CN117820378A

CN117820378A - Organic electroluminescent material and device thereof

Info

Publication number: CN117820378A
Application number: CN202211158620.9A
Authority: CN
Inventors: 赵春亮; 桑明; 田学超; 蔡刘欢; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2022-09-27
Filing date: 2022-09-27
Publication date: 2024-04-05

Abstract

An organic electroluminescent material and a device thereof are disclosed. The organic electroluminescent material is a compound having the structure of formula 1, which can be used as a light emitting material in an organic electroluminescent device, and can provide better device performance, such as higher current efficiency and higher external quantum efficiency. Also disclosed is a compound composition comprising the structure of formula 1.

Description

Organic electroluminescent material and device thereof

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. And more particularly, to a compound having a structure of formula 1, and an organic electroluminescent device and a compound composition including 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.

US20210167303A1 discloses a device with M ₁ (L ₁₁ ) _n11 (L ₁₂ ) _n12 Organometallic complexes of the general formula, wherein n11 is 1, n12 is 0,1 or 2, L ₁₁ Is thatRepresented structure, wherein ring A ₂₀ Is thatThe indicated structure, the application discloses in specific structures the following compounds: />This application is directed primarily to specific positions in the platinum complex (ring a ₂₀ ) Is a study of aromatic (heteroaromatic) aromatic fused ring structures, but it does not disclose or teach the use of aromatic (heteroaromatic) aromatic ring fused (heteroaromatic) hydrocarbon structures in platinum complexes in organic electroluminescent devices. Moreover, the compounds of the examples in this application all have a luminescence wavelength of about 440nm, and it is found that the compounds are too blue to be suitable for commercial applications.

US20200392172A1 discloses a novel platinum complex as guest luminescent material, which has the general formulaWherein part Z is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings, wherein each ring is a 5-membered ring or a 6-membered ring. The following compounds are disclosed in the specific structure of this application:this application is primarily directed to the study of the platinum complex ring Z as a plurality of heterocyclic or carbocyclic fused structures, but again does not disclose or teach the use of the platinum complex with aromatic (heteroaromatic) aromatic ring fused (hetero) cyclic hydrocarbon structures in organic electroluminescent devices. Also, since moiety Z of the claimed compounds is a structure comprising multiple condensed rings, its triplet state is relatively low, ultimately resulting in a reduced EQE of the device. In addition, the compound of the example in this application has an emission wavelength of 550nm, and blue emission cannot be achieved.

The prior art has a lot of researches on luminescent materials of platinum complexes, but there are few reports on the introduction of condensed (hetero) cyclic hydrocarbon structures in aromatic (hetero) aromatic rings of platinum complexes. In addition, in the research of blue light devices, the device efficiency, the color saturation and the like of the blue light devices have certain limitations, so that the application potential of the materials is worth continuing to be deeply researched and developed.

Disclosure of Invention

The present invention aims to provide a series of compounds having the structure of formula 1 to solve at least part of the above problems. The compounds are useful as light emitting materials in organic electroluminescent devices. These novel compounds can provide better device performance, such as higher current efficiency and higher external quantum efficiency.

According to one embodiment of the present invention, a compound having the structure of formula 1 is disclosed:

in the formula (1) of the present invention,

ring a, ring B, ring E are, identically or differently, selected for each occurrence from an unsaturated carbocycle having 5-30 carbon atoms, an unsaturated heterocycle having 3-30 carbon atoms, or a combination thereof; ring D is, identically or differently, selected for each occurrence from unsaturated heterocycles having 3 to 30 carbon atoms;

the metal M is selected from metals with relative atomic mass of more than 40;

L ₁ ，L ₂ is selected identically or differently on each occurrence from single bonds, O, S, se, (SiR "R") _y ，PR”，NR”，(CR”R”) _y A substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

K ₁ -K ₄ the groups are selected identically or differently on each occurrence from single bonds, O, S or Se;

y is selected identically or differently on each occurrence from 1,2,3,4 or 5;

Z ₁ -Z ₃ selected identically or differently on each occurrence from C or N;

at least one of ring a, ring B, ring E, ring D has two adjacent atoms as carbon atoms and is respectively connected with two "×" in formula 2;

z is selected identically or differently on each occurrence from C (R _z ) ₂ ，NR _z O, S or Se;

n is selected identically or differently on each occurrence from 0,1,2,3,4 or 5;

R _a ，R _b ，R _c ，R _d each occurrence, identically or differently, is represented as mono-substituted, poly-substituted or unsubstituted;

R，R”，R _a ，R _b ，R _c ，R _d ，R _z and is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

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

According to another embodiment of the present invention, there is also disclosed an electroluminescent device including an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including the compound having the structure of formula 1.

According to another embodiment of the present invention, there is also disclosed a compound composition comprising the compound having the structure of formula 1.

The invention discloses a series of compounds with a structure shown in a formula 1. The compounds can be used as luminescent materials in organic electroluminescent devices, and can provide better device performance, such as higher current efficiency and higher external quantum efficiency.

Drawings

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

Fig. 2 is a schematic view of another organic light emitting device that may contain the compounds 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. Is incorporated by reference in its entiretyExamples of cathodes are disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference, and include composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sublayers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.

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

The OLED also requires an encapsulation layer, such as the organic light emitting device 200 shown schematically and without limitation in fig. 2, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film packages are described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.

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

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

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

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

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

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

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

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

Definition of terms for substituents

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

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

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

Heteroalkyl-as used herein, a heteroalkyl comprises an alkyl chain in which one or more carbons is replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl. 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-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, thietane trienyl, azepanyl and tetrahydrothiophenyl. 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 pyridine, thienodipyridine, benzoselenophene bipyridine, 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.

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 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, any one or more of which may be substituted with one or more groups selected from deuterium, halogen, unsubstituted alkyl having from 1 to 20 carbon atoms, unsubstituted cycloalkyl having from 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having from 1 to 20 carbon atoms, unsubstituted heterocyclic group having from 3 to 20 carbon atoms, unsubstituted aryl having from 7 to 20 carbon atoms, unsubstituted alkoxy having from 3 to 20 carbon atoms, unsubstituted alkenyl having from 3 to 20 carbon atoms, unsubstituted alkoxy having from 3 to 30 carbon atoms, unsubstituted aryl having from 3 to 30 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered equivalent.

In the compounds mentioned in this disclosure, the hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because of their enhanced efficiency and stability of the device.

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

In the compounds mentioned in this disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring. In the compounds mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, both in the case where adjacent substituents can be linked to form a ring and in the case where adjacent substituents are not linked to form a ring. Where adjacent substituents can optionally be joined to form a ring, the ring formed may be monocyclic or polycyclic, 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:

furthermore, the expression that adjacent substituents can be optionally linked to form a ring is also intended to be taken to mean that, in the case where one of the two substituents bonded to carbon atoms directly bonded to each other 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:

in the formula (1) of the present invention,

the metal M is selected from metals with relative atomic mass of more than 40;

y is selected identically or differently on each occurrence from 1,2,3,4 or 5;

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

In this embodiment, n in formula 2 represents "- (Z) _n The number of Z in- (O) -and wherein n Z are ring atoms in formula 2, and formula 2 is linked to formula 1 by two- (X) -to form an (n+4) -membered ring. For example, when n=1, there are 3Z in formula 2, and formula 2 is linked to formula 1 by two "+; when n=2, there are 4Z in formula 2, and formula 2 is linked to formula 1 by two "×" to form a six membered ring; when n is selected from 3,4 or 5, the same is true as in the case exemplified above.

As used herein, "unsaturated carbocycle having 5 to 30 carbon atoms" includes aromatic unsaturated carbocycle having 5 to 30 carbon atoms and non-aromatic unsaturated carbocycle; "unsaturated heterocyclic ring having 3 to 30 carbon atoms" includes aromatic unsaturated heterocyclic ring having 3 to 30 carbon atoms and non-aromatic unsaturated heterocyclic ring.

Herein, "adjacent substituents R, R", R _a ，R _b ，R _c ，R _d ，R _z 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 two substituents R _d Between two substituents R _z Between two substituents R' and substituents R and R _d Between which any one or more of these substituent groups may be linked to form a ring. Obviously, none of these adjacent substituents may be linked to form a ring.

According to one embodiment of the invention, wherein the compound has M (L _a )(L _b ) A structure represented by the general formula, wherein L _a And L _b A first ligand and a second ligand coordinated to the metal M, respectively, the L _a Has a structure represented by formula A:wherein "#" in formula A represents a value equal to L _b The position of the connection; the L is _b Has a structure represented by formula B:wherein>Representation and L _a The location of the connection.

According to one embodiment of the invention, wherein said M is selected from Cu, ag, au, ru, rh, pd, os, ir or Pt.

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

According to one embodiment of the invention, wherein said M is selected from Pt.

According to one embodiment of the invention, wherein the rings a, B, E are, identically or differently, selected at each occurrence from five-membered unsaturated carbocycles, aromatic rings having 6-30 carbon atoms, heteroaromatic rings having 3-30 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein the rings a, B, E are, identically or differently, selected at each occurrence from five-membered unsaturated carbocycles, aromatic rings having 6-18 carbon atoms, heteroaromatic rings having 3-18 carbon atoms, or combinations thereof.

According to one embodiment of the invention, wherein the rings a, B, E are selected identically or differently for each occurrence from benzene rings, pyridine rings, indene rings, fluorene rings, indole rings, carbazole rings, indolocarbazole rings, benzofuran rings, dibenzofuran rings, benzothiophene rings, dibenzothiazole rings, benzothiophene rings, dibenzothiophene rings, dibenzoselenophene rings, cyclopentadiene rings, furan rings, thiophene rings, silole rings, or combinations thereof.

According to one embodiment of the invention, wherein the rings D are chosen, identically or differently, for each occurrence, from unsaturated heterocycles having 3 to 18 carbon atoms.

According to one embodiment of the invention, wherein the ring D is selected identically or differently on each occurrence from the group consisting of imidazole carbene rings or benzimidazole carbene rings.

According to one embodiment of the invention, wherein said L ₁ Is selected identically or differently on each occurrence from single bonds, O, S, (SiR "R") _y ，NR”，(CR”R”) _y Or a combination thereof.

According to one embodiment of the invention, wherein said L ₁ And are selected identically or differently on each occurrence from single bonds, O or S.

According to one embodiment of the invention, wherein said L ₁ Selected from single bonds.

According to one embodiment of the invention, wherein the K ₁ -K ₄ Selected from single bonds.

According to one embodiment of the invention, wherein said Z ₁ Selected from N, Z ₂ ，Z ₃ Selected from C.

According to one embodiment of the invention, two adjacent atoms in the ring E are carbon atoms and are respectively connected with two "x" in formula 2.

In this embodiment, wherein two adjacent atoms in the ring E are carbon atoms and are respectively connected to two "×" in formula 2, it is intended to mean that the compound has the following structure:wherein ring E is linked to the ring comprising Z through two adjacent carbon atoms in ring E (i.e., ring E is fused to the ring comprising Z through two adjacent carbon atoms in ring E).

According to one embodiment of the invention, wherein said R _a ，R _b ，R _c ，R _d And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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, and combinations thereof.

According to one embodiment of the invention, wherein said R _a ，R _b ，R _c ，R _d And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, methyl, deuterated methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

According to one embodiment of the invention, the R _a ，R _b ，R _c ，R _d And at least one of R is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 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 6 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, the R _a ，R _b ，R _c ，R _d And at least one of R is selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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.

According to one embodiment of the invention, the R _a ，R _b ，R _c ，R _d And at least one of R is selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

According to one embodiment of the invention, the R _z At least one selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted Or an 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.

According to one embodiment of the invention, the R _z At least one selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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.

According to one embodiment of the invention, the R _z At least one selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

According to an embodiment of the present invention, wherein the compound has a structure represented by one of formulas 1-1 to 1-15:

/>

in the formulae 1-1 to 1-15,

L ₂ is selected identically or differently on each occurrence from single bonds, O, S, se, (SiR "R") _y ，PR”，NR”，(CR”R”) _y A substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;

n, y are selected, identically or differently, for each occurrence, from 0,1,2,3,4 or 5; the method comprises the steps of carrying out a first treatment on the surface of the

X ₁ -X ₂₀ Is selected identically or differently on each occurrence from C, CR _x Or N;

R，R”，R _x ，R _z and is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

Adjacent substituents R, R ", R _x ，R _z Can optionally be linked to form a ring.

In this embodiment, in formula 1-1, X ₁₁ -X ₁₃ Wherein two adjacent atoms are selected from C and are respectively as in formula 1-1Is a "x" linkage; in the formula 1-2, X ₁₁ -X ₁₃ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-2; in the formulae 1 to 3, X ₁₁ -X ₁₃ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-3; in formulae 1 to 4, X ₈ -X ₁₀ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-4; in formulae 1 to 5, X ₈ -X ₁₀ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-5; in formulas 1 to 6, X ₆ -X ₈ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-6; in formulas 1 to 7, X ₁₄ -X ₁₆ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-7; in formulae 1 to 8, X ₁₄ -X ₁₆ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-8; in formulae 1 to 10, X ₁₁ -X ₁₄ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" of formulae 1-10; in the formulae 1 to 11, X ₉ -X ₁₁ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-11; in formulae 1 to 12, X ₆ -X ₈ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" in formulas 1-12; in formulae 1 to 13, X ₆ -X ₈ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" of formulae 1-13; in formulae 1 to 14, X ₉ -X ₁₁ Wherein two adjacent atoms are selected from C and are respectively linked to two "+" of formulae 1-14; in formulae 1 to 15, X ₆ -X ₈ Wherein two adjacent atoms are selected from C and are respectively linked to two of formulae 1-15.

In this embodiment, "adjacent substituents R, R", 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 Between two substituents R' and substituents R and R _x Between, any of these substituent groupsOne or more may be joined to form a ring. Obviously, none of these adjacent substituents may be linked to form a ring.

According to an embodiment of the present invention, the compound has a structure represented by formula 1-1 or formula 1-2.

According to one embodiment of the invention, wherein said X ₁ -X ₂₀ Is selected from CR, identically or differently at each occurrence _x 。

According to one embodiment of the invention, wherein n is 1 or 2.

According to one embodiment of the invention, wherein said L ₂ Is selected identically or differently on each occurrence from single bonds, O, S, (SiR "R") _y ，NR”，(CR”R”) _y Or a combination thereof.

According to one embodiment of the invention, wherein said L ₂ And are selected identically or differently on each occurrence from single bonds, O or S.

According to one embodiment of the invention, wherein said L ₂ Selected from O.

According to one embodiment of the invention, wherein Z is chosen identically or differently for each occurrence from C (R _z ) ₂ 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 groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein Z is chosen identically or differently for each occurrence from C (R _z ) ₂ And R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof.

According to one embodiment of the invention, wherein R, R ", R _x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 arylsilane having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R, R ", R _x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, methyl, deuterated methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

According to one embodiment of the present invention, in formulas 1-1 to 1-15, the R and R _x At least one selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl germanium 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.

According to one embodiment of the present invention, in formulas 1-1 to 1-15, the R and R _x At least one selected from the group consisting of: deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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.

According to one embodiment of the present invention, in formulas 1-1 to 1-15, the R and R _x At least one selected from the group consisting of: deuterium, fluoro, methyl, deuteromethyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

According to one embodiment of the invention, wherein the compound has Pt (L _a )(L _b ) Represented structure, wherein L _a And L _b A first ligand and a second ligand coordinated to the metal Pt, respectively, the L _a Selected from the group consisting of L _a 1-1 to L _a 1-37，L _a 2-1 to L _a 2-34，L _a 3-1 to L _a 3-25，L _a 4-1 to L _a 4-37，L _a 5-1 to L _a 5-23, and L _a 6-1 to L _a 6-16, said L _b Selected from the group consisting of L _b 1-1 to L _b 1-22，L _b 2-1 to L _b 2-29，L _b 3-1 to L _b 3-26，L _b 4-1 to L _b 4-25, and L _b 5-1 to L _b 5-11; the L is _a 1-1 to L _a 1-37，L _a 2-1 to L _a 2-34，L _a 3-1 to L _a 3-25，L _a 4-1 to L _a 4-37，L _a 5-1 to L _a 5-23，L _a 6-1 to L _a 6-16，L _b 1-1 to L _b 1-22，L _b 2-1 to L _b 2-29，L _b 3-1 to L _b 3-26，L _b 4-1 to L _b 4-25, and L _b 5-1 to L _b The specific structure of 5-11 is shown in claim 15.

According to one embodiment of the invention, wherein the compound has Pt (L _a )(L _b ) The structure represented is selected from the group consisting of compounds Pt1 to Pt664, the specific structure of compounds Pt1 to Pt664 being shown in claim 15.

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, the organic layer comprising a compound having a structure of formula 1, the compound having a structure of formula 1 being as described in any one of the embodiments above.

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

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

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

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

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

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

According to another embodiment of the present invention, a compound composition is disclosed, which comprises a compound having the structure of formula 1, wherein the compound having the structure of formula 1 is as shown in any one of the above 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 Pt2

The first step: synthesis of intermediate 1

3, 5-Dibromobenzyl bromide (32.8 g,100 mmol) was dissolved in tetrahydrofuran (100 mL) under nitrogen, cooled to-78deg.C, and then 2-methallyl magnesium chloride (0.5M, 200 mL) was slowly added dropwise, and the reaction was slowly warmed to room temperature and stirred overnight. After quenching by adding saturated ammonium chloride solution and extracting three times with dichloromethane, the organic phases are combined, dried by spin and purified by column chromatography to give intermediate 1 (27.4 g,90 mmol).

And a second step of: synthesis of intermediate 2

9- (4- (tert-butyl) pyridin-2-yl) -9H-carbazol-2-ol (15.8 g,50 mmol), intermediate 1 (18.2 g,60 mmol), copper iodide (0.95 g,5 mmol), 2-picolinic acid (1.2 g,10 mmol), potassium phosphate (21.2 g,100 mmol) were added to the flask under nitrogen, DMSO (200 mL) was added, and the reaction was warmed to 150℃and heated overnight. After cooling to room temperature, a large amount of water was added, the organic phases were combined after extraction three times with dichloromethane, and after spin-drying, intermediate 2 (21.56 g,40 mmol) was purified by column chromatography.

And a third step of: synthesis of intermediate 3

Intermediate 2 (2.69 g,5 mmol), N1- ([ 1,1':3', 1' -terphenyl) was reacted under nitrogen]-2 '-yl-2, 2", 3", 4", 5",6, 6' -d 10) benzene-1, 2-diamine (2 g,6 mmol), pd (OAc) ₂ (80 mg,0.35 mmol), S-Phos (290 mg,0.7 mmol), naOt-Bu (0.96 g,10 mmol), xylene (50 mL) were added to the flask, the reaction was warmed to 140℃and stirred overnight, cooled to room temperature, and after spin-drying, intermediate 3 (2.4 g,3 mmol) was obtained by means of column chromatography.

Fourth step: synthesis of intermediate 4

Intermediate 3 (2.4 g,3 mmol), triethyl orthoformate (14.8 g,100 mmol), concentrated hydrochloric acid (0.5 mL) were added to the flask under nitrogen, the reaction was warmed to 100deg.C and stirred overnight, after which the reaction was detected by TLC, cooled to room temperature, dried by spin-on, and intermediate 4 (1.6 g,2 mmol) was obtained by column chromatography.

Fifth step: synthesis of intermediate 5

Intermediate 4 (1.6 g,2 mmol), ag under nitrogen ₂ O(0.26g，1.2 mmol) of DCE (20 mL) was added to the flask, reacted at room temperature for 12 hours, the solvent was evaporated under reduced pressure after the reaction was completed, and (1, 5-cyclooctadiene) platinum dichloride (Pt (COD) Cl) was added ₂ 0.8g,2.2 mmol) and dichlorobenzene (20 mL) were added, the reaction was warmed to 200℃and stirred for 24h, after cooling to room temperature, intermediate 5 (1 g,1.2 mmol) was obtained by column chromatography.

Sixth step: synthesis of Compound Pt2

Intermediate 5 (1 g,1.2 mmol) was dissolved in anhydrous dichloromethane under nitrogen, cooled to 0deg.C, then aluminum chloride (0.27 g,2 mmol) was added, the reaction was warmed to room temperature and stirred for 4 hours, and compound Pt2 (0.8 g,0.8 mmol) was obtained by column chromatography. The product was identified as the target product and had a molecular weight of 1007.3.

Synthesis of comparative example 1: synthesis of Compound Pt-A

The first step: synthesis of intermediate 6

1, 3-dibromo-5-tert-butylbenzene (20.7 g,71 mmol), 9- (4- (tert-butyl) pyridin-2-yl) -9H-carbazol-2-ol (15 g,47.4 mmol), cuprous iodide (0.76 g,4 mmol), 2-picolinic acid (0.98 g,8 mmol), potassium phosphate (17 g,80 mmol) and DMSO (160 mL) were added to the flask under nitrogen, the reaction was warmed to 110℃and stirred overnight, after detection by TLC to the end of the reaction, cooled to room temperature, a large amount of water was added, after extraction three times with dichloromethane, the organic phases were combined and intermediate 6 (17.8 g,35 mmol) was obtained by means of column chromatography after spin-drying.

And a second step of: synthesis of intermediate 7

Intermediate 6 (9.4 g,17.8 mmol), N1- ([ 1,1':3',1'' -terphenyl) was reacted under nitrogen]-2' -yl-2, 2", 3", 4", 5",6,6"-d 10) benzene-1, 2-diamine (6.2 g,17.8 mmol), pd (OAc) ₂ (0.16 g,0.7 mmol), SPhos (0.58 g,1.4 mmol), naOt-Bu (3.4 g,35.6 mmol), xylene (180 mL) were added to the flask, the reaction was warmed to 110℃and stirred overnight, after detection by TLC to completion, cooled to room temperature, and after spin-drying, intermediate 7 (11 g,13.8 mmol) was obtained by means of column chromatography.

And a third step of: synthesis of intermediate 8

Intermediate 7 (10.4 g,13.1 mmol), triethyl orthoformate (9.7 g,65.5 mmol), concentrated hydrochloric acid (1.3 mL) were added to the flask under nitrogen, the reaction was warmed to 100deg.C and stirred overnight, after detection by TLC to completion, cooled to room temperature, dried by spin-drying to give intermediate 8 (7 g,8.3 mmol) by column chromatography.

And a third step of: synthesis of Compound Pt-A

Nitrogen conditions, intermediate 8 (3 g,3.58 mmol), ag ₂ O (0.43 g,1.86 mmol) was added to DCE (35 mL), reacted at room temperature for 24 hours, after the reaction was completed, the solvent was evaporated under reduced pressure, platinum (1.2 g,3.2 mmol) dichloride (1, 5-cyclooctadiene) was added to a flask, dichlorobenzene (35 mL) was added, and after the reaction was warmed to 190℃and stirred for 60 hours, cooled to room temperature, and then compound Pt-A (2.5 g,2.4 mmol) was obtained by means of column chromatography. The product was identified as the target product and had a molecular weight of 995.3.

Synthesis of comparative example 2: synthesis of Compound Pt-B

The first step: synthesis of intermediate 9

2-bromo-9- (4- (tert-butyl) pyridin-2-yl) -9H-carbazole (7.0 g,18.0 mmol), m-chlorophenol (3.0 g,23.3 mmol), cuprous iodide (0.348 g,1.8 mmol), 2-picolinic acid (0.4472 g,3.6 mmol), and potassium phosphate (7.6 g,36.0 mmol) were added to a 500mL flask under nitrogen and dimethyl sulfoxide 72mL was added. Heating to 150deg.C, stirring overnight, and purifying by column chromatography to obtain intermediate 9 (4.1 g,9.6 mmol).

And a second step of: synthesis of intermediate 10

Intermediate 9 (4.1 g,9.6 mmol), N1- ([ 1,1':3', 1' -terphenyl) was reacted under nitrogen]-2 '-yl-2, 2", 3", 4", 5",6, 6' -d 10) benzene-1, 2-diamine (2 g,6 mmol), pd (OAc) ₂ (197mg, 0.48 mmol), S-Phos (390 mg,0.96 mmol), naOt-Bu (1.84 g,19.2 mmol), xylene (100 mL) were added to the flask, the reaction was warmed to 140℃and stirred overnight, cooled to room temperature, and after spin-drying, intermediate 10 (2.3 g,3.1 mmol) was obtained by column chromatography.

And a third step of: synthesis of intermediate 11

Intermediate 10 (2.3 g,3.1 mmol), triethyl orthoformate (23.0 g,155 mmol), concentrated hydrochloric acid (0.4 mL) were added to the flask under nitrogen, the reaction was warmed to 100deg.C and stirred overnight, after which the reaction was detected by TLC, cooled to room temperature, and after spin-drying, intermediate 11 (3.0 g,2.5 mmol) was obtained by column chromatography.

Fourth step: synthesis of Compound Pt-B

Nitrogen conditions, intermediate 11 (2.0 g,2.5 mmol), ag ₂ O (0.29 g,1.3 mmol) was added to DCE (25 mL), reacted at room temperature for 12h, after the reaction was completed, the solvent was evaporated to dryness under reduced pressure, platinum (1, 5-cyclooctadiene) dichloride (0.94 g,2.5 mmol) was added to a flask, dichlorobenzene (25 mL) was added, and after the reaction was warmed to 200℃and stirred for 24h, cooled to room temperature, and then the compound Pt-B (0.95 g,1.0 mmol) was obtained by means of column chromatography. The product was identified as the target product and had a molecular weight of 939.3.

Synthesis of comparative example 3: synthesis of Compound Pt-C

The first step: synthesis of intermediate 12

Bromine-9- (4- (tert-butyl) pyridin-2-yl) -9H-carbazole (19 g,50 mmol), 2- (tert-butyl) -5-chlorophenol (9.2 g,50 mmol), cuprous iodide (0.95 g,5 mmol), ferric acetylacetonate (3.5 g,10 mmol), potassium phosphate (21.2 g,100 mmol) were added to the flask under nitrogen, DMSO (200 mL) was added, and the reaction was warmed to 150℃and heated overnight. After cooling to room temperature, a large amount of water was added, the organic phases were combined after extraction three times with dichloromethane, and after spin-drying, intermediate 12 (5.8 g,12 mmol) was purified by column chromatography.

And a second step of: synthesis of intermediate 13

Intermediate 12 (5.8 g,12 mmol), N1- ([ 1,1':3', 1' -terphenyl) was reacted under nitrogen]-2' -yl-2, 2", 3", 4", 5",6,6"-d 10) benzene-1, 2-diamine (6.2 g,18 mmol), pd (OAc) ₂ (80 mg,0.35 mmol), S-Phos (290 mg,0.7 mmol), naOt-Bu (1.92 g,20 mmol), xylene (50 mL) were added to the flask, the reaction was warmed to 140℃and stirred overnight, cooled to room temperature, and after spin-drying, intermediate 13 (3.9 g,5 mmol) was obtained by means of column chromatography.

And a third step of: synthesis of intermediate 14

Intermediate 13 (3.9 g,5 mmol), triethyl orthoformate (29.6 g,200 mmol), concentrated hydrochloric acid (1 mL) were added to the flask under nitrogen, the reaction was warmed to 100deg.C and stirred overnight, after which the reaction was detected by TLC, cooled to room temperature, dried by spin-drying to give intermediate 14 (3.2 g,4 mmol) by column chromatography.

Fourth step: synthesis of Compound Pt-C

Nitrogen conditions, intermediate 14 (3.2 g,4 mmol), ag ₂ O (0.52 g,2.4 mmol) was added to DCE (40 mL), reacted at room temperature for 12h, after the reaction was completed, the solvent was evaporated under reduced pressure, platinum (1.6 g,4.4 mmol) dichloride (1, 5-cyclooctadiene) was added to a flask, dichlorobenzene (40 mL) was added, and after the reaction was warmed to 200℃and stirred for 24h, cooled to room temperature, and then compound Pt-C (85 mg,0.082 mmol) was obtained by means of column chromatography. The product was identified as the target product and had a molecular weight of 995.3.

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

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. 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.

Device embodiment

Device example 1

First, a glass substrate having an 80nm 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 The deposition was performed sequentially on the ITO anode by thermal vacuum deposition at a rate of 0.2 to 2 a/s in the case of a tray. Co-evaporation of Compound HI and Compound HT as Hole Injection Layer (HIL) with thickness ofThe compound HT is used as a Hole Transport Layer (HTL) with a thickness of +.>Compound EB is used as Electron Blocking Layer (EBL) with thickness +.>Then co-evaporating a compound EB as a first host, a compound HB as a second host, and a first compound Pt2 as a dopant to be used as an emission layer (EML) with a thickness +.>Using compound HB as a Hole Blocking Layer (HBL) with a thickness of/>On the hole blocking layer, co-evaporating compound ET and 8-hydroxyquinoline-lithium (Liq) as Electron Transport Layer (ETL) with thickness of +.>Finally, vapor deposition->LiF as electron injection layer of thickness and vapor depositionIs used as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device.

Device comparative example 1

The embodiment of device comparative example 1 was the same as device example 1 except that compound Pt-a was used in place of compound Pt2 in the light-emitting layer.

Device comparative example 2

The embodiment of device comparative example 2 was the same as device example 1 except that compound Pt-B was used in place of compound Pt2 in the light-emitting layer.

Device comparative example 3

The embodiment of device comparative example 3 is the same as device example 1 except that compound pt—c is used in the light-emitting layer instead of compound Pt2.

The detailed device layer structure and thickness are shown in the following table. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.

Table 1 partial device structures of device examples and comparative examples

The material structure used in the device is as follows:

table 2 shows the data at 1000cd/m ² CIE values of example 1 and comparative examples 1 to 3 measured below, maximum emission wavelength (λ _max ) Current Efficiency (CE) and External Quantum Efficiency (EQE).

Table 2 device data

From the data in table 2, it can be seen that the examples have excellent device performance relative to the comparative examples. In example 1, the light-emitting material having the structure of the specific formula 1 according to the present invention was used, and compared with comparative example 1, comparative example 2 and comparative example 3, the current efficiency was improved by 27.5%,92.7% and 112%, respectively, and the external quantum efficiency was improved by 6%,27.6% and 42%, respectively, thereby achieving a great improvement. In addition, the compound can obtain blue light with the wavelength of about 470nm, and is suitable for commercial application. The above data all demonstrate the advantages that the luminescent materials of the specific structure of the invention exhibit in device performance.

The comparison of the results shows that the compound can realize higher current efficiency and external quantum efficiency by introducing a condensed (hetero) cyclic hydrocarbon structure on the ring E of the structure of the formula 1, compared with alkane substituted compounds (such as Pt-A and Pt-C) with single positions on the ring E of the structure of the formula 1 and compounds (such as Pt-B) without substitution on the ring E, the novel compound can be applied to an organic electroluminescent device, and thus the comprehensive performance of the device is improved.

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

Claims

1. A compound having the structure of formula 1:

in the formula (1) of the present invention,

The metal M is selected from metals with relative atomic mass of more than 40;

y is selected identically or differently on each occurrence from 1,2,3,4 or 5;

2. The compound of claim 1, wherein said M is selected from Cu, ag, au, ru, rh, pd, os, ir, or Pt; preferably, wherein said M is selected from Pt or Pd; more preferably, wherein said M is selected from Pt.

3. The compound of claim 1 or 2, wherein the ring a, ring B, ring E are, identically or differently, selected from five-membered unsaturated carbocycles, aromatic rings having 6-30 carbon atoms, heteroaromatic rings having 3-30 carbon atoms, or combinations thereof;

preferably, wherein the rings a, B, E are identically or differently selected at each occurrence from five-membered unsaturated carbocycles, aromatic rings having 6-18 carbon atoms, heteroaromatic rings having 3-18 carbon atoms, or combinations thereof;

more preferably, wherein the ring a, ring B, ring E are selected identically or differently at each occurrence from a benzene ring, a pyridine ring, an indene ring, a fluorene ring, an indole ring, a carbazole ring, an indolocarbazole ring, a benzofuran ring, a dibenzofuran ring, a benzothiophene ring, a dibenzosilole ring, a benzothiophene ring, a dibenzothiophene ring, a dibenzoselenophene ring, a cyclopentadiene ring, a furan ring, a thiophene ring, a silole ring, or a combination thereof.

4. A compound according to any one of claims 1 to 3, wherein the rings D are, identically or differently, selected from unsaturated heterocycles having 3 to 18 carbon atoms;

preferably, wherein the ring D is selected identically or differently on each occurrence from an imidazole carbene ring or a benzimidazole carbene ring.

5. The compound of any one of claims 1-4, wherein the L ₁ Is selected identically or differently on each occurrence from single bonds, O, S, (SiR "R") _y ，NR”，(CR”R”) _y Or a combination thereof;

preferably, wherein said L ₁ Each occurrence of which is identically or differently selected from a single bond, O or S;

more preferably, wherein said L ₁ Selected from single bonds.

6. The compound of any one of claims 1-5, wherein the K ₁ -K ₄ Selected from single bonds.

7. The compound of any one of claims 1-6, wherein the Z ₁ Selected from N, Z ₂ ，Z ₃ Selected from C.

8. The compound of any one of claims 1-7, wherein two adjacent atoms in the ring E are carbon atoms and are each linked to two "x" in formula 2.

9. The compound according to claim 1 or 2, wherein the compound has a structure represented by one of formula 1-1 to formula 1-15:

in the formulae 1-1 to 1-15,

10. The compound of claim 9, wherein said X ₁ -X ₂₀ Is selected from CR, identically or differently at each occurrence _x 。

11. The compound of any one of claims 1-10, wherein n is 1 or 2.

12. The compound of any one of claims 1-11, wherein said L ₂ Is selected identically or differently on each occurrence from single bonds, O, S, (SiR "R") _y ，NR”，(CR”R”) _y Or a combination thereof;

preferably, wherein said L ₂ Each occurrence of which is identically or differently selected from a single bond, O or S;

more preferably, wherein said L ₂ Selected from O.

13. The compound of any one of claims 1-12, wherein the Z is identically or differently selected from C (R _z ) ₂ 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 groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, and combinations thereof;

preferably, R _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof.

14. The compound of claim 9, wherein said R, R ", R _x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 arylsilane having 6 to 20 carbon atoms, and combinations thereof;

preferably, wherein said R, R ", R _x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, methyl, deuterated methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, carbazolyl, indolyl, benzofuranyl Dibenzofuranyl, benzothiophenyl, dibenzosilol, benzothiophenyl, dibenzothienyl, dibenzoselenophenyl, and combinations thereof.

15. The compound of claim 1, wherein the compound has Pt (L _a )(L _b ) Represented structure, wherein L _a And L _b A first ligand and a second ligand coordinated to the metal Pt, respectively, the L _a Selected from the group consisting of:

/>

"t-Bu" in the structure represents tert-butyl, and "i-Pr" represents isopropyl;

the L is _a "#" in the structure indicates that the structure is identical to L _b The position of the connection;

wherein ligand L _b Selected from the group consisting of:

/>

the L is _b In the structure ofRepresenting the structure and L _a The position of the "#" connection in (a);

preferably, the compound is selected from the group consisting of compounds Pt1 to Pt664, compounds Pt1 to Pt664 having Pt (L) _a )(L _b ) Represented structure, the L _a And said L _b Respectively correspond to the structures selected from the following table:

/>

16. an organic electroluminescent device, comprising:

an anode is provided with a cathode,

a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of any one of claims 1-15.

17. The organic electroluminescent device of claim 16, wherein the organic layer is a light emitting layer and the compound is a light emitting material.

18. The organic electroluminescent device of claim 17, wherein the device emits blue or white light.

19. The organic electroluminescent device of claim 17, wherein the light emitting layer comprises at least one host material; preferably, the light emitting layer comprises at least two host materials; more preferably, the host material is selected from the group consisting of chemical groups: 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.

20. A compound composition comprising a compound of any one of claims 1-15.