CN117209542A

CN117209542A - Organic electroluminescent material and device thereof

Info

Publication number: CN117209542A
Application number: CN202210598714.1A
Authority: CN
Inventors: 张晗; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2022-05-31
Filing date: 2022-05-31
Publication date: 2023-12-12

Abstract

An organic electroluminescent material and a device thereof are disclosed. The organic electroluminescent material is a material comprising L having the structure of formula 1 _a Metal complexes of ligands which are useful as luminescent materials in electroluminescent devices. The metal complex can be applied to electroluminescent devices to obtain deep red emitted light while maintaining excellent device performance, such as narrow peak width, low voltage, long service life and the like. An electroluminescent device comprising the metal complex and a compound combination comprising the metal complex 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 electroluminescent devices. And more particularly, to an L having the structure of formula 1 _a Metal complexes of ligands, electroluminescent devices and compound compositions 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 in flexible substrate fabrication.

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.

With the widespread use of OLEDs, new and higher demands are being placed on deep red light emitting materials as well as on long wavelength light emitting materials in the near infrared. For example, in the medical and cosmetic field, the low-energy deep red light radiation of 660nm-670nm can reach deep skin more effectively, and has the effects of relieving seborrheic dermatitis, stimulating hair follicle growth, inhibiting optic nerve aging and the like; in the agricultural field, the deep red light with the wavelength of 660nm can be absorbed by chlorophyll a to promote photosynthesis, and the whole process from germination to vegetative growth to flowering of plants can be controlled by the deep red light; in the field of vehicle lighting, recently developed OLED taillights use materials that are also deep red; other near infrared luminescent materials have important functions in the special fields of detection, sensing, optical communication, night vision and the like; therefore, the development of the luminescent material with deep red or even near infrared and the electroluminescent device thereof have important practical significance.

CN112851714a discloses iridium metal complexes having the following structure and iridium metal complexes containing the sameOrganic light emitting device of object:and discloses the compounds in specific structures:What is claimed in this application are metal complexes of ligands having a polycyclic structure bridged at specific positions of the quinoline by heteroatoms such as O, S. The application does not disclose and teach metal complexes of ligands having other polycyclic structures.

US20190252627A1 discloses a type of a liquid crystal display havingMetal complexes of ligand structure, wherein Y is selected from O, S, se, NR ³ CRR ', siRR ', geRR ' or single bond, ring a is a five or six membered carbocyclic or heterocyclic ring, and specific compounds are disclosed:However, this application discloses only metal complexes having three condensed ring structure ligands, and does not disclose metal complexes having different skeleton structure ligands of more condensed rings.

At present, some red light and deep red light materials are reported, but with the increasing performance requirements of the industry on the deep red light materials, deep red light emitting materials with excellent properties such as long emission wavelength, low voltage, high efficiency and long service life still need to be researched and developed.

Disclosure of Invention

The present invention aims to provide a series of novel metal complexes to solve at least part of the above problems. The metal complex comprises a metal M and a ligand L having the structure of formula 1 _a . When the metal complex is used as a luminescent material in an organic electroluminescent device, dark red emitted light is obtained while excellent device performance such as narrow peak width, low voltage, long service life and the like can be maintained.

According to one embodiment of the invention For example, a metal complex is disclosed comprising a metal M and a ligand L coordinated to the metal M _a The metal M is selected from metals with a relative atomic mass of more than 40, and the ligand L _a Has a structure represented by formula 1:

wherein X is ₁ And X ₂ Wherein one of the N atoms is N and the N atom is bonded to the metal M through a metal-N bond, when X ₁ When N is N, X ₂ Selected from CR _A ，X ₃ Selected from N or CR _x The method comprises the steps of carrying out a first treatment on the surface of the When X is ₂ When N is N, X ₁ And X ₃ One of them is selected from CR _A Another is selected from N or CR _x The method comprises the steps of carrying out a first treatment on the surface of the The R is _A Has a structure represented by formula A:

ring a, ring B and ring C are, identically or differently, selected for each occurrence from a 5-membered unsaturated carbocycle, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms;

R _x and R is _z Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;

Y ₁ and Y ₂ One of which is a single bond and the other is selected from O, S, se, BR _y Or NR (NR) _y ；

R _x ，R _y 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 alkoxy having 6 to 30 carbon atoms An aryloxy group of atoms, a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group of 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group of 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group of 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermanium group of 3 to 20 carbon atoms, a substituted or unsubstituted arylgermanium group of 6 to 20 carbon atoms, a substituted or unsubstituted amino group of 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R _x ，R _z Can optionally be linked to form a ring;

in formula A, "x" represents R _A And X in 1 ₁ ，X ₂ Or X ₃ The position of the connection; "#" means R _A And a position connected with the metal M.

According to another embodiment of the present invention, an electroluminescent device is disclosed, comprising an anode, a cathode, an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex of the previous embodiment.

According to yet another embodiment of the present invention, a compound composition comprising the metal complex of the previous embodiment is also disclosed.

The invention discloses a L with a structure of formula 1 _a Metal complexes of ligands. The metal complex can be used as a luminescent material in an organic electroluminescent device to obtain dark red luminescent color and excellent device performance, such as narrow peak width, low voltage, long service life and the like.

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, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F 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 luminescent materials with small mono-triThe triplet energy gap (DeltaE) _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, 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, multiple substitution is meant to encompass double substitution 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:

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 metal M is selected from metals with a relative atomic mass of more than 40, and the ligand L _a Has a structure represented by formula 1:

wherein X is ₁ And X ₂ Wherein one of the N atoms is N and the N atom is bonded to the metal M through a metal-N bond, when X ₁ When N is N and the N atom is connected with the metal M through a metal-N bond, X ₂ Selected from CR _A ，X ₃ Selected from N or CR _x The method comprises the steps of carrying out a first treatment on the surface of the When X is ₂ When N is N and the N atom is connected with the metal M through a metal-N bond, X ₁ And X ₃ One of them is selected from CR _A Another is selected from N or CR _x The method comprises the steps of carrying out a first treatment on the surface of the The R is _A Has a structure represented by formula A:

R _x ，R _y 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 _x ，R _z Can optionally be linked to form a ring;

in formula A, "+" represents R _A X in 1 ₁ ，X ₂ Or X ₃ The position of the connection; "#" means R _A And a position connected with the metal M.

Herein, "adjacent substituent R _x ，R _z Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g. two substituents R _x Between two substituents R _z 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 present invention, wherein, in formula 1, X ₂ Is N, and the N atom is connected with the metal M through a metal-N bondConnect X ₃ Is CR (CR) _A The R is _A Has a structure represented by formula A.

According to one embodiment of the invention, wherein ring a, ring B and ring C are, identically or differently, selected from the group consisting of 5-membered unsaturated carbocycles, benzene rings, 6-membered heteroaromatic rings, or 5-membered heteroaromatic rings.

According to one embodiment of the invention, wherein the ligand L _a Has a structure represented by one of formulas 2 to 13:

in the formulae 2 to 13, Y ₁ Or Y ₂ Is selected identically or differently on each occurrence from O, S, se, BR _y Or NR (NR) _y ；

X ₁ ，X ₃ -X ₁₂ Is selected identically or differently on each occurrence from N or CR _x ；

X ₁₃ Selected from O, S, se, BR _x ，NR _x ，CR _x R _x Or SiR _x R _x ；

Z ₁ -Z ₄ Is selected identically or differently on each occurrence from N or CR _z ；

R _x 、R _y 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 aryl having 3 to 30 carbon atomsA 3-20 carbon alkylsilyl group, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylgermanium group having 3-20 carbon atoms, a substituted or unsubstituted arylgermanium group having 6-20 carbon atoms, a substituted or unsubstituted amino group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphine group, and combinations thereof;

Wherein adjacent substituents R _x ，R _z Can optionally be linked to form a ring.

According to one embodiment of the present invention, wherein, in formula 2 to formula 13, Y ₁ Or Y ₂ And is selected identically or differently on each occurrence from O, S or Se.

According to one embodiment of the present invention, wherein, in formula 2 to formula 13, Y ₁ Or Y ₂ Is O.

According to one embodiment of the present invention, wherein, in formulas 2 to 13, X ₁ ，X ₃ -X ₁₂ Is selected from CR, identically or differently at each occurrence _x ；X ₁₃ Selected from O, S, NRx, CRxRx or SiRxRx; and said R is _x 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 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 alkylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted arylgermyl having 6 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted germyl having 6 to 20 carbon atoms Amino groups of 0 to 20 carbon atoms, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof;

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

Herein, "adjacent substituent R _x Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g. two substituents R _x Can be connected 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 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 heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof;

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

According to one embodiment of the invention, wherein R _x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, mercapto, vinyl, phenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, phenyldimethylsilyl, trimethylsilyl, pyridinyl, pyrimidinyl, triazinyl, and combinations thereof;

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

According to one embodiment of the invention, wherein R _x And is selected identically or differently on each occurrence from hydrogen, deuterium or fluorine.

In accordance with one embodiment of the present invention,wherein in the formulae 2 to 13, X ₁ Or X ₃ One of which is N.

According to one embodiment of the present invention, wherein, in formulas 2 to 13, X ₄ -X ₁₂ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x And is selected, identically or differently, on each occurrence, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted aryl having 0 to 20 carbon atoms, cyano, and combinations thereof.

According to one embodiment of the present invention, wherein, in formulas 2 to 13, X ₄ -X ₆ At least one of them is selected from CR _x And/or X ₇ -X ₁₀ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxyMercapto, and combinations thereof.

According to one embodiment of the present invention, wherein, in formulas 2 to 7, X ₄ -X ₆ At least one of them is selected from CR _x And/or X ₇ -X ₁₀ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the In formula 8 and formula 9, X ₇ -X ₁₀ At least one of them is selected from CR _x And/or X ₁₁ Selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the In the formulae 10 to 13, X ₄ -X ₆ At least one of them is selected from CR _x And/or X ₁₁ And X ₁₂ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof.

According to one embodiment of the present invention, wherein, in formulas 2 to 13, X ₆ Selected from CR _x 。

According to one embodiment of the invention, wherein R _x And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof.

According to one embodiment of the invention, wherein R _x And is selected identically or differently on each occurrence from the group consisting of: deuteriumFluorine, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, hydroxy, mercapto, vinyl, phenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, phenyldimethylsilyl, trimethylsilyl, pyridinyl, pyrimidinyl, triazinyl, and combinations thereof.

According to one embodiment of the present invention, wherein, in formula 2 to formula 13, Z ₁ -Z ₄ Is selected from CR, identically or differently at each occurrence _z The method comprises the steps of carrying out a first treatment on the surface of the And said 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 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, and combinations thereof;

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

In this embodiment, "adjacent substituent R _z Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g. two substituents R _z Can be connected to form a ring. Obviously, these substituents may not all be linked to form a ring.

According to one embodiment of the present invention, wherein, in formula 2 to formula 13, Z ₁ -Z ₄ Two adjacent substituents R _z And are linked to form a benzene ring or a heteroaromatic ring. For example, Z ₁ Substituent R in (a) _z And Z ₂ Substituent R in (a) _z Connected to form benzene rings or heteroaromatic ringsThe method comprises the steps of carrying out a first treatment on the surface of the Also e.g. Z ₂ Substituent R in (a) _z And Z ₃ Substituent R in (a) _z A benzene ring or a heteroaromatic ring; also e.g. Z ₃ Substituent R in (a) _z And Z ₄ Substituent R in (a) _z And are linked to form a benzene ring or a heteroaromatic ring. In the present embodiment, Z ₁ -Z ₄ Two adjacent substituents R _z The benzene or heteroaryl ring formed by the connection may be optionally substituted with any one or more substituents selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.

According to one embodiment of the invention, wherein R _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, heteroalkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted silyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 3 to 20 carbon atomsArylsilane groups having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the present invention, wherein, in formula 2 to formula 13, Z ₁ -Z ₃ At least one or two of them is/are selected from CR _z And said R _z And is selected identically or differently on each occurrence 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 heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R _z And is selected identically or differently on each occurrence from the group consisting of: deuterium, fluoro, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, hydroxy, mercapto, vinyl, trimethylsilyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, pyridyl, and combinations thereof.

According to one embodiment of the invention, wherein L _a Selected from the group consisting of L _a1 To L _a834 A group consisting of said L _a1 To L _a834 See claim 10 for a specific structure of (c).

According to one embodiment of the invention, wherein the L _a1 To L _a834 Hydrogen in the structure can be partially or fully replaced by deuterium.

According to one embodiment of the invention, wherein the metal complex has M (L _a ) _m (L _b ) _n (L _c ) _q Is of a structure of (2); the metal M is selected from metals with relative atomic mass of more than 40; 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 1,2 or 3; n is 0,1 or 2; q is 0,1 or 2; m+n+q is equal to the oxidation state of the metal M; when m is greater than 1, a plurality of L _a The same or different; when n is 2, two L _b The same or different; when q is 2, two L _c 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 is _a 、R _b And R is _c 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 _a 、R _b 、R _c 、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 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 unsubstitutedSubstituted aryloxy groups having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

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

Herein, adjacent substituents R _a ，R _b ，R _c ，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 _a Between two substituents R _b Between two substituents R _c Between, substituent R _a And R is _b Between, substituent R _a And R is _c Between, substituent R _b And R is _c Between, substituent R _a And R is _N1 Between, substituent R _b And R is _N1 Between, substituent R _a And R is _C1 Between, substituent R _a And R is _C2 Between, substituent R _b And R is _C1 Between, substituent R _b And R is _C2 Between, substituent R _a And R is _N2 Between, substituent R _b 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 _a ，R _b Can optionally beThe connection forms a ring, which may form one or more of the following structures including, but not limited to:

Wherein W is selected from O, S, se, NR ' or CR ' R '; wherein said R', R _a ’，R _b ' definition and R _a 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, rh, re, os, pt, au or Cu.

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:

wherein R is ₁ –R ₇ 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 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 alkenyl having 6 to 20 carbon atomsA substituted or unsubstituted arylsilyl group having 3 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 hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

Adjacent substituents R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ Can optionally be linked to form a ring.

Herein, "adjacent substituent R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g., substituents 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 ₄ And R is ₅ Between, substituent R ₄ And R is ₆ Between, substituent R ₅ And R is ₆ 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 ₁ -R ₃ 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 ₄ -R ₆ 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 ₁ -R ₃ At least two of which are selected identically or differently on each occurrence from substituted or unsubstituted having from 2 to 20Alkyl of carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms, or a combination thereof; and/or R ₄ -R ₆ 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 the metal complex has Ir (L _a ) _m (L _b ) _3-m And has a structure represented by one of formulas 14 to 16:

wherein m is 1 or 2;

X ₁ or X ₃ Is selected from CR, identically or differently at each occurrence _x Or N; x is X ₄ -X ₁₀ Is selected from CR, identically or differently at each occurrence _x Or N;

Z ₁ -Z ₄ Is selected from CR, identically or differently at each occurrence _z Or N;

R _x ，R _y ，R _z ，R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ 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 6-membered An aryloxy group having 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermanium group having 3 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 hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R _x ，R _z ，R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ Can optionally be linked to form a ring.

According to one embodiment of the invention, wherein R ₁ -R ₃ 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 ₄ -R ₆ 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, and substituted or unsubstituted rings having from 3 to 20 ring carbon atomsAlkyl, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms, or a combination thereof.

According to an embodiment of the present invention, wherein the metal complex has a structure represented by formula 16.

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 15 for a specific structure.

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 15 for a specific structure.

According to one embodiment of the invention, wherein the metal complex has Ir (L _a ) ₂ (L _b ) Or Ir (L) _a ) ₂ (L _c ) Or Ir (L) _a )(L _c ) ₂ Is of a structure of (2);

wherein when the metal complex has Ir (L _a ) ₂ (L _b ) In the structure of (2), L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a834 Either or both of the groups, 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), L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a834 Either or both of the groups, 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), L _a Selected from the group consisting of L _a1 To L _a834 Any one of the group consisting of 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 an embodiment of the invention, wherein the metal complex is selected from the group consisting of compounds 1 to 1040, the specific structure of compounds 1 to 1040 is seen in claim 16.

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 electroluminescent device emits red or white light.

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

According to one embodiment of the invention, the 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 418

Step 1: synthesis of intermediate 1

5-bromoisoquinoline (5.0 g,24.0 mmol) was added to a 100mL round bottom flask, N ₂ Sulfuryl chloride (5 mL) is slowly added under protection, the temperature is raised to 60 ℃ for reaction for 5 minutes, then sulfuryl chloride (5 mL) is added again, the reaction is carried out for 30 minutes at 60 ℃, the temperature of the reaction solution is reduced to 0 ℃, and water is added for quenching reaction. After being neutralized with sodium bicarbonate solution, the organic phases were combined by washing three times with ethyl acetate/water. Spin-drying the solvent gives the crude product as a pale yellow oil. The crude product was purified by column chromatography eluting with petroleum ether ethyl acetate=2:1 (v/v) to give intermediate 1 (2.0 g, 34.5%).

Step 2: synthesis of intermediate 2

Intermediate 1 (2.0 g,8.3 mmol), o-hydroxyphenylboronic acid (1.4 g,9.9 mmol), potassium carbonate (2.3 g,13.8 mmol), and tetrakis triphenylphosphine palladium (0.48 g,0.34 mmol) were added to a 250mL three-necked flask, 40mL dioxane and 10mL water were added, the reaction was heated to 80 ℃ under nitrogen protection, and allowed to react overnight, after TLC showed completion of the reaction, to cool to room temperature. The organic phases were combined after three aqueous extractions with ethyl acetate, dried over anhydrous magnesium sulfate, filtered and concentrated to give intermediate 2 (1.8 g, 85.5%) as a pale yellow solid.

Step 3: synthesis of intermediate 3

Intermediate 2 (1.8 g,7.1 mmol), cuBr (129 mg,0.7 mmol), TMDH (2, 6-tetramethyl-3, 5-heptanedione) (1.33 g,7.2 mmol) and Cs ₂ CO ₃ (4.6 g,14.2 mmol) was added to a 250mL three-necked flask, and 50mL of DMF (N, N-dimethylformamide) was added. The reaction was carried out at 130℃for 5 hours under nitrogen protection. After the reaction solution was cooled to room temperature, water was added to precipitate a product, and the product was filtered. The solid was washed with water, methanol and petroleum ether and dried. The product was purified by column chromatography on silica gel using petroleum ether ethyl acetate=4:1 (v/v) as eluent to give intermediate 3 (1.1 g, 77.4%) as a white solid.

Step 4: synthesis of intermediate 4

In a 250mL round bottom flask was added intermediate 3 (1.0 g,4.6 mmol), m-chloroperoxybenzoic acid (mCPBA, 1.6g,9.2 mmol) and dichloromethane (50 mL), respectively, and the resulting reaction mixture was stirred overnight at room temperature, quenched with 100mL of water, extracted three times with dichloromethane/water, combined organic phases and dried by spinning. The crude product was purified by column chromatography on silica gel with methanol: dichloromethane = 1:50 (v/v) to afford intermediate 4 (1.1 g, 100%) as a pale yellow solid.

Step 5: synthesis of intermediate 5

In a 250mL round bottom flask was added intermediate 4 (1.1 g,4.6 mmol) and phosphorus oxychloride (15 mL), respectively, followed by dropwise addition of 2 drops of DMF as catalyst, followed by heating the reaction mixture to reflux for 3 hours, after cooling to room temperature, slowly pouring into ice water for quenching, and then successively adding sodium hydroxide to adjust the pH to neutral. The organic phases were combined, dried and spin-dried, and the crude product was purified by column chromatography on silica gel eluting with petroleum ether: ethyl acetate=2:1 (v/v) to give intermediate 5 (0.6 g, 52%) as a pale yellow solid.

Step 6: synthesis of intermediate 6

Intermediate 5 (0.6 g,2.4 mmol), 3, 5-dimethylbenzylboronic acid (0.5 g,3.6 mmol), tetrakis triphenylphosphine palladium (0.14 g,0.12 mmol), sodium carbonate (0.46 g,4.8 mmol), 1, 4-dioxane (16 mL) and water (4 mL) were added to a 100mL round bottom flask, followed by heating the reaction to 80 ℃ under nitrogen protection with stirring overnight, after TLC showed completion of the reaction, it was cooled to room temperature. Then ethyl acetate was added to the reaction, the liquid was separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried, and spin-dried to give a crude product, which was separated by silica gel column chromatography, and petroleum ether, ethyl acetate=2: 1 (v/v) to give the desired product as a white solid intermediate 6 (0.6 g, 79.5%).

Step 7: synthesis of Iridium dimers

A mixture of intermediate 6 (0.6 g,1.91 mmol), iridium trichloride trihydrate (193 mg,0.55 mmol), 2-ethoxyethanol (18 mL) and water (6 mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, the solution was distilled off with water, and the iridium dimer in ethoxyethanol was obtained and used directly in the next reaction without further purification.

Step 8: synthesis of Compound 418

An ethoxyethanol solution of the iridium dimer obtained in step 7, 3, 7-diethyl-3-methylnonane-4, 6-dione (200 mg,0.83 mmol) and potassium carbonate (0.38 g,2.75 mmol) were added to a 100mL round bottom flask and reacted at 60℃under nitrogen for 24 hours. It was then poured into a funnel containing celite, filtered and washed with ethanol. Dichloromethane was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated. The product was further purified by column chromatography with petroleum ether: ethyl acetate=10: 1 (v/v) to give compound 418 (0.3 g, yield 14.7%). The product was confirmed by LC-MS as the target product and had a molecular weight of 1062.39.

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 obtain the structure of the compound of the present invention by modifying it.

The method of manufacturing the electroluminescent device is not limited, and the following examples are only examples and should not be construed as limiting. Those skilled in the art will be able to make reasonable modifications to the preparation methods of the following examples in light of the prior art. The proportion of the various materials in the luminescent layer is not particularly limited, and a person skilled in the art can reasonably select the materials within a certain range according to the prior art, for example, the main material can occupy 80% -99% and the luminescent material can occupy 1% -20% based on the total weight of the luminescent layer; or the main material can account for 90% -99%, and the luminescent material can account for 1% -10%; or the main material may occupy 95% -99% and the luminescent material may occupy 1% -5%. In addition, the main material may be one or two materials, wherein the proportion of the two main materials to the main material may be 100:0 to 1:99, a step of; alternatively, the ratio may be 80:20 to 20:80; alternatively, the ratio may be 60:40 to 40:60.

Device embodiment

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 HT and HI as dopants were evaporated and used as hole injection layer (HIL, weight ratio of compound HT to compound HI 97:3,). The compound HT serves as a hole transport layer (HTL,). Compound EB is used as electron blocking layer (EBL, -/-for)>). Then the host compound RH and the compound 418 according to the invention as dopant are evaporated for use as a light-emitting layer (EML, weight ratio of compound RH and compound 418 98:2, + by weight>). Compound HB is used as hole blocking layer (HBL, -/->). On the HBL, a mixture of a compound ET and 8-hydroxyquinoline-lithium (Liq) was deposited as an electron transport layer (ETL, weight ratio of compound ET and Liq 40:60,/weight ratio of compound ET to Liq>). 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.

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 418 of the present application in the light-emitting layer (EML).

Comparative example 2

Device comparative example 2 was prepared in the same manner as device example 1 except that compound RD-B was used in place of compound 418 of the present application in the light-emitting layer (EML).

The detailed device layer structure and thickness are shown in table 1. 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 example 1 and comparative examples 1-2

The material structure used in the device is as follows:

at 15mA/cm ² CIE color coordinates, maximum emission wavelength lambda were measured for examples and comparative examples at current densities _max (nm), full width at half maximum FWHM (nm), and drive Voltage (V), at 80mA/cm ² Life LT97 was measured at current density and these data are recorded and shown in table 2.

Table 2 device data for example 1 and comparative examples 1-2

Discussion:

as can be seen from the data in table 2, example 1 uses the metal complex comprising the ligand of the structure of formula 1 of the present application as a light-emitting material, and can make the emission spectrum red-shifted to a deep red region of 660nm or more, and when the metal complex of the present application is applied to an electroluminescent device as a light-emitting dopant, the electroluminescent device has very saturated deep red emission. Compared with comparative example 1 using the compound RD-a having no heteroatom-bridging structure, the half-width of example 1 was narrower by 4nm, the voltage was reduced by 0.09V, and at the same time, a red shift of the maximum emission wavelength exceeding 40nm was achieved, and the device lifetime was greatly improved by 8.4 times.

In comparative example 2, compound RD-B, whose maximum emission wavelength is far below 600nm, was not able to achieve deep red emission at all, and it should be noted that although the half-width of example 1 was slightly larger than that of comparative example 2, it was still at a very narrow level; more importantly, compared with comparative example 2, the metal complex of example 1 has lower driving voltage and unique deep red light emitting effect, and the maximum emission wavelength is red shifted by more than 100nm, and more importantly, the service life of the device of example 1 is greatly improved by nearly 100 times.

In summary, the metal complex with the ligand of the polycyclic structure of formula 1 disclosed by the invention can enable the luminescence spectrum of the electroluminescent device to be greatly red shifted to a deep red region, can obtain deep red luminescence of a narrow spectrum, and has low driving voltage and greatly improved long service life of the device. These advantages highlight the uniqueness of the invention and the potential of commercial application of the compounds of the invention as deep red light emitting materials.

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. Metal complexComprising a metal M and a ligand L coordinated to the metal M _a The metal M is selected from metals with a relative atomic mass of more than 40, and the ligand L _a Has a structure represented by formula 1:

R _x ，R _y 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 alkoxy having 6 to 30 carbon atoms Aryloxy, 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;

adjacent substituents R _x ，R _z Can optionally be linked to form a ring;

2. The metal complex of claim 1, wherein ring a, ring B, and ring C are, identically or differently, selected from the group consisting of a 5-membered unsaturated carbocycle, a benzene ring, a 6-membered heteroaromatic ring, or a 5-membered heteroaromatic ring.

3. The metal complex according to claim 1 or 2, wherein the ligand L _a Has a structure represented by one of formulas 2 to 13:

R _x 、R _y 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, in the formulae 2 to 13, Y ₁ Or Y ₂ Is selected identically or differently on each occurrence from O, S or Se; preferably Y ₁ Or Y ₂ Is O.

5. The metal complex as claimed in claim 3, wherein, in the formulae 2 to 13, X ₁ ，X ₃ -X ₁₂ Each time go outAt the present time are identically or differently selected from CR _x ；X ₁₃ Selected from O, S, NR _x ，CR _x R _x Or SiR _x R _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x 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 aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, and combinations thereof;

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

preferably, said R _x 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 heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof;

more preferably, the R _x Is selected identically or differently on each occurrence from the group consisting ofThe group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, mercapto, vinyl, phenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, phenyldimethylsilyl, trimethylsilyl, pyridinyl, pyrimidinyl, triazinyl, and combinations thereof.

6. The metal complex as claimed in claim 3, wherein, in the formulae 2 to 13, X ₁ Or X ₃ One of which is N.

7. The metal complex as claimed in claim 3 or 5, wherein, in the formulae 2 to 13, X ₄ -X ₁₂ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x And is selected, identically or differently, on each occurrence, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl 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 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 alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 0 to 20 carbon atoms, cyano, and combinations thereof;

Preferably X ₄ -X ₆ At least one of them is selected from CR _x And/or X ₇ -X ₁₀ At least one of them is selected from CR _x The method comprises the steps of carrying out a first treatment on the surface of the And said R is _x The same or different at each occurrenceIs selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, hydroxy, mercapto, and combinations thereof;

more preferably X ₆ Selected from CR _x 。

8. The metal complex according to claim 7, wherein R is _x And is selected identically or differently on each occurrence from the group consisting of: deuterium, fluorine, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, hydroxy, mercapto, vinyl, phenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, phenyldimethylsilyl, trimethylsilyl, pyridinyl, pyrimidinyl, triazinyl, and combinations thereof.

9. The metal complex as claimed in claim 3, wherein, in the formulae 2 to 13, Z ₁ -Z ₄ Is selected from CR, identically or differently at each occurrence _z The method comprises the steps of carrying out a first treatment on the surface of the And said 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atomsA substituted or unsubstituted alkyl silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl silyl group having 6 to 20 carbon atoms, and combinations thereof;

adjacent substituents R _z Can optionally be linked to form a ring;

preferably, in formulae 2 to 13, Z ₁ -Z ₃ At least one or two of them is/are selected from CR _z And said R _z And is selected identically or differently on each occurrence from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 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, and combinations thereof;

more preferably, the R _z And is selected identically or differently on each occurrence from the group consisting of: deuterium, fluoro, methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, hydroxy, mercapto, vinyl, trimethylsilyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-triisopropylphenyl, pyridyl, and combinations thereof.

10. The metal complex according to claim 1, wherein L _a And is selected identically or differently on each occurrence from the group consisting of:

optionally, said L _a1 To L _a834 Hydrogen in the structure can be partially or fully replaced by deuterium.

11. The metal complex according to claim 1, wherein the metal complex has a structure of M (L _a ) _m (L _b ) _n (L _c ) _q Is of a structure of (2); the metal M is selected from metals with relative atomic mass of more than 40; 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 1,2 or 3; n is 0,1 or 2; q is 0,1 or 2; m+n+q is equal to the oxidation state of the metal M; when m is greater than 1, a plurality of L _a The same or different; when n is 2, two L _b The same or different; when q is 2, two L _c The same or different;

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

R _a 、R _b 、R _c 、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 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 aryl having 6 to 30 carbon atomsAryloxy groups of carbon atoms, substituted or unsubstituted alkenyl groups of 2 to 20 carbon atoms, substituted or unsubstituted aryl groups of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups of 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups of 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups of 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups of 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups of 6 to 20 carbon atoms, substituted or unsubstituted amino groups of 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

12. The metal complex of claim 1 or 11, wherein the metal M is selected from Ir, rh, re, os, pt, au or Cu; preferably, the metal M is selected from Ir, pt or Os; more preferably, the metal M is Ir.

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

wherein R is ₁ –R ₇ 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 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 atomsSubstituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

Adjacent substituents R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ Can optionally be linked to form a ring;

preferably, wherein R ₁ -R ₃ 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 ₄ -R ₆ 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;

more preferably, wherein R ₁ -R ₃ 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 ₄ -R ₆ 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.

14. The metal complex according to claim 1 or 11, wherein the metal complex has Ir (L _a ) _m (L _b ) _3-m And has a structure represented by one of formulas 14 to 16:

wherein m is 1 or 2;

R _x ，R _y ，R _z ，R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ 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 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 groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

adjacent substituents R _x ，R _z ，R ₁ ，R ₂ ，R ₃ ，R ₄ ，R ₅ ，R ₆ ，R ₇ Can optionally be linked to form a ring;

15. The metal complex of claim 11, 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:

16. the metal complex according to claim 11, wherein the metal complex has Ir (L _a ) ₂ (L _b ) Or Ir (L) _a ) ₂ (L _c ) Or Ir (L) _a )(L _c ) ₂ Is of a structure of (2);

wherein when the metal complex has Ir (L _a ) ₂ (L _b ) In the structure of (2), L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a834 Either or both of the groups, 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), L _a Is selected identically or differently on each occurrence from the group consisting of L _a1 To L _a834 Either or both of the groups, 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), L _a Selected from the group consisting of L _a1 To L _a834 Any one of the group consisting of 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 1040, the compounds 1 to 1040 having Ir (L _a ) ₂ (L _b ) Wherein two L _a Identical, L _a And L _b Respectively correspond to structures selected from the list of:

17. an electroluminescent device, 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 cathode, wherein the organic layer comprises the metal complex of any one of claims 1-16.

18. The electroluminescent device of claim 17 wherein the organic layer is a light emitting layer and the metal complex is a light emitting material.

19. An electroluminescent device as claimed in claim 17 or 18 wherein the electroluminescent device emits red or white light.

20. The electroluminescent device of claim 18 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.

21. A compound composition comprising the metal complex of any one of claims 1-16.