CN117534710A

CN117534710A - Organic electroluminescent material and device thereof

Info

Publication number: CN117534710A
Application number: CN202210894384.0A
Authority: CN
Inventors: 代志洪; 鹿学宇; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2022-07-28
Filing date: 2022-07-28
Publication date: 2024-02-09

Abstract

An organic electroluminescent material and a device thereof are disclosed. The organic electroluminescent material is a metal complex containing 3-deuterium substituted azadibenzothiophene ligands and can be used as a luminescent material in electroluminescent devices. These novel metal complexes can effectively improve the efficiency and lifetime of devices, providing better device performance. An electroluminescent device and a compound composition are also disclosed.

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. And more particularly, to a metal complex comprising a 3-deuterium substituted azadibenzothiophene ligand, and an organic electroluminescent device and a compound composition comprising the same.

Background

Organic electronic devices include, but are not limited to, the following: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLEDs), organic photovoltaic devices (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 electroluminescent devices.

In 1987, tang and Van Slyke of Isomandah reported a double-layered 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). Once biased into the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). Most advanced OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Because OLEDs are self-emitting solid state devices, they offer 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 fabrication on flexible substrates.

OLEDs can be divided into three different types according to their light emission mechanism. The OLED of the Tang and van Slyke invention is a fluorescent OLED. It uses only singlet light emission. The triplet states generated in the device are wasted through non-radiative decay channels. Thus, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation prevents commercialization of OLEDs. In 1997, forrest and Thompson reported phosphorescent OLEDs using triplet emission from heavy metals containing complexes as emitters. Thus, both singlet and triplet states can be harvested, achieving a 100% IQE. Because of its high efficiency, the discovery and development of phosphorescent OLEDs has contributed directly to the commercialization of Active Matrix OLEDs (AMOLEDs). Recently, adachi achieved high efficiency by 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 can generate singlet excitons by reverse intersystem crossing, resulting in high IQE.

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

Various methods of OLED fabrication exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymeric OLEDs are manufactured by solution processes such as spin coating, inkjet printing and nozzle printing. Small molecule OLEDs can also be fabricated by solution processes if the material can be dissolved or dispersed in a solvent.

The emission color of an OLED can be achieved by the structural design of the luminescent material. The OLED may include a light emitting layer or layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full color OLED displays typically employ a mixing strategy using blue fluorescent and phosphorescent yellow, or red and green. Currently, a rapid decrease in efficiency of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of metal complexes comprising 3-deuterium substituted azadibenzothiophene ligands. The compounds are useful as light emitting materials in organic electroluminescent devices. These novel metal complexes can effectively improve the efficiency and lifetime of devices, providing better device performance.

According to one embodiment of the present invention, a metal complex is disclosed comprising a metal M, and a ligand L coordinated to the metal M _a The method comprises the steps of carrying out a first treatment on the surface of the Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, and the ligand L _a Has a structure represented by formula 1 or formula 2:

wherein,

ring a and ring B are, identically or differently, selected for each occurrence from a five-membered unsaturated carbocycle, an aromatic ring having 6 to 30 carbon atoms or a heteroaromatic ring having 3 to 30 carbon atoms;

k is selected from single bond, O or S;

X ₁ selected from CR _a Or N;

Z ₁ selected from CR _z R _z ，SiR _z R _z ，GeR _z R _z ，NR _z ，PR _z O, S or Se;

R _b and R attached to ring A _a Each occurrence, identically or differently, represents mono-substituted, poly-substituted or unsubstituted;

R _a ，R _b and R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _a ，R _b ，R _z Can optionally be linked to form a ring。

According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a metal complex having a specific structure as in the above embodiment.

According to another embodiment of the present invention, there is also disclosed a compound composition comprising a metal complex, the specific structure of which is as shown in the above embodiment.

The novel metal complex containing 3-deuterium substituted azadibenzothiophene ligands disclosed by the invention can be used as a luminescent material in an electroluminescent device. These novel metal complexes can effectively improve the efficiency and lifetime of devices, providing better device performance.

Drawings

Fig. 1 is a schematic view of an organic light emitting device that may contain the metal complex and compound compositions disclosed herein.

Fig. 2 is a schematic view of another organic light emitting device that may contain the metal complex and compound compositions disclosed herein.

Detailed Description

OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically illustrates, without limitation, an organic light-emitting device 100. The drawings are not necessarily to scale, and some of the layer structures in the drawings 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, a light emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the layers described. The nature and function of the layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2, columns 6-10, the entire contents of which are incorporated herein by reference.

There are more instances of each of these layers. For example, U.S. Pat. No. 5,844,363, incorporated by reference in its entirety, discloses a flexible and transparent linerBottom-anode combination. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio ₄ m-MTDATA of TCNQ as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in 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. Examples of cathodes are disclosed in U.S. Pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, including composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the 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 sublayers. 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, such as the organic light emitting device 200 shown schematically and without limitation in fig. 2, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to prevent 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 an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film packages are 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 a variety of 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, heads-up displays, displays that are fully or partially transparent, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptops, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.

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

As used herein, "top" means furthest from the substrate and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed" on "the second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed on" an anode even though various organic layers are present between the cathode and the anode.

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

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

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

On the other hand, the E-type delayed fluorescence does not depend on the collision of two triplet states, but on the transition between the triplet states and the singlet excited state. Compounds capable of generating E-type delayed fluorescence need to have very small mono-triplet gaps in order for the conversion between the energy states. The thermal energy may activate a 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 delay component increases with increasing temperature. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet states. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrically generated excitons.

Type E delayed fluorescence features can be found in excitation complex systems or in single compounds. Without being bound by theory, it is believed that E-delayed fluorescence requires a luminescent material with a small mono-triplet energy gap (Δe _S-T ). Organic non-metal containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor Charge Transfer (CT) type emission. The spatial separation of HOMO from LUMO in these donor-acceptor compounds generally results in a small Δe _S-T . These states may include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).

Definition of terms for substituents

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

Alkyl-as used herein, includes straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.

Cycloalkyl-as used herein, includes cyclic alkyl. Cycloalkyl groups may be cycloalkyl groups having 3 to 20 ring carbon atoms, preferably 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl are preferred. In addition, cycloalkyl groups may be optionally substituted.

Heteroalkyl-as used herein, a heteroalkyl comprises an alkyl chain in which one or more carbons is replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, t-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl. In addition, heteroalkyl groups may be optionally substituted.

Alkenyl-as used herein, covers straight chain, branched chain, and cyclic alkylene groups. Alkenyl groups may be alkenyl groups containing 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups include ethenyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2-diphenylvinyl, 1-methallyl, 1-dimethylallyl, 2-methallyl, 1-phenylallyl, 2-phenylallyl, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, straight chain alkynyl is 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 groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 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 the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed 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 '-methylbiphenyl-4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl. In addition, aryl groups may be optionally substituted.

Heterocyclyl or heterocycle-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 nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms including at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxacycloheptatrienyl, thietaneyl, azepanyl and tetrahydrosilol. 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 nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. 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, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furodipyridine, benzothiophene, thienodipyridine, benzoselenophene, selenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-boron, 1, 3-aza-boron, 1-aza-boron-4-aza, boron-doped compounds, and the like. In addition, heteroaryl groups 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 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 alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy group 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 aryloxy groups include phenoxy and biphenoxy. In addition, the aryloxy group may be optionally substituted.

Aralkyl-as used herein, encompasses aryl-substituted alkyl. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthyl-ethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthyl-ethyl, 2- β -naphthyl-ethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, cyano, o-cyanobenzyl, o-chlorobenzyl, 1-chlorophenyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl. In addition, aralkyl groups may be optionally substituted.

Alkyl-as used herein, alkyl-substituted silicon groups are contemplated. The silyl group may be a silyl group having 3 to 20 carbon atoms, preferably a silyl group having 3 to 10 carbon atoms. Examples of the alkyl silicon group include trimethyl silicon group, triethyl silicon group, methyldiethyl silicon group, ethyldimethyl silicon group, tripropyl silicon group, tributyl silicon group, triisopropyl silicon group, methyldiisopropyl silicon group, dimethylisopropyl silicon group, tri-t-butyl silicon group, triisobutyl silicon group, dimethyl-t-butyl silicon group, and methyldi-t-butyl silicon group. In addition, the alkyl silicon group may be optionally substituted.

Arylsilane-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 arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenyl silyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl. In addition, arylsilane groups may be optionally substituted.

Alkyl germanium group-as used herein, alkyl substituted germanium groups are contemplated. The alkylgermanium group may be an alkylgermanium group having 3 to 20 carbon atoms, preferably an alkylgermanium group having 3 to 10 carbon atoms. Examples of alkyl germanium groups include trimethyl germanium group, triethyl germanium group, methyl diethyl germanium group, ethyl dimethyl germanium group, tripropyl germanium group, tributyl germanium group, triisopropyl germanium group, methyl diisopropyl germanium group, dimethyl isopropyl germanium group, tri-t-butyl germanium group, triisobutyl germanium group, dimethyl-t-butyl germanium group, methyl-di-t-butyl germanium group. In addition, alkyl germanium groups may be optionally substituted.

Arylgermanium group-as used herein, encompasses at least one aryl or heteroaryl substituted germanium group. The arylgermanium group may be an arylgermanium group having 6-30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of aryl germanium groups include triphenylgermanium group, phenylbiphenyl germanium group, diphenylbiphenyl germanium group, phenyldiethyl germanium group, diphenylethyl germanium group, phenyldimethyl germanium group, diphenylmethyl germanium group, phenyldiisopropylgermanium group, diphenylisopropylgermanium group, diphenylbutylgermanium group, diphenylisobutylglycol group, and diphenyltert-butylgermanium group. In addition, the arylgermanium group may be optionally substituted.

The term "aza" in azadibenzofurans, azadibenzothiophenes and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives will be readily apparent to those of ordinary skill in the art, and all such analogs are intended to be included in the terms described herein.

In the present disclosure, when any one of the terms from 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 alkylgermanium, substituted arylgermanium, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, which may be substituted with one or more groups selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted cycloalkyl having 1 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, unsubstituted arylgermanium groups having 6 to 20 carbon atoms, 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, phosphine groups, and combinations thereof.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to 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 equivalent.

In the compounds mentioned in this disclosure, the hydrogen atoms 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 of their enhanced efficiency and stability of the device.

In the compounds mentioned in this disclosure, polysubstituted means inclusive of disubstituted up to the maximum available substitution range. When a substituent in a compound mentioned in this disclosure means multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), it means that the substituent may be present at a plurality of available substitution positions on its linking structure, and the substituent present at each of the plurality of available substitution positions may be of the same structure or of different structures.

In the compounds mentioned in this disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring. In the compounds mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, both in the case where adjacent substituents can be linked to form a ring and in the case where adjacent substituents are not linked to form a ring. Where adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic (including spiro, bridged, fused, etc.), as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. 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 further distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and 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 be taken 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:

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

furthermore, the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

wherein,

K is selected from single bond, O or S;

X ₁ selected from CR _a Or N;

Adjacent substituents R _a ，R _b ，R _z Can optionally be linked to form a ring.

Herein, adjacent substituents R _a ，R _b ，R _z Can optionally be linked to form a ring, intended to mean any adjacent group of substituents therein, e.g. adjacent substituents R _a Adjacent substituents R _b Adjacent substituents R _z And adjacent substituents R _a And R is _z Any one or more of these adjacent groups of substituents can be linked to form a ring. Obviously, none of these adjacent groups of substituents may be linked to form a ring.

According to one embodiment of the present invention, wherein in formula 1 or formula 2, at least one or two or three R are present _a And said R _a Deuterium.

According to one embodiment of the present invention, wherein in formula 1 or formula 2, at least one or two or three R are present _b And said R _b Deuterium.

According to one embodiment of the invention, wherein the ligand L _a At least two or three or four deuterium are present.

According to one embodiment of the present invention, wherein, in formula 1 or formula 2, X ₁ Selected from CR _a And said R _a Is deuterium.

According to one embodiment of the invention, wherein in formula 1 or formula 2, ring a and ring B are, identically or differently, selected for each occurrence from aromatic rings having 6 to 18 carbon atoms or heteroaromatic rings having 3 to 18 carbon atoms.

According to one embodiment of the invention, wherein in formula 1 or formula 2, ring a and ring B are, identically or differently, selected for each occurrence from a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, a selenophene ring, a benzofuran ring, a benzothiophene ring, a benzoselenophene ring, an azabenzofuran ring, an azabenzothiophene ring, a dibenzofuran ring or a dibenzothiophene ring.

According to one embodiment of the invention, wherein in formula 1 or formula 2, ring a and ring B are, identically or differently, selected for each occurrence from a benzene ring, a pyridine ring, a naphthalene ring, a furan ring, a thiophene ring, a dibenzofuran ring or a dibenzothiophene ring.

According to one embodiment of the invention, wherein in formula 1 or formula 2, the K is selected from single bonds.

According to one embodiment of the invention, wherein the L _a Has a structure represented by any one of formulas 3 to 15:

wherein,

X ₁ -X ₅ is selected identically or differently on each occurrence from N or CR _a ；

Z ₁ And Z ₂ Independently at each occurrence selected from CR _z R _z ，SiR _z R _z ，GeR _z R _z ，NR _z ，PR _z O, S or Se;

B ₁ -B ₆ is selected identically or differently on each occurrence from N or CR _b ；

R _a 、R _b And R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano Isocyano, hydroxy, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, X ₁ -X ₅ At least one of which is selected from N.

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, X ₁ Selected from N.

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, B ₁ -B ₆ Is selected from CR, identically or differently at each occurrence _b The R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _b Can optionally be linked to form a ring.

Herein, adjacent substituents R _b Can optionally beIs linked to form a ring, intended to mean any adjacent substituent R therein _b Can be joined to form a ring. Obviously, any adjacent substituents R _b Or none may be joined to form a ring.

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, B ₁ -B ₆ Is selected from CR, identically or differently at each occurrence _b The method comprises the steps of carrying out a first treatment on the surface of the The R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 arylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted arylgermyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, cyano, mercapto, and combinations thereof;

Adjacent substituents R _b Can optionally be linked to form a ring.

According to one embodiment of the present invention, wherein, in the formulas 3 to 5, B ₂ ，B ₄ And B ₅ At least one of which is selected, identically or differently, at each occurrence, from CR _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 8 to 14, B ₂ And/or B ₄ Is selected from CR, identically or differently at each occurrence _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 6, 7 and 15, B ₁ And/or B ₂ Is selected from CR, identically or differently at each occurrence _b The method comprises the steps of carrying out a first treatment on the surface of the And said R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkanes having 1-20 carbon atomsA group, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heterocyclyl 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 alkylgermanium group having 6 to 20 carbon atoms, a substituted or unsubstituted arylgermanium group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a cyano group, a hydroxy group, a mercapto group, and combinations thereof;

Adjacent substituents R _b Can optionally be linked to form a ring.

According to one embodiment of the present invention, wherein, in the formulas 3 to 7 and 15, B ₂ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 8 to 14, B ₂ And B ₄ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the And said R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof.

According to one embodiment of the present invention, wherein, in the formulas 3 to 7 and 15, B ₂ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 8 to 14, B ₂ And B ₄ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the The R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, methyl, t-butyl, neopentyl, cyclopentyl, cyclohexyl, trifluoromethyl, trimethylsilyl, phenyl, methoxy, N-dimethylamino, and combinations thereof.

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, X ₁ -X ₅ Is selected from CR, identically or differently at each occurrence _a The R is _a And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _a Can optionally be linked to form a ring.

Herein, adjacent substituents R _a Can optionally be linked to form a ring, intended to mean any adjacent substituent R therein _a Can be joined to form a ring. Obviously, any adjacent substituents R _a Or none may be joined to form a ring.

According to one embodiment of the invention, wherein, in the followingIn the formulas 3 to 11 and 15, X ₃ And/or X ₅ Is selected from CR, identically or differently at each occurrence _a In the formulae 12 to 14, X ₃ And/or X ₂ Is selected from CR, identically or differently at each occurrence _a And said R _a And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; substituted or unsubstituted alkyl germanium groups having 3 to 20 carbon atoms, hydroxy groups, mercapto groups, and combinations thereof.

According to one embodiment of the present invention, wherein, in the formulas 3 to 11 and 15, X ₃ And/or X ₅ Is selected from CR, identically or differently at each occurrence _a In the formulae 12 to 14, X ₃ And/or X ₂ Is selected from CR, identically or differently at each occurrence _a And said R _a And is selected identically or differently on each occurrence from the group consisting of: deuterium, fluoro, cyano, trifluoromethyl, methyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydropyranyl, norbornyl, adamantyl, trimethylsilyl, trimethylgermanium, phenyl, triazinyl, methoxy, methylthio, dimethylamino, N-diphenylamino, and combinations thereof.

According to one embodiment of the present invention, wherein, in the formulas 3 to 15, Z ₁ And Z ₂ Independently each occurrence is selected from O, S or Se.

According to one embodiment of the invention, wherein the ligand L _a Has a structure represented by formula 3-1:

wherein,

Z ₁ selected from O, S or Se;

Q ₁ to Q ₁₁ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents Q ₁ To Q ₁₁ Can optionally be linked to form a ring.

Herein, adjacent substituents Q ₁ To Q ₁₁ Can optionally be linked to form a ring, intended to mean groups of adjacent substituents therein, e.g. adjacent substituents Q ₁ And Q ₂ Adjacent substituents Q ₂ And Q ₃ Adjacent substituents Q ₃ And Q ₄ Adjacent substituents Q ₄ And Q ₅ Adjacent substituents Q ₆ And Q ₇ Adjacent substituents Q ₇ And Q ₈ Adjacent substituents Q ₈ And Q ₉ Adjacent substituents Q ₉ And Q ₁₀ And adjacent substitutionsBase Q ₁₀ And Q ₁₁ Any one or more of these adjacent groups of substituents can be linked to form a ring. Obviously, none of these adjacent groups of substituents may be linked to form a ring.

According to one embodiment of the invention, wherein Q ₃ 、Q ₅ 、Q ₇ 、Q ₉ And Q ₁₀ Is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein Q ₅ And/or Q ₇ And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring 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 germanium groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the present invention, wherein in formula 3-1, Q ₁ -Q ₄ Deuterium, Q ₅ Selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring 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 germanium groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the present invention, wherein in formula 3-1, Q ₆ ，Q ₈ -Q ₁₁ Deuterium, Q ₇ Selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring 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 germanium groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein the ligand L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 A group of; the L is _a1 To L _a1588 See claim 9 for a specific structure.

According to one embodiment of the invention, wherein the metal complex has M (L _a ) _m (L _b ) _n (L _c ) _q Is of the general formula (I); the metal M is selected from Ir, rh, re, os, pt, au or Cu; l (L) _a 、L _b And L _c A first ligand, a second ligand and a third ligand coordinated to the metal M, respectively; m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q is equal to the oxidation state of the metal M; when m is equal to 2 or 3, a plurality of L _a Are the same or different; when n is equal to 2, 2L _b Are the same or different; when q is equal to 2, 2L _c Are the same or different;

L _a 、L _b and L _c Can optionally be linked to form a multidentate ligand;

L _b and L _c And is selected identically or differently on each occurrence from the group consisting of:

wherein,

R ₁ 、R ₂ and R is ₃ Each occurrence, identically or differently, represents mono-substituted, poly-substituted or unsubstituted;

X _b and is selected identically or differently on each occurrence from the group consisting of: o, S, se, NR _N1 And CR (CR) _C1 R _C2 ；

X _c And X _d And is selected identically or differently on each occurrence from the group consisting of: o, S, se and NR _N2 ；

R ₁ 、R ₂ 、R ₃ 、R _N1 、R _N2 、R _C1 And R is _C2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R ₁ ，R ₂ ，R ₃ ，R _N1 ，R _N2 ，R _C1 And R is _C2 Can optionally be linked to form a ring.

Herein, adjacent substitutionsRadical R ₁ ，R ₂ ，R ₃ ，R _N1 ，R _N2 ，R _C1 And R is _C2 Can optionally be linked to form a ring, intended to mean groups of substituents adjacent thereto, e.g. two substituents R ₁ Between two substituents R ₂ Between two substituents R ₃ Between, substituent R ₁ And R is ₂ Between, substituent R ₁ And R is ₃ Between, substituent R ₂ And R is ₃ Between, substituent R ₁ And R is _N1 Between, substituent R ₂ And R is _N1 Between, substituent R ₁ And R is _C1 Between, substituent R ₁ And R is _C2 Between, substituent R ₂ And R is _C1 Between, substituent R ₂ And R is _C2 Between, substituent R ₁ And R is _N2 Between, substituent R ₂ And R is _N2 Between, and R _C1 And R is _C2 In between, any one or more of these substituent groups may be linked to form a ring. For example, the number of the cells to be processed,r is an adjacent substituent ₁ ，R ₂ Can optionally be linked to form a ring, which can form a ring comprising, but not limited to, one or more of the following structures:

Wherein W is selected from O, S, se, NR ' or CR ' R '; wherein said R', R ₁ ’，R ₂ ' definition and R ₁ The same applies. Obviously, these substituents may not all be linked to form a ring.

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

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

According to one embodiment of the invention, wherein，L _b Each occurrence is identically or differently selected from the following structures:

R _t to R _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _t ，R _u ，R _v ，R _w ，R _x ，R _y ，R _z Can optionally be linked to form a ring.

Herein, "adjacent substituent R _t ，R _u ，R _v ，R _w ，R _x ，R _y ，R _z Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g., substituents R _u And R is _v Between, substituent R _u And R is _w Between, substituent R _v And R is _w Between, substituent R _x And R is _y Between, substituent R _x And R is _z Between, substituent R _y And R is _z Between, substituent R _u And R is _t Between, substituent R _v And R is _t Between, substituent R _w And R is _t Between, substituent R _x And R is _t Between, substituent R _y And R is _t Between and substituent R _z And R is _t In between, any one or more of these substituent groups may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.

According to one embodiment of the invention, wherein R _x ，R _y And R is _z At least one or two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, or combinations thereof; and/or R _u ，R _v And R is _w At least one or two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein R _x ，R _y And R is _z At least two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof; and/or R _u ，R _v And R is _w At least two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein L _b Selected from the group consisting of L _b1 To L _b322 A group consisting of said L _b1 To L _b322 See claim 12 for a specific structure of (c).

According to one embodiment of the invention, wherein L _c Selected from the group consisting of L _c1 To L _c231 A group consisting of said L _c1 To L _c231 See claim 12 for a specific structure of (c).

According to one embodiment of the invention, wherein the metal complex is an Ir complex and has a structure as shown in Ir (L _a )(L _b )(L _c )、Ir(L _a ) ₂ (L _b )、Ir(L _a ) ₂ (L _c ) And Ir (L) _a )(L _c ) ₂ Any of the structures shown; when the metal complex has Ir (L) _a )(L _b )(L _c ) In the structure of (2), the L _a Selected from the group consisting of L _a1 To L _a1588 Any one of the group consisting of the L _b Selected from the group consisting of L _b1 To L _b322 Any one of the group consisting of the L _c Selected from the group consisting of L _c1 To L _c231 Any one of the group consisting of; when the metal complex has Ir (L) _a ) ₂ (L _b ) In the structure of (2), the L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 Either or both of the group consisting of, L _b Selected from the group consisting of L _b1 To L _b322 Any one of the group consisting of; when the metal complex has Ir (L) _a ) ₂ (L _c ) In the structure of (2), the L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 Either or both of the group consisting of, L _c Selected from the group consisting of L _c1 To L _c231 Any one of the group consisting of; when the metal complex has Ir (L) _a )(L _c ) ₂ In the structure of (2), the L _a Selected from the group consisting of L _a1 To L _a1588 Any one of the group consisting of the L _c Is selected identically or differently on each occurrence from the group consisting of L _c1 To L _c231 Either or both of the groups.

According to one embodiment of the invention, wherein the metal complex is selected from the group consisting of compound 1 to compound 422; the specific structure of compounds 1 to 422 is seen in claim 13.

According to one embodiment of the present invention, an electroluminescent device is disclosed, comprising:

an anode is provided with a cathode,

a cathode electrode, which is arranged on the surface of the cathode,

And an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex of any of the previous embodiments.

According to one embodiment of the invention, wherein the organic layer is a light emitting layer and the metal complex is a light emitting material.

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

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

According to one embodiment of the present invention, the at least one host material may be a conventional host material of the prior art, for example, may typically, but not limited to, include the following host materials:

according to one embodiment of the present invention, a compound composition is disclosed comprising the metal complex of any of the previous embodiments.

Combined with other materials

The materials described herein for specific 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 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

Materials described herein as useful for specific layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein may be used in combination with a variety of light-emitting dopants, hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

In the examples of material synthesis, all reactions were carried out under nitrogen protection, unless otherwise indicated. All reaction solvents were anhydrous and used as received from commercial sources. The synthetic products were subjected to structural confirmation and characterization testing using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai's optical technique fluorescence spectrophotometer, wuhan Koste's electrochemical workstation, anhui Bei Yi g 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, a vapor deposition machine manufactured by Angstrom Engineering, an optical test system manufactured by Frieda, st. John's, an ellipsometer manufactured by Beijing, etc.), in a manner well known to those skilled in the art. Since those skilled in the art are aware of the relevant contents of the device usage and the testing method, and can obtain the intrinsic data of the sample certainly and uninfluenced, the relevant contents are not further described in this patent.

Material synthesis examples:

the preparation method of the compound of the present invention is not limited, and is typically, but not limited to, exemplified by the following compounds, the synthetic routes and preparation methods thereof are as follows:

synthesis example 1: synthesis of Compound 63

Step 1: synthesis of intermediate 2

N, N-dimethylethanolamine (2-dimethylethanolamine, 3.266g,36.64 mmol) in N-hexane (76 mL) was cooled at 0℃under nitrogen atmosphere, butyllithium (25.65 mL,64.12 mmol) was added dropwise thereto and reacted for 30 minutes, then Compound 1 (9.7 g,22.9 mmol) was dissolved in N-hexane (38 mL), the reaction was added, and after 1 hour of reaction, heavy water (2.75 mL,137.4 mmol) was added thereto, and the temperature was raised naturally and the reaction was continued overnight. The reaction solution was concentrated and separated by column chromatography to obtain intermediate 2 (5.6 g).

Step 2: synthesis of Iridium dimer 3

Intermediate 2 (510 mg,1.2 mmol) was mixed with iridium chloride trihydrate (141 mg,0.4 mmol) in a mixed solution of 2-ethoxyethanol and water (6 mL/2 mL), reacted at 130 ℃ for 24 hours under nitrogen protection, cooled to room temperature, and filtered to give a crude iridium dimer 3 product which was used directly in the next reaction without further purification.

Step 3: synthesis of Compound 63

Iridium dimer 3 obtained in step 2 was reacted with 3, 7-diethyl-3, 7-dimethyl-nonane-4, 6-dione (144 mg,0.6 mmol), K ₂ CO ₃ (277 mg,2 mmol) and ethoxyethanol (6 mL) were mixed and reacted overnight at 55℃under nitrogen. After completion of the reaction by TLC, the reaction was cooled to room temperature. The filter cake was filtered through celite, washed with a suitable amount of EtOH, the crude product was dissolved with DCM, etOH was added thereto, concentrated to a solid precipitate, filtered, and the filter cake was further washed with a suitable amount of EtOH, and dried to give compound 63 (190 mg), the product was confirmed to be the target product, molecular weight 1278.6.

Synthesis example 2: synthesis of Compound 317

Step 1: synthesis of Iridium dimer 5

Intermediate 4 (340 mg,0.8 mmol) was mixed with iridium chloride trihydrate (100 mg,0.29 mmol) in a mixed solution of 2-ethoxyethanol and water (6 mL/2 mL), reacted at 130 ℃ for 24 hours under nitrogen protection, cooled to room temperature, and filtered to give crude iridium dimer 5 which was used directly in the next reaction without further purification.

Step 2: synthesis of Compound 317

Iridium dimer 5 obtained in step 1 was reacted with 3, 7-diethyl-3, 7-dimethyl-nonane-4, 6-dione (108 mg,0.45 mmol) and K ₂ CO ₃ (207 mg,1.5 mmol) in ethoxyethanol (6 mL), nitrogenUnder the protection of gas, the reaction is carried out at 55 ℃. After TLC monitored the reaction was complete, the reaction solution was filtered through celite, the filter cake was washed with a suitable amount of EtOH, the crude product was dissolved with DCM, etOH (about 10 mL) was added thereto, concentrated to solid precipitation at normal temperature, it was filtered, washed with a suitable amount of EtOH, and dried to give compound 317 (120 mg), the product was confirmed to be the target product, molecular weight 1280.6.

Synthesis example 3: synthesis of Compound 331

Step 1: synthesis of Iridium dimer 7

Intermediate 6 (570 mg,1.35 mmol) was mixed with iridium chloride trihydrate (159 mg,0.45 mmol) in 2-ethoxyethanol and aqueous solution (12 mL/4 mL), reacted at 130℃for 24 hours under nitrogen protection, cooled to room temperature and filtered to give crude iridium dimer 7 which was used directly in the next reaction.

Step 2: synthesis of Compound 331

Iridium dimer 7 obtained in step 1 was reacted with 3, 7-diethyl-3, 7-dimethyl-nonane-4, 6-dione (163 mg,0.68 mmol) and K ₂ CO ₃ (311 mg,2.25 mmol) was mixed in ethoxyethanol (12 mL) and reacted overnight at 55℃under nitrogen. After completion of the reaction, TLC monitored it was cooled to room temperature. The filter cake was filtered through celite, washed with a suitable amount of EtOH, the crude product was dissolved with DCM, etOH (about 10 mL) was added thereto, concentrated at normal temperature until solid precipitated, which was filtered, washed with a suitable amount of EtOH, and dried to give compound 331 (290 mg), the product was identified as the target product, molecular weight 1296.7.

Those skilled in the art will recognize that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other compound structures of the present invention.

Device embodiment

Device example 1

First, a glass substrate having a 120nm thick Indium Tin Oxide (ITO) anode was cleaned, and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was baked in a glove box to remove moisture. The substrate is then mounted on a substrate support and loaded into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 ^-8 In the case of the support, vapor deposition was sequentially performed on the ITO anode by thermal vacuum vapor deposition at a rate of 0.2 to 2 Angstrom/sec. Compound HI was doped in compound HT to serve as a hole injection layer (HIL, weight ratio 3:97), thicknessCompound HT is used as Hole Transport Layer (HTL), thickness +.>Compound EB is used as Electron Blocking Layer (EBL), thickness +.>Then, the compound 63 of the present invention was doped in the host compound RH to serve as a light emitting layer (EML, weight ratio 2:98), thickness +.>Compound HB is used as Hole Blocking Layer (HBL), thickness +.>On the HBL, the compound ET and 8-hydroxyquinoline-lithium (Liq) are co-deposited as electron transport layers (ETL, weight ratio 40:60), thickness>Finally, liq 1nm thick was deposited as an electron injection layer, and Al 120nm was deposited as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device.

Device example 2

Device example 2 was prepared in the same manner as device example 1 except that inventive compound 317 was used in place of inventive compound 63 in the light-emitting layer (EML).

Device example 3

Device example 3 was prepared in the same manner as device example 1 except that inventive compound 331 was used in place of inventive compound 63 in the light-emitting layer (EML).

Device comparative example 1

Device comparative example 1 was prepared in the same manner as device example 1 except that compound RD-a was used in place of compound 63 of the present invention in the light-emitting layer (EML).

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

Table 1 partial device structures of device examples and comparative examples

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

IVL and lifetime characteristics of the devices were measured. Table 2 shows the results at 15mA/cm ² Color Coordinates (CIE), maximum emission wavelength (lambda) _max ) External Quantum Efficiency (EQE) data; at 80mA/cm ² Life time measured at current density (LT 97) data.

Table 2 device data

Device numbering	λ _max (nm)	CIE(x,y)	EQE(％)	LT97(h)
					Example 1	624	(0.687,0.313)	25.95	187
Example 2	625	(0.686,0.313)	26.16	195
					Example 3	624	(0.686,0.314)	26.23	291
Comparative example 1	624	(0.687,0.313)	25.42	141

Discussion:

as can be seen from the data shown in table 2, the color coordinates and the maximum emission wavelength of example 1, example 2 and example 3 are substantially equivalent to those of comparative example 1; however, the device efficiency and lifetime of examples 1-3 are both significantly further improved on the basis of the extremely high level already achieved in comparative example 1, which is very difficult to achieve, and in particular the lifetime is significantly improved by a very significant amount, which is even more difficult to achieve. Specifically, the external quantum efficiency of example 1 is improved by 2.0% compared with comparative example 1, and the lifetime of example 1 is greatly improved by 32.6% compared with comparative example 1; the external quantum efficiency of example 2 is improved by 2.9% compared with comparative example 1, and the lifetime is greatly improved by 38.3% compared with comparative example 1; the external quantum efficiency of example 3 was improved by 3.2% as compared with comparative example 1, and the lifetime was significantly improved by more than one time as compared with comparative example 1, which is quite remarkable. The comparison of the data shows that the metal complex of the invention can bring about both life and efficiency improvement due to the introduction of deuteration into the azadibenzothiophene ligand, and especially the life improvement proves the uniqueness and importance of the metal complex of the invention.

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

Claims

1. A metal complex comprising a metal M, and a ligand L coordinated to the metal M _a The method comprises the steps of carrying out a first treatment on the surface of the Wherein the metal M is selected from metals having a relative atomic mass of greater than 40, and the ligand L _a Has a structure represented by formula 1 or formula 2:

wherein,

k is selected from single bond, O or S;

X ₁ selected from CR _a Or N;

R _a ，R _b and R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted aryl having 0 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, Isocyano, hydroxy, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

2. The metal complex of claim 1, wherein in formula 1 or formula 2, ring a and ring B are, identically or differently, selected for each occurrence from an aromatic ring having 6 to 18 carbon atoms or a heteroaromatic ring having 3 to 18 carbon atoms;

preferably, ring a and ring B are, identically or differently, selected for each occurrence from a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, a selenophene ring, a benzofuran ring, a benzothiophene ring, a benzoselenophene ring, an azabenzofuran ring, an azabenzothiophene ring, a dibenzofuran ring or a dibenzothiophene ring;

more preferably, ring a and ring B are, identically or differently, selected for each occurrence from a benzene ring, a pyridine ring, a naphthalene ring, a furan ring, a thiophene ring, a dibenzofuran ring or a dibenzothiophene ring.

3. The metal complex of claim 1, wherein K is selected from single bonds;

preferably, the L _a Has a structure represented by any one of formulas 3 to 15:

wherein,

R _a 、R _b And R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

4. The metal complex as claimed in claim 3, wherein X is represented by the formulae 3 to 15 ₁ -X ₅ At least one of which is selected from N; preferably X ₁ Selected from N.

5. The metal complex according to claim 3, wherein in the formulae 3 to 5, B ₂ ，B ₄ And B ₅ At least one of which is selected, identically or differently, at each occurrence, from CR _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 8 to 14, B ₂ And/or B ₄ Is selected from CR, identically or differently at each occurrence _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 6, 7 and 15, B ₁ And/or B ₂ Each time it occurs, the sameOr is variously selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the And said R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 arylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted arylgermyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, cyano, mercapto, and combinations thereof;

Adjacent substituents R _b Can optionally be linked to form a ring;

preferably, in the formulas 3 to 7 and 15, B ₂ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the In the formulas 8 to 14, B ₂ And B ₄ Selected from CR _b The method comprises the steps of carrying out a first treatment on the surface of the And said R is _b And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof;

more preferably, the R _b Identical or at each occurrenceDifferently selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, t-butyl, neopentyl, cyclopentyl, cyclohexyl, trifluoromethyl, trimethylsilyl, phenyl, methoxy, N-dimethylamino, and combinations thereof.

6. The metal complex as claimed in claim 3, wherein, in the formulae 3 to 15, X ₁ -X ₅ Is selected from CR, identically or differently at each occurrence _a The R is _a And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _a Can optionally be linked to form a ring;

preferably, in the formulas 3 to 11 and 15, X ₃ And/or X ₅ Is selected from CR, identically or differently at each occurrence _a In the formulae 12 to 14, X ₃ And/or X ₂ Is selected from CR, identically or differently at each occurrence _a And said R _a Identical or different at each occurrenceAnd is selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; substituted or unsubstituted alkyl germanium groups having 3 to 20 carbon atoms, hydroxyl groups, mercapto groups, and combinations thereof;

more preferably, the R _a And is selected identically or differently on each occurrence from the group consisting of: deuterium, fluoro, cyano, trifluoromethyl, methyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydropyranyl, norbornyl, adamantyl, trimethylsilyl, trimethylgermanium, phenyl, triazinyl, methoxy, methylthio, dimethylamino, N-diphenylamino, and combinations thereof.

7. The metal complex as claimed in claim 3, wherein, in the formulae 3 to 15, Z ₁ And Z ₂ Independently each occurrence is selected from O, S or Se.

8. The metal complex according to claim 1, wherein the ligand L _a Has a structure represented by formula 3-1:

wherein,

Z ₁ selected from O, S or Se;

Q ₁ to Q ₁₁ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atomsA heteroatom, a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkylgermanium group having 6 to 20 carbon atoms, a substituted or unsubstituted arylgermanium 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 mercapto group, a sulfonyl group, a phosphono group, and combinations thereof;

Adjacent substituents Q ₁ To Q ₁₁ Can optionally be linked to form a ring;

preferably Q ₃ 、Q ₅ 、Q ₇ 、Q ₉ And Q ₁₀ Is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, and combinations thereof;

more preferably, Q ₅ And/or Q ₇ And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted hetero ring having 3 to 30 carbon atomsAryl, substituted or unsubstituted alkyl silicon group with 3-20 carbon atoms; substituted or unsubstituted alkyl germanium groups having 3 to 20 carbon atoms, and combinations thereof.

9. The metal complex according to claim 1, wherein the ligand L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 A group of;

wherein the L is _a1 To L _a1408 Has a structure represented by formula 3-1:

wherein Z is ₁ ，Q ₁ To Q ₁₁ Respectively correspond to structures selected from the list of:

at said L _a1 To L _a1408 In the structure of (1), T ₁ To T ₃₂ The structure of (2) is as follows: t (T) ₁ ＝H；T ₂ ＝D；T ₃ ＝F；T ₄ ＝Me；T ₅ ＝CF ₃ ； T ₂₉ ＝OMe；T ₃₀ ＝SMe； T ₃₂ ＝CN。

10. The metal complex of any one of claims 1-9, wherein the metal complex has M (L _a ) _m (L _b ) _n (L _c ) _q Is of the general formula (I); the metal M is selected from Ir, rh, re, os, pt, au or Cu; l (L) _a 、L _b And L _c A first ligand, a second ligand and a third ligand coordinated to the metal M, respectively; m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, and m+n+q is equal to the oxidation state of the metal M; when m is equal to 2 or 3, a plurality of L _a Are the same or different; when n is equal to 2, 2L _b Are the same or different; when q is equal to 2, 2L _c Are the same or different;

L _a 、L _b and L _c Can optionally be linked to form a multidentate ligand;

wherein,

Adjacent substituents R ₁ ，R ₂ ，R ₃ ，R _N1 ，R _N2 ，R _C1 And R is _C2 Can optionally be linked to form a ring;

preferably, the metal M is selected from Ir, pt or Os;

more preferably, the metal M is Ir.

11. The metal complex of claim 10, wherein L _b Each occurrence is identically or differently selected from the following structures:

wherein R is _t To R _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 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 alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R _t ，R _u ，R _v ，R _w ，R _x ，R _y ，R _z Can optionally be linked to form a ring;

preferably, wherein R _x ，R _y And R is _z At least one or two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, or combinations thereof; and/or R _u ，R _v And R is _w At least one or both of which are identically or differently selected from the group consisting of substituted orUnsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or a combination thereof;

more preferably, wherein R _x ，R _y And R is _z At least two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof; and/or R _u ，R _v And R is _w At least two of which are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof.

12. The metal complex of claim 10, wherein L _b And is selected identically or differently on each occurrence from the group consisting of:

wherein L is _c And is selected identically or differently on each occurrence from the group consisting of:

13. the metal complex according to claim 1, wherein the metal complex is an Ir complex and has a structure as shown in Ir (L _a )(L _b )(L _c )、Ir(L _a ) ₂ (L _b )、Ir(L _a ) ₂ (L _c ) And Ir (L) _a )(L _c ) ₂ Any of the structures shown; when the metal complex has Ir (L) _a )(L _b )(L _c ) In the structure of (2), the L _a Selected from the group consisting of L _a1 To L _a1588 Any one of the group consisting of the L _b Selected from the group consisting of L _b1 To L _b322 Any one of the group consisting of the L _c Selected from the group consisting of L _c1 To L _c231 Any one of the group consisting of; when the metal complex has Ir (L) _a ) ₂ (L _b ) In the structure of (2), the L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 Either or both of the group consisting of, L _b Selected from the group consisting of L _b1 To L _b322 Any one of the group consisting of; when the metal complex has Ir (L) _a ) ₂ (L _c ) In the structure of (2), the L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a1588 Either or both of the group consisting of, L _c Selected from the group consisting of L _c1 To L _c231 Any one of the group consisting of; when the metal complex has Ir (L) _a )(L _c ) ₂ In the structure of (2), the L _a Selected from the group consisting of L _a1 To L _a1588 Any one of the group consisting of the L _c Is selected identically or differently on each occurrence from the group consisting of L _c1 To L _c231 Either or both of the group consisting of;

preferably, the metal complex is selected from the group consisting of compounds 1 to 422, the compounds 1 to 422 having Ir (L _a )(L _b ) ₂ Wherein two L _b Identical, L _a And L _b Respectively correspond to structures selected from the list of:

14. an electroluminescent device, comprising:

an anode is provided with a cathode,

a cathode electrode, which is arranged on the surface of the cathode,

an organic layer disposed between the anode and cathode, wherein the organic layer comprises the metal complex of any one of claims 1 to 13.

15. The device of claim 14, wherein the organic layer is a light emitting layer and the metal complex is a light emitting material.

16. The device of claim 14, wherein the electroluminescent device emits red or white light.

17. The device of claim 15, wherein the light emitting layer further comprises at least one host material; preferably, the at least one host material comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

18. A compound composition comprising the metal complex of any one of claims 1 to 13.