered. Washing with methanol and n-hexane respectivelyAfter 2 times, 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 17(0.73g, 25.3% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 963.3.

Synthetic example 4: synthesis of Metal Complex 163

A dry 250mL round bottom flask was charged with intermediate 1(1.3g, 3.7mmol), iridium complex 2(2.2g, 2.6mmol), 2-ethoxyethanol (30mL) and DMF (30mL), N in that order₂The reaction is heated at 90 ℃ for 144h under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above 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 163(0.78g, 30.4% yield) as a yellow solid. The product was identified as the target product and had a molecular weight of 986.3.

Synthesis example 5: synthesis of Metal Complex 43

A dry 250mL round bottom flask was charged with intermediate 1(1.5g, 4.9mmol), iridium complex 3(3.0g, 3.6mmol), 2-ethoxyethanol (30mL) and DMF (30mL), N in that order₂The reaction is heated at 95 ℃ for 144h under protection. After the reaction was cooled, the celite was filtered. Methanol and n-hexane were washed 2 times, respectively, and the yellow solid above 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 43(1.23g, 35.4% yield) as a yellow solid. The product structure is determined as the target product and has the molecular weight of 964.4.

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 example 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^-8In 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). Compound H1 was used as Electron Blocking Layer (EBL). The metal complex 13 of the present invention is then doped in a compound H1 and a compound H2 to co-deposit as a light-emitting layer (EML). On EML, compound H2 acts as a Hole Blocking Layer (HBL). On the HBL, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-deposited as an Electron 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 absorber to complete the device.

Device example 3

Device example 3 was carried out in the same manner as in device example 1 except that the compound metal complex 17 was used in the light-emitting layer (EML) in place of the metal complex 13 of the present invention.

Device comparative example 1

Device comparative example 1 was conducted in the same manner as in device example 1 except that the metal complex 13 of the present invention was replaced with the compound GD1 in the light-emitting layer (EML).

Device comparative example 2

Device comparative example 2 was implemented in the same manner as in device example 1 except that the metal complex 13 of the present invention was replaced with the compound GD2 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 example 1 and comparative examples 1 to 2

The material structure used in the device is as follows:

the IVL characteristics of the device were measured. At 1000cd/m²The CIE data of the device is measured, the maximum emission wavelength lambda_maxFull width at half maximum (FWHM). The deposition temperature (Sub T) of the material was about 10 degrees in vacuum^-8The temperature obtained in the case of torr was measured at a rate of 0.2 a/sec when the metal complex was evaporated by hot vacuum. Lifetime (LT97) data was at 80mA/cm²The test was performed at constant current. These data are recorded and presented in table 2.

TABLE 2 device data for example 1 and example 3 and comparative examples 1-2

As can be seen from the data in table 2: the half-peak width of example 1 was 3.3nm narrower than that of comparative example 1 and 3.0nm narrower than that of comparative example 2. Meanwhile, the deposition temperature in device example 1 was reduced by approximately 33 ℃ compared to comparative example 1 and by approximately 29 ℃ compared to comparative example 2. The lower evaporation temperature is beneficial to keeping the stability of the complex in the evaporation process, and meanwhile, the low evaporation temperature is beneficial to the industrial application of materials, so that the energy consumption can be reduced. In addition, the lifetime of example 1 increased by as much as 51.5% compared to comparative example 1; device example 1 also had a 15.4% increase in lifetime compared to comparative example 2. Similarly, in example 3, the metal complex 17 is applied to the device, and in example 3, compared with comparative examples 1 and 2, the half-peak width is respectively narrowed by 4.6nm and 4.3nm, the evaporation temperature is respectively reduced by nearly 40 ℃ and 37 ℃, meanwhile, the device lifetime is respectively improved by 88.5% and 43.6%, namely, the device has narrower half-peak width, lower evaporation temperature and greatly improved excellent device lifetime, and the comprehensive performance of the device is greatly improved.

The metal complex 13 used in example 1 had the same ligand L as the metal complexes GD1 and GD2 used in comparative examples 1 and 2_bIs only L_aDifferences in substituents on the ligands, in the examples L with specific substitution is used_aThe ligands have narrower half-peak widths, lower evaporation temperatures, and superior device lifetimes compared to the unsubstituted or methyl-substituted comparative examples. The metal complex 17 used in example 3 is further present in L_bThe ligand has deuterium substitution, so that various performances of the device are further improved, and the comprehensive performance of the device is finally improved.

Device example 2

Device example 2 was carried out in the same manner as in device example 1 except that the metal complex 7 was used in the light-emitting layer (EML) in place of the metal complex 13 of the present invention.

Device comparative example 3

Device comparative example 3 was implemented in the same manner as in device example 1 except that the metal complex 13 of the present invention was replaced with the compound GD3 in the light-emitting layer (EML).

Table 3 device structures of example 2 and comparative example 3

The structure of the material used in the device is as follows:

the IVL characteristics of the device were measured. At 1000cd/m²The CIE data of the device is measured, the maximum emission wavelength lambda_maxFull width at half maximum (FWHM). The deposition temperature (Sub T) of the material was about 10 degrees of vacuum^-8The temperature obtained in the case of torr was measured at a rate of 0.2 a/sec when the metal complex was evaporated by hot vacuum. Lifetime (LT97) data was at 80mA/cm²The test was performed at constant current. These data are recorded and presented in table 4.

Table 4 device data for example 2 and comparative example 3

As can be seen from the data in table 4: the device example 2 has a narrower half-peak ratio of 2.3nm than the device comparative example 3 and a lower deposition temperature of approximately 26 ℃ than the device comparative example 3. In addition, the lifetime of example 2 was increased by 16.4% compared to comparative example 3. The metal complex 7 used in example 2 had the same ligand L as the metal complex GD3 used in comparative example 3_bIs simply L_aThe difference in substituents on the ligand, example 2 has a narrower half-peak width, lower evaporation temperature, and more excellent device lifetime than comparative example 3, again demonstrating the excellent effects of the present invention.

Sublimation data

The metal complex of the present invention and the comparative compound were sublimated using a sublimation apparatus of model BOF-A1-3-60 manufactured by Anhui Bezike Equipment Co. The metal complex 13, the metal complex 17, the metal complex 7 and the reference complexes GD1, GD2 and GD3 of the invention are respectively placed in a sublimation tube of a sublimator, and the degree of vacuum of the sublimation tube is reduced to 9.9 x 10-⁴pa, heating to 300-370 ℃, and stably sublimating to obtain the metal complex. Data on the sublimation yields of these materials are recorded and shown in table 5. Wherein the sublimation yield is the ratio of the mass after sublimation to the mass before sublimation.

TABLE 5 sublimation data

Compound numbering	Sublimation yield (%)
		Metal complexes 13	85.3
Metal complexes 17	88.8
		Metal complexes 7	71.1
Compound GD1	32.5
		Compound GD2	58.9
Compound GD3	48.8

As can be seen from the data in table 5: in the invention at L_aThe metal complex 13 and the metal complex 17 having specific substitutions on the ligand showed excellent sublimation properties, and the sublimation yields reached 85.3% and 88.8%, respectively, which were nearly 1.6 and 1.7 times higher than the sublimation yield (32.8%) of the reference compound GD1, respectively. Likewise, the sublimation yield (58.9%) compared to the reference compound GD2 increased by 44.8% and 50.7%, respectively. Furthermore, the sublimation yield of metal complex 7 reached 71.1% compared to the referenceThe sublimation yield (48.8%) of compound GD3 increased by 45.6%. The results show that the present invention is disclosed in L_aCompared with a metal complex without the specific substitution, the metal complex with the specific (cyclo) alkyl substitution introduced into the ligand structure has high sublimation yield, the sublimation yield is unpredictably increased greatly, and the improvement of the sublimation yield has great significance for realizing industrial mass production of the metal complex.

Device example 4

Device example 4 was implemented in the same manner as device example 1, except that compound H2 was replaced with compound H3 in the light-emitting layer (EML) and the proportions of compound H1, compound H3, and metal complex 13 were 63:31:6 in the light-emitting layer.

Device comparative example 4

Device comparative example 4 was implemented in the same manner as in device example 4 except that the metal complex 13 of the present invention was replaced with a compound GD2 in the light emitting layer (EML).

Device comparative example 5

Device comparative example 5 was implemented in the same manner as in device example 4 except that the metal complex 13 of the present invention was replaced with the compound GD4 in the light-emitting layer (EML).

Device comparative example 6

Device comparative example 6 was the same as device example 4 except that the compound GD5 was used in place of the metal complex 13 of the present invention in the light-emitting layer (EML).

Device comparative example 7

Device comparative example 7 was the same as device example 4 except that the compound GD6 was used in place of the metal complex 13 of the present invention in the light-emitting layer (EML).

The detailed device layer structure and thickness are shown in table 6 below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.

Table 6 device structures of example 4 and comparative examples 4 to 7

The structure of the material used in the device is as follows:

the IVL characteristics of the device were measured. At 1000cd/m²The CIE data of the devices, the maximum emission wavelength lambda, were measured_maxFull width at half maximum (FWHM). Lifetime (LT95) of initial light emission luminance of 10000cd/m²The time required to decay to 95% of the initial time. These data are recorded and presented in table 7.

TABLE 7 device data for example 4 and comparative examples 4-7

Device ID	CIE(x，y)	λ_max(nm)	FWHM(nm)	LT95(h)
					Example 4	(0.346，0.632)	531	37.5	1159
Comparative example 4	(0.342，0.634)	529	37.9	829
					Comparative example 5	(0.353，0.623)	531	58.9	1001
Comparative example 6	(0.352，0.623	528	60.3	910
					Comparative example 7	(0.355，0.621)	531	59.5	940

As can be seen from the data in table 7: at 10000cd/m²The life of example 4 reached 1159h, which was significantly improved over comparative examples 4 to 7, and compared to L_aComparative example 4, which has no specific substituent on the ligand, is increased by 39.8% over L_bComparative examples 5 and 7, which have no cyano substitution on the ligand, have improved by nearly 15.8% and 23.3%, respectively, relative to L_aAnd L_bComparative example 6, which has no specific substituent, is improved by 27.4%. In addition, the half-peak width of example 4 is only 37.5nm, which is much lower than about 59nm of comparative examples 5 and 7, which is very rare in the green phosphorescent device.

When L is_bWhen the ligand has no cyano substituent, L_aSpecific on the ligandComparative example 5 with fixed substitution vs. L_aComparative example 6, which has no specific substitution on the ligand, has only a 10% increase in device lifetime; when L is_bWhen the ligand has a cyano substituent, L_aExample 4 with specific substitutions on the ligand with respect to L_aComparative example 4, which has no specific substitution on the ligand, has an increase in device lifetime of 39.8%. Likewise, in the same L_aIn the case of (1), L_bExample 4 with cyano substitution of the ligand in comparison with L_bComparative example 5, in which the ligand is not cyano-substituted, has a 15.8% increase in device lifetime, while L_bThe device lifetime of comparative example 7 with fluorine substitution on the ligand was rather slightly reduced compared to comparative example 5. The above results all show that the compounds of the present invention comprising L having specific substitutions_aLigands and L with cyano substitution_bThe metal complex of the ligand can achieve excellent device performance, and particularly greatly prolongs the service life of the device.

In summary, the present invention includes compounds having specific substitutions L_aAnd L_bThe metal complex of the ligand can be used as a light-emitting material in a light-emitting layer of an electroluminescent device, and can achieve excellent device performance when used in combination with host materials of different structures. The invention discloses L's comprising specific substitutions_aAnd L_bThe metal complex of the ligand can keep the half-peak width of a related device at an industrial high level, and can greatly improve the service life of the device. In addition, the metal complex of the invention also has great improvement in sublimation yield and evaporation temperature, and has great advantages and broad prospects in industrial application.

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

Claims

1. A metal complex having M (L)_a)_m(L_b)_n(L_c)_qIn the general formula (I) of (A),

wherein the content of the first and second substances,

L_a、L_band L_cAre respectively a first, a second and a third ligand coordinated to the metal M, and L_cAnd said L_aOr L_bAre the same or different; wherein L is_a、L_bAnd L_cOptionally linked to form a multidentate ligand;

m is 1 or 2, n is 1 or 2, q is 0 or 1, M + n + q is equal to the oxidation state of M; when m is 2, two L_aAre the same or different; when n is 2, two of L_bAre the same or different;

wherein the content of the first and second substances,

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

U₁-U₄selected from CR, identically or differently at each occurrence_uOr N;

W₁-W₄selected from CR, identically or differently at each occurrence_wOr N;

R，R_x，R_y，R_u，R_weach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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;

U₁–U₄at least one or more selected from CR_uAnd said R is_uIs a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, or a combination thereof, and all of said R_uThe sum of the number of carbon atoms of (a) is at least 4;

R_xat least one of which is cyano;

wherein the content of the first and second substances,

2. The metal complex of claim 1, wherein L_bHas a structure represented by formula 1Ba-1 Bd:

wherein the content of the first and second substances,

X₁-X₈selected from CR, identically or differently at each occurrence_x；

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

R，R_x，R_yeach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino 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_x，R_yCan optionally be linked to form a ring.

3. The metal complex according to claim 1, wherein the metal complex has a structure represented by formula 2:

wherein, the first and the second end of the pipe are connected with each other,

m is selected from 1 or 2; when m is 1, two L_bAre the same or different; when m is 2, two L_aIs a phaseThe same or different;

X₃-X₈selected from CR, identically or differently at each occurrence_x；

Y₁-Y₄Selected from CR, identically or differently at each occurrence_yOr N;

U₁-U₄selected from CR, identically or differently at each occurrence_uOr N;

W₁-W₄selected from CR, identically or differently at each occurrence_wOr N;

U₁–U₄at least one or more selected from CR_uAnd said R is_uIs a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 ring carbon atoms, or a combination thereof; and all of said R_uThe sum of the number of carbon atoms is at least 4;

R_xat least one of which is cyano;

4. A metal complex according to any one of claims 1 to 3, wherein Z is selected from O and S;

preferably, Z is O.

5. The metal complex according to any one of claims 1 to 4, wherein R is_xOne of which is cyano and at least one further R_xSelected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof, having from 0 to 20 carbon atoms;

preferably, R_xOne of which is cyano and at least one further R_xSelected 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 heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkyl having 6 to 20 carbon atomsSubstituted or unsubstituted amino groups having 0 to 20 carbon atoms, cyano groups, hydroxyl groups, mercapto groups, and combinations thereof;

more preferably, R_xOne of which is cyano and at least one further R_xSelected 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.

6. The metal complex according to any one of claims 1 to 5, wherein R_xOne of which is cyano and at least one further R_xIs selected from the group consisting of: substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 15 carbon atoms, and combinations thereof.

7. The metal complex according to any one of claims 1 to 5, wherein R_xOne of which is cyano and at least one further R_xIs selected from the group consisting of: fluorine, deuterium, methyl, deuterated isopropyl, cyclohexyl, deuterated cyclohexyl, phenyl, deuterated phenyl, methylphenyl, deuterated methylphenyl.

8. A metal complex as claimed in any one of claims 1 to 7, wherein X₅-X₈CR of_xIn (1), at least one R_xIs cyano; preferably, X₇Is CRx, and said R_xIs cyano; or X₈Is CR_xAnd said R is_xIs cyano.

9. A metal complex according to any one of claims 1 to 8, wherein U is₁-U₄Each occurrence, identically or differently, being CR_u，R_uAt least one selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted alkyl groups having 3 to 20 ring carbon atomsOr a combination thereof, and all of said R_uThe sum of the number of carbon atoms is at least 4.

10. A metal complex according to any one of claims 1 to 8, wherein U is₁-U₄Selected from N or CR, identically or differently at each occurrence_uAnd at least one is CR_uAnd R is_uSelected from substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 ring carbon atoms, or combinations thereof, and all of said R_uThe sum of the number of carbon atoms is at least 4.

11. The metal complex of any one of claims 1 to 10, wherein R_uAt least one selected from substituted or unsubstituted alkyl groups having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 20 carbon atoms, or combinations thereof;

preferably, R_uAt least one of which is selected from the group consisting of substituted or unsubstituted substituents as follows:

wherein "-" represents the position of the bond of the substituent to carbon.

12. A metal complex according to any one of claims 1 to 11, wherein U is₂Or U₃Is CR_uAnd said R is_uSelected from substituted or unsubstituted alkyl groups having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 4 to 20 carbon atoms, or combinations thereof;

preferably, R_uIs selected fromA substituted or unsubstituted alkyl group having 4 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 6 carbon atoms, or a combination thereof.

13. A metal complex according to any one of claims 1 to 11, wherein U is₂And U₃Is CR_uAnd said R is_uEach occurrence identically or differently selected from substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 ring carbon atoms, or combinations thereof, and wherein at least one R is_uThe number of carbon atoms of the substituent is 4 or more.

14. A metal complex according to claim 13, wherein U is₁And U₄Is CR_u，R_uSelected from hydrogen, deuterium, methyl and deuterated methyl.

15. A metal complex according to any one of claims 1 to 14, wherein W₁-W₄Each occurrence, identically or differently, being CR_w，Y₁-Y₄Each occurrence, identically or differently, being CR_y，R_wAnd R_yEach 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, and combinations thereof;

preferably, R_wAnd R_yEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, and combinations thereof;

more preferably, R_wAnd R_yEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstitutedUnsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, and combinations thereof.

16. A metal complex according to any one of claims 1 to 14, wherein W is₁-W₄Each occurrence, identically or differently, being CR_wAt least one R_wIs 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; and/or Y₁-Y₄Each occurrence, identically or differently, being CR_yAt least one R_yIs 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.

17. A metal complex according to claim 1, wherein L is_aEach occurrence, the same or different, is selected from the group consisting of:

18. the metal complex of claim 1, wherein L_bEach occurrence, the same or different, is selected from the group consisting of:

19. the metal complex of claim 1 or 3, wherein the metal complex has Ir (L)_a)₂L_bStructure of (1), two L_aThe same; l is_aIs selected from L_a1-L_a206Group of (I) L_bIs selected from L_b1-L_b972Group (i) of (ii);

preferably, the metal complex is selected from the group consisting of metal complex 1 to metal complex 448, wherein metal complex 1 to metal complex 448 have Ir (L)_a)₂L_bStructure of (1), two L_aSame, L_aAnd L_bRespectively corresponding to the structures indicated in the following table:

20. an electroluminescent device, comprising:

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

a cathode electrode, which is provided with a cathode,

and an organic layer disposed between the anode and the cathode, at least one of the organic layers 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 21, wherein the light emitting layer emits green light.

23. The electroluminescent device of claim 21 wherein the light-emitting layer further comprises at least one first host compound;

preferably, the light-emitting layer further comprises at least two host compounds;

more preferably, at least one of the host compounds 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 3:

wherein the content of the first and second substances,

R_vand R_tEach occurrence, identically or differently, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amino 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 groupSulfonyl, phosphino, and combinations thereof;

adjacent substituents R_vAnd R_tCan optionally be linked to form a ring;

preferably, wherein the second host compound has a structure represented by one of formulae 3-a to 3-j:

25. the electroluminescent device of claim 23, wherein a metal complex is doped in the first host compound and the second host compound, the weight of the metal complex being 1% to 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.

26. A combination of compounds comprising the metal complex of any one of claims 1-19.