CN116813597A

CN116813597A - Organic electroluminescent material and device thereof

Info

Publication number: CN116813597A
Application number: CN202210262961.4A
Authority: CN
Inventors: 李锋; 王阳; 杨刚; 姚剑飞; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2022-03-17
Filing date: 2022-03-17
Publication date: 2023-09-29
Also published as: KR20230136057A; JP2023138428A; KR102840831B1; JP7557895B2

Abstract

Organic electroluminescent materials and devices thereof are disclosed. The organic electroluminescent material is a compound with the structure of Formula 1. These new compounds can be used in electroluminescent devices, such as being used as host materials, transmission materials, etc. in organic electroluminescent devices, and can provide better device performance. , especially the improvement of device life. An organic electroluminescent device containing the compound and a compound composition containing the compound 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 a heterocyclic 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.

CN113227085a discloses an organic compound of the following formula and an organic light emitting device comprising the compound:wherein Ar is ₂ And Ar is a group ₃ Each independently is hydrogen, or substituted or unsubstituted C _6-60 Aryl, L is phenylene, biphenyldiyl, terphenyldiyl, naphthalenediyl, or phenylene substituted with naphthalene. The application discloses in specific structures the following compounds:This application discloses triazine backbone compounds which must have directly bonded dibenzothiophene groups, and does not disclose and teach the compounds of the present application having the structure of formula 1, and their use in organic electroluminescent devices.

WO2019190101A1 discloses an organic light emitting device, the light emitting layer of which comprises an organic compound having the following general structural formula:wherein X is ² Is N-L ⁶ -Ar ⁷ O, S, or CR' R ", further discloses that the compounds may have the following secondary general structure:The application discloses in specific structures the following compounds:The application does not disclose and teach the compounds of the present application having the structure of formula 1, in particular the method of the present application by L ³ Or L ⁵ A compound with substituted or unsubstituted phenyl substituent at the 1-position of the diphenyl five-membered ring connected with triazine, and application thereof in an organic electroluminescent device.

US20190198775A1 discloses a combination comprising a compound having the general structure:and Ar is Ar ¹ To Ar ³ At least one of which has the following structure:It is further disclosed that the compounds may have the following secondary general structure:The specific structure disclosed therein is:although a large number of compounds having both dibenzofive-membered heterocyclic and triazine structures are disclosed in this application, the compounds of the present application having the structure of formula 1, and their effects on device performance, are not disclosed and taught.

CN108250189a discloses an organic compound of the following formula and an organic light emitting device comprising the compound:wherein X is O, S or SiR ₅ R ₆ ；R _1a To R _4a Each independently is L ₁ -HAr ₁ Or A ₁ ，R _1a To R _4a At least one of them is-HAr ₁ ；R _1b To R _4b Each independently is L ₂ -HAr ₂ Or A ₂ ，R _1b To R _4b At least one of them is-HAr ₂ ；HAr ₁ And HAr ₂ Can each independently be->And at least two of X1 to X3 are selected from N. The application discloses in specific structures the following compounds:This application does not disclose and teach the compounds of the present application having the structure of formula 1, and in particular does not disclose and teach compounds wherein the 1-position of the dibenzofuran is a substituted or unsubstituted phenyl group and its effect on device performance.

CN110294703a discloses a compound represented by chemical formula 1 and A compound represented by a combination of chemical formula 2 and an organic light emitting device including the same:wherein X is ¹ And X ² Independently O or S, adjacent two of formula 1 are linked to a formula 2. The application discloses in specific structures the following compounds:this application does not disclose or teach the compounds of the present application having the structure of formula 1 and their effect on device performance.

Disclosure of Invention

The present application aims to provide a series of heterocyclic compounds having the structure of formula 1, to solve at least some of the above problems. These novel compounds can be used in organic electroluminescent devices, for example as host materials, transport materials, etc. in organic electroluminescent devices, and can provide better device performance, especially improved device lifetime.

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

wherein,,

x is selected from O, S or Se;

X ₁ -X ₆ is selected from CR, identically or differently at each occurrence _x Or N;

Z ₁ -Z ₈ is selected from C, CR identically or differently on each occurrence _z Or N, and Z ₁ -Z ₄ One of which is selected from C and is with L ₂ Are connected;

ar is selected, identically or differently, for each occurrence, from a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having from 3 to 30 carbon atoms, or a combination thereof;

L ₁ Each occurrence is identically or differently selected from the group consisting of substituentsOr an unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 16 carbon atoms, or a combination thereof;

L ₂ each occurrence is identically or differently selected from a single bond, 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;

R _y each occurrence, identically or differently, represents mono-, poly-or unsubstituted;

R _x 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;

R _y 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 heterocycle having 3 to 20 ring atomsA group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl silyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyl germanium group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl germanium group having 6 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 Can optionally be linked to form a ring;

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

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

According to another embodiment of the present invention, an organic electroluminescent device is disclosed, which includes: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising the compound of the previous embodiment.

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

The invention discloses a series of heterocyclic compounds with a structure shown in a formula 1. The novel compounds can be applied to organic electroluminescent devices, can provide better device performance, especially the service life of the devices is prolonged, and the comprehensive performance of the devices is greatly improved.

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. 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. U.S. patent application publication No. 2, which may be incorporated by reference in its entirety A description of protective layers is found in 004/0174116.

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 thatE-delayed fluorescence requires that the luminescent material have a small mono-triplet energy gap (Δe _S-T ). Organic non-metal containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor Charge Transfer (CT) type emission. The spatial separation of HOMO from LUMO in these donor-acceptor compounds generally results in a small Δe _S-T . These states may include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).

Definition of terms for substituents

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

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

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

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

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

Alkynyl-as used herein, straight chain alkynyl is contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl and the like. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and phenylethynyl. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl-4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl. In addition, aryl groups may be optionally substituted.

Heterocyclyl or heterocycle-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms including at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxacycloheptatrienyl, thietaneyl, azepanyl and tetrahydrosilol. In addition, the heterocyclic group may be optionally substituted.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, more preferably a heteroaryl group having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furodipyridine, benzothiophene, thienodipyridine, benzoselenophene, selenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-boron, 1, 3-aza-boron, 1-aza-boron-4-aza, boron-doped compounds, and the like. In addition, heteroaryl groups may be optionally substituted.

Alkoxy-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy group may be optionally substituted.

Aryloxy-as used herein, is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenoxy. In addition, the aryloxy group may be optionally substituted.

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

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

Arylsilane-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenyl silyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl. In addition, arylsilane groups may be optionally substituted.

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

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

The term "aza" in azadibenzofurans, azadibenzothiophenes and the like means that one or at least two C-H groups in the corresponding aromatic fragment are replaced by nitrogen atoms. 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, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, alkylgermanium, arylgermanium, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, any one or more of which may be substituted with one or at least two groups selected from 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 heteroaryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkoxy having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 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 compound having the structure of formula 1 is disclosed:

wherein,,

x is selected from O, S or Se;

L ₁ The same or different at each occurrence is selected from the group consisting of substituted or unsubstituted arylene groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylene groups having 3 to 16 carbon atoms, or a combination thereof;

R _x and R is _z And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted, having 1-20 carbonsAn alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, 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 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;

R _y And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, acyl, carbonyl, carboxylic acidA 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 Can optionally be linked to form a ring;

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

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

Herein, "adjacent substituent R _x Can optionally be linked to form a ring ", is intended to mean groups of substituents adjacent thereto, e.g. any two substituents R _x 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.

Herein, "adjacent substituent R _y Can optionally be linked to form a ring ", is intended to mean groups of substituents adjacent thereto, e.g. any two substituents R _y 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.

Herein, "adjacent substituent R _z Can optionally be linked to form a ring ", is intended to mean groups of substituents adjacent thereto, e.g. any 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 invention, wherein X is selected from O or S.

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

According to one embodiment of the invention, wherein X ₁ -X ₆ Is selected from CR, identically or differently at each occurrence _x 。

According to one embodiment of the invention, wherein X ₁ -X ₆ Is selected from CR, identically or differently at each occurrence _x Or N, and X ₁ -X ₆ At least one of which is selected from N, e.g. X ₁ -X ₆ One or both of which are selected from N.

According to one embodiment of the invention, wherein Z ₁ -Z ₈ Is selected identically or differently on each occurrence from C or CR _z And Z is ₁ -Z ₄ One of which is selected from C and is with L ₂ Are connected.

According to one embodiment of the invention, wherein Z ₁ -Z ₈ Is selected from C, CR identically or differently on each occurrence _z Or N, and Z ₁ -Z ₈ At least one of which is selected from N, e.g. Z ₁ -Z ₈ One or both of which are selected from N.

According to one embodiment of the invention, wherein L ₁ And is selected identically or differently on each occurrence from substituted or unsubstituted arylene groups having 6 to 20 carbon atoms.

According to one embodiment of the invention, wherein L ₁ And is selected identically or differently on each occurrence from substituted or unsubstituted arylene groups having 6 to 12 carbon atoms.

According to one embodiment of the invention, wherein L ₁ The same or different at each occurrence is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, or a combination thereof.

According to one embodiment of the invention, wherein L ₂ The groups are selected, identically or differently, on each occurrence from single bonds, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroarylene groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein L ₂ The groups are selected, identically or differently, on each occurrence from single bonds, substituted or unsubstituted arylene groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroarylene groups having 3 to 12 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein L ₂ Each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, or a combination thereof.

According to one embodiment of the invention, wherein L ₂ And is selected identically or differently on each occurrence from a single bond or a phenylene group.

According to one embodiment of the invention, wherein the compound has the structure of formula 1-1:

wherein,,

L ₁ The same or different at each occurrence is selected from substituted or unsubstituted arylene groups having 6 to 30 carbon atoms;

L ₂ each occurrence is identically or differently selected from a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms;

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 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, and combinations thereof;

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

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

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

According to one embodiment of the invention, wherein 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 groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R _x ，R _y And R is _z Each occurrence is identically or differently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

According to one embodiment of the invention, wherein R _x And R is _z Each occurrence is identically or differently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, and combinations thereof.

According to one embodiment of the invention, wherein Ar is selected, identically or differently, for each occurrence, from a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having from 3 to 20 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein Ar is selected, identically or differently, for each occurrence, from a substituted or unsubstituted aryl group having from 6 to 12 carbon atoms, a substituted or unsubstituted heteroaryl group having from 3 to 12 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein Ar is selected identically or differently for each occurrence from the group consisting of: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

According to an embodiment of the invention, the compound is selected from the group consisting of compounds a-1 to a-262, wherein the specific structure of compounds a-1 to a-262 is shown in claim 8.

According to one embodiment of the invention, wherein the hydrogen energy in compounds a-1 to a-262 is partially or fully substituted by deuterium.

According to an embodiment of the present invention, an organic electroluminescent device is disclosed, which includes: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising a compound according to any one of the preceding embodiments.

According to one embodiment of the invention, the organic layer comprising the compound is a light emitting layer, the compound is a host compound, and the light emitting layer comprises at least a first metal complex.

According to one embodiment of the present invention, wherein the first metal complex has M (L _a ) _m (L _b ) _n (L _c ) _q Is of the general formula (I);

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

ligand L _a 、L _b And L _c A first ligand, a second ligand and a third ligand which are coordinated with the metal M respectively, and a ligand L _a 、L _b And L _c May be the same or different;

ligand L _a 、L _b And L _c Can optionally be connected to Forming a multidentate ligand; for example, L _a 、L _b And L _c Any two of which may be linked to form a tetradentate ligand; also for example, L _a 、L _b And L _c Can be interconnected to form a hexadentate ligand; or also e.g. L _a 、L _b And L _c None are linked so as not to form a multidentate ligand;

m is 1, 2 or 3; n is 0, 1 or 2; q is 0, 1 or 2; the sum of M, n, q is equal to the oxidation state of the metal M; when m is greater than or equal to 2, a plurality of L _a May be the same or different; when n is 2, two L _b May be the same or different; when q is 2, two L _c May be the same or different;

ligand L _a Has a structure as shown in formula 2:

ring C ₁ And ring C ₂ The same or different at each occurrence is selected from an aromatic ring having 5 to 30 ring atoms, a heteroaromatic ring having 5 to 30 ring atoms, or a combination thereof;

Q ₁ and Q ₂ Selected identically or differently on each occurrence from C or N;

R ₁₁ and R is ₁₂ Each occurrence, identically or differently, represents mono-substituted, poly-substituted or unsubstituted;

R ₁₁ and R is ₁₂ And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted Aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

adjacent substituents R ₁₁ 、R ₁₂ Can optionally be linked to form a ring;

ligand L _b And L _c The same or different at each occurrence is selected from monoanionic bidentate ligands.

According to one embodiment of the invention, wherein the ligand L _b And L _c And is selected identically or differently on each occurrence from the group consisting of:

wherein,,

R _a and R is _b 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 alkyl having 1 to 20 ring carbon atomsA heteroatom of carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminogermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aminogroup having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfonyl group, a phosphono group, and combinations thereof;

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

In this embodiment, "adjacent substituent 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, 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, and R _C1 And R is _C2 Between, substituent R _a And R is _N2 Between, substituent R _b And R is _N2 Between, any of these substituent groupsOne or more may be joined to form a ring. Obviously, these substituents may not all be linked to form a ring.

According to one embodiment of the invention, wherein the first metal complex has Ir (L _a ) _m (L _b ) _3-m And a structure represented by formula 3:

wherein,,

m is 0, 1, 2 or 3; when m is 2 or 3, a plurality of L _a The same or different; when m is 0 or 1, a plurality of L _b The same or different;

T ₁ -T ₆ each occurrence is identically or differently selected from CR _T Or N;

R _a 、R _b and R is _d Each occurrence, identically or differently, represents mono-substituted, poly-substituted, or unsubstituted;

R _a 、R _b 、R _d And R is _t 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 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 having 6 to 20 carbon atomsGermanium groups, 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, mercapto groups, hydroxyl groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof;

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

adjacent substituents R _d ，R _T Can optionally be linked to form a ring.

In this embodiment, "adjacent substituent R _a ，R _b Can optionally be linked to form a ring ", is intended to mean groups of adjacent substituents therein, e.g. two adjacent substituents R _a Between two adjacent substituents R _b Between, and adjacent substituents R _a And R is _b 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.

In this embodiment, "adjacent substituent R _d ，R _T Can optionally be linked to form a ring ", is intended to mean groups of adjacent substituents therein, e.g. two adjacent substituents R _T Between two adjacent substituents R _d 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 T ₁ -T ₆ At least one of them is selected from CR _T And said R _T Selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

According to one embodiment of the invention, wherein T ₁ -T ₆ At least one of them is selected from CR _T And said R _T Selected from fluorine or cyano.

According to one embodiment of the invention, wherein T ₁ -T ₆ At least two of them are selected from CR _T And one of R _T Selected from fluorine or cyano, another R _T Selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

According to one embodiment of the invention, wherein T ₁ -T ₆ Is selected from CR, identically or differently at each occurrence _T Or N, and T ₁ -T ₆ At least one of which is selected from N, e.g. T ₁ -T ₆ One or both of which are selected from N.

According to one embodiment of the present invention, wherein the first metal complex is selected from the group consisting of, but not limited to, GD1 to GD76, wherein the specific structure of GD1 to GD76 is as follows:

according to one embodiment of the invention, wherein the organic layer comprising the compound is an electron transporting layer and the compound is an electron transporting compound.

According to one embodiment of the invention, wherein the light emitting layer in the organic electroluminescent device further comprises a second host compound comprising 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 invention, wherein the light emitting layer in the organic electroluminescent device further comprises a second host compound comprising at least one chemical group selected from the group consisting of: benzene, carbazole, indolocarbazole, fluorene, silafluorene, and combinations thereof.

According to one embodiment of the present invention, wherein the second host compound in the organic electroluminescent device has a structure represented by formula 3:

wherein,,

L _T each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;

t is selected identically or differently for each occurrence from C, CR _t Or N;

R _t 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 aralkyl having 1 to 20 carbon atoms An alkoxy group of atoms, a substituted or unsubstituted aryloxy group of atoms having from 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group of atoms having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group of atoms having from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of atoms having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group of atoms having from 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group of atoms having from 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group of atoms having from 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermanium group of atoms having from 3 to 20 carbon atoms, a substituted or unsubstituted arylgermanium group of atoms having from 6 to 20 carbon atoms, a substituted or unsubstituted amino group of atoms having from 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

Ar ₁ the same or different at each occurrence is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, and combinations thereof;

adjacent substituents R _t Can optionally be linked into a ring.

Herein, "adjacent substituent R _t Can optionally be linked to form a ring ", is intended to mean groups of substituents adjacent thereto, e.g. any two substituents R _t In between, any one or more of these substituent groups may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.

According to one embodiment of the present invention, wherein the second host compound in the organic electroluminescent device has a structure represented by formula 4:

wherein,,

g is selected identically or differently on each occurrence from C (R _g ) ₂ 、NR _g O or S;

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

adjacent substituents R _t 、R _g Can optionally be linked to form a ring.

Herein, "adjacent substituent R _t 、R _g Can optionally be linked to form a ring ", intended to mean two adjacent substituents R _t Between, individualAdjacent substituents R _g Between and adjacent substituents R _t And R is _g Between which any one or more of these adjacent 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 in formula 3 and formula 4, T is selected identically or differently for each occurrence from C and CR _t 。

According to one embodiment of the invention, wherein, in formula 3, T is selected, identically or differently, for each occurrence, from C, CR _t Or N, and at least one of them is selected from N, for example one T or two T are selected from N.

According to one embodiment of the invention, wherein, in formula 4, T is selected, identically or differently, for each occurrence, from C, CR _t Or N, and at least one of them is selected from N, for example one T or two T are selected from N.

According to an embodiment of the present invention, wherein the second host compound in the organic electroluminescent device has a structure represented by one of formulas 3-a to 3-j:

wherein,,

t is selected identically or differently for each occurrence from CR _t Or N;

R _t 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 unsubstitutedA heterocyclic group having 3 to 20 ring atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylgermyl group having 3 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 hydroxy group, a mercapto group, a sulfinyl group, a phosphono group, and combinations thereof;

adjacent substituents R _t Can optionally be linked into a ring.

According to one embodiment of the invention, wherein, in formulae 3-a to 3-j, T is selected identically or differently for each occurrence from CR _t Or N, and at least one of them is selected from N, for example one T or two T are selected from N.

According to an embodiment of the present invention, wherein the second host compound in the organic electroluminescent device has a structure represented by one of formulae 4-a to 4-f:

wherein,,

t is selected identically or differently for each occurrence from CR _t Or N;

adjacent substituents R _t 、R _g Can optionally be linked to form a ring.

According to one embodiment of the invention, wherein, in formulae 3-a to 3-j and formulae 4-a to 4-f, T is selected identically or differently for each occurrence from CR _t 。

According to one embodiment of the invention, wherein, in formulae 4-a to 4-f, T is selected identically or differently from CR for each occurrence _t Or N, and at least one of them is selected from N, for example one T or two T are selected from N.

According to one embodiment of the invention, wherein at least one of all T is selected from N, e.g. one or two are N.

According to one embodiment of the invention, the organic electroluminescent device emits green light.

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

According to one embodiment of the present invention, the first metal complex is doped in the compound and the second compound, and the first compound accounts for 1% -30% of the total weight of the first organic layer.

According to one embodiment of the present invention, the first metal complex is doped in the compound and the second compound, and the first compound accounts for 3% -13% of the total weight of the first organic layer.

According to one embodiment of the present invention, a compound composition is disclosed comprising a compound according to any of the preceding embodiments.

According to one embodiment of the present invention, an electronic device is disclosed, which comprises the organic electroluminescent device according to 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 hosts, a variety of luminescent dopants, 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 A-1

Step 1: synthesis of intermediate C

A (11.0 g,29.7 mmol), B (12.6 g,44.6 mmol), pd (PPh) were combined in a three neck round bottom flask ₃ ) ₄ (0.69g,0.59mmol)，K ₂ CO ₃ (8.21 g,59.4 mmol) was added to toluene (80 mL), etOH (20 mL), H ₂ O (20 mL), in N ₂ Under protection, heat reflux overnight. TLC plate confirmed the end of the reaction, stopped heating, cooled to room temperature, separated, aqueous phase extracted with DCM, combined organic phases, anhydrous Na ₂ SO ₄ Drying, filtering, and concentrating under reduced pressure. The crude product was chromatographed on silica gel (PE) to give intermediate C (11.2 g,28.05 mmol) as a white solid in 94.4% yield.

Step 2: synthesis of intermediate D

In a three neck round bottom flask, C (11.2 g,28.05 mmol), pinacol biborate (10.7 g,42.07 mmol), pd (dppf) Cl ₂ (0.41 g,0.56 mmol) KOAc (5.51 g,56.1 mmol) was added to 1, 4-dioxane (120 mL), at N ₂ Under protection, heat reflux overnight. The TLC plate confirms the end of the reaction, stops heating, and cools to room temperature. The reaction was filtered through celite and the filtrate concentrated under reduced pressure, and the crude product was chromatographed on silica gel (PE/dcm=5:1 to 2:1) to give intermediate D (10.3 g,23.08 mmol) as a white solid in 82.3% yield.

Step 3: synthesis of Compound A-1

In a three neck round bottom flask, D (4.0 g,8.96 mmol), E (3.2 g,8.96 mmol), pd (PPh ₃ ) ₄ (0.31g,0.27mmol)，K ₂ CO ₃ (2.48 g,17.92 mmol) was added to toluene (48 mL), etOH (12 mL), H ₂ O (12 mL), in N ₂ Under protection, heat reflux overnight. The TLC plate confirms the end of the reaction, stops heating, cools to room temperature, and suction-filters under reduced pressure, the resulting solid being washed sequentially with water and methanol. The solid was recrystallized from toluene to give compound A-1 (5.0 g,7.79 mmol) as a white solid in 87.0% yield. The product was identified as the target product compound A-1, molecular weight 641.2.

Synthesis example 2: synthesis of Compound A-3

Step 1: synthesis of Compound A-3

In a three neck round bottom flask, D (4.46 g,10.0 mmol), F (3.58 g,10.0 mmol), pd (PPh ₃ ) ₄ (0.35g,0.30mmol)，K ₂ CO ₃ (2.76 g,20.0 mmol) was added to toluene (48 mL), etOH (12 mL), H ₂ O (12 mL), in N ₂ Under protection, heat reflux overnight. The TLC plate confirms the end of the reaction, stops heating, cools to room temperature, and suction-filters under reduced pressure, the resulting solid being washed sequentially with water and methanol. The solid was recrystallized from toluene to give compound A-3 (5.0 g,7.79 mmol) as a white solid in 77.9% yield. The product was identified as the target product compound A-3, molecular weight 641.2.

Synthesis example 3: synthesis of Compound A-4

Step 1: synthesis of Compound A-4

In a three neck round bottom flask, D (4.46G, 10.0 mmol), G (3.58G, 10.0 mmol), pd (PPh ₃ ) ₄ (0.23g,0.20mmol)，K ₂ CO ₃ (2.76 g,20.0 mmol) was added to toluene (40 mL), etOH (10 mL), H ₂ O (10 mL), in N ₂ Under protection, heat reflux overnight. The TLC plate confirms the end of the reaction, stops heating, cools to room temperature, and is pumped under reduced pressureThe solid obtained was filtered and washed successively with water and methanol. The solid was recrystallized from toluene to give compound A-4 (5.8 g,9.04 mmol) as a white solid in 90.4% yield. The product was identified as the target product compound A-4, molecular weight 641.2.

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

Device embodiment

Device example 1

First, a glass substrate having 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 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. The compound HI is used as a Hole Injection Layer (HIL). The compound HT serves as a Hole Transport Layer (HTL). Compound H1 acts as an Electron Blocking Layer (EBL). Then, the compound GD23 was doped in the compound H1 and the compound a-1 of the present invention, and co-evaporation was used as an emission layer (EML). Compound H2 was used as a Hole Blocking Layer (HBL). On the hole blocking layer, the compound ET and 8-hydroxyquinoline-lithium (Liq) were co-evaporated as an Electron Transport Layer (ETL). Finally, 8-hydroxyquinoline-lithium (Liq) with a thickness of 1nm was evaporated as an electron injection layer, and 120nm of aluminum was evaporated as a cathode. The device was then transferred back to the glove box and packaged with a glass lid to complete the device.

Device example 2

Device example 2 was prepared the same as device example 1 except that compound a-3 was used in place of compound a-1 in the light emitting layer (EML).

Device example 3

Device example 3 was prepared the same as device example 1 except that compound a-4 was used in place of compound a-1 in the light emitting layer (EML).

Device comparative example 1

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

Device comparative example 2

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

Device comparative example 3

Device comparative example 3 was prepared the same as device example 1 except that compound C-3 was used in place of compound a-1 in the light emitting layer (EML).

Device comparative example 4

Device comparative example 4 was prepared the same as device example 1 except that compound C-4 was used in place of compound a-1 in the light emitting layer (EML).

Device comparative example 5

Device comparative example 5 was prepared the same as device example 1 except that compound C-5 was used in place of compound a-1 in the light emitting layer (EML).

Device comparative example 6

Device comparative example 6 was prepared the same as device example 1 except that compound C-6 was used in place of compound a-1 in the light emitting layer (EML).

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 device structures of device examples 1 to 3 and comparative examples 1 to 6

The material structure used in the device is as follows:

table 2 shows the results at 15mA/cm ² CIE data, external Quantum Efficiency (EQE) and Current Efficiency (CE) measured at constant current; at 80mA/cm ² Device lifetime measured at constant current (LT 95). Normalization processing was performed based on the data of comparative example 1.

Table 2 device data for examples 1 to 3 and comparative examples 1 to 6

Discussion:

in example 3 and comparative example 1, the phosphorescent dopant GD23 was doped in the compound a-4 of the invention and the compound C-1 of the non-invention, respectively. Compounds A-4 and C-1 differ only in that the dibenzofuranyl group directly bonded to the triazine is replaced with a dibenzothienyl group, and EQE and CE of example 3 are comparable to comparative example 1, but the device lifetime is greatly improved by 61%. The compound with the structure shown in the formula 1 has longer service life compared with the compound in which dibenzothiophene is directly connected with triazine, and is applied to electroluminescent devices.

In example 2 and comparative example 2, the phosphorescent dopant GD23 was doped in the compound a-3 of the invention and the compound C-2 of the non-invention, respectively. The only difference between compounds A-3 and C-2 is the substitution of aryl groups on dibenzofuranyl groups linked to the triazine via phenylene groups, and EQE and CE of example 2 are comparable to those of comparative example 2, but the device lifetime is greatly improved by 136%. The compound with the structure shown in the formula 1 has longer service life when being applied to electroluminescent devices compared with a compound with aryl substituent at the non-1-position of dibenzofive-membered ring with bridging group between triazine.

In example 2 and comparative example 3, the phosphorescent dopant GD23 was doped in the compound a-3 of the invention and the compound C-3 of the non-invention, respectively. The only difference between compounds A-3 and C-3 is whether the dibenzofuran linked to the triazine through the phenylene group forms a fused ring through the 1-substituted phenyl group, the EQE and CE of example 2 are slightly improved, and the device lifetime is improved by 53%. The compound with the structure of the formula 1 is shown to have higher efficiency and longer service life in electroluminescent devices compared with the compound with the condensed aryl substituent on the 1-position of the dibenzofive-membered ring with the bridging group between the compound and the triazine.

In example 1 and comparative example 4, the phosphorescent dopant GD23 was doped in the compound a-1 of the invention and the compound C-4 of the non-invention, respectively. The difference between compounds A-1 and C-4 is mainly that the phenyl substituent of dibenzofuranyl linked through phenylene is replaced by a substituted triazinyl, the EQE and CE of example 1 are improved by about 36% and the device lifetime is improved by 45.4%. The compound with the structure shown in the formula 1 has higher efficiency and longer service life when being applied to electroluminescent devices compared with a compound with substituted six-membered heteroaryl at the 1-position of dibenzofive-membered ring with bridging group between triazine.

In example 2 and comparative example 5, the phosphorescent dopant GD23 was doped in the compound a-3 of the invention and the compound C-5 of the non-invention, respectively. The difference between compounds A-3 and C-5 is mainly whether the dibenzofuranyl group with the 1-position phenyl substitution is linked to the triazine via a phenylene group, the EQE and CE of example 2 are improved by about 5% and the device lifetime is improved by 28.2%. The compound with the structure shown in the formula 1 can be applied to electroluminescent devices to improve the comprehensive performance of the devices compared with the compound in which the dibenzofive-membered ring with aryl substituent at the 1-position is directly connected with triazine.

In example 2 and comparative example 6, the phosphorescent dopant GD23 was doped in the compound a-3 of the present invention and the compound C-6 of the non-present invention, respectively, and the compound a-3 and the compound C-6 were different only in that the 1-position of the dibenzofuranyl group linked to the triazine through the phenylene group had an aryl substituent. The EQE and CE of example 2 are comparable to those of comparative example 6, but the device lifetime is improved by 28.7%. The compound with the structure shown in the formula 1 has longer service life when being applied to electroluminescent devices compared with a compound without aryl substituent on dibenzofive-membered ring with bridging group between triazine.

In summary, when the compound of the present invention is used as a host material of a light emitting layer, the balance between electron and hole transport of the material is improved, and compared with the use of a non-compound of the present invention as a host material of a light emitting layer, the device efficiency (EQE and CE) is equivalent or improved to a certain extent, and the lifetime of the device is greatly improved, so that the overall performance of the device is greatly improved. This is an important aid to the industry.

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:

wherein,,

x is selected from O, S or Se;

R _y 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 alkyl having 3 to 20 ring carbon atomsSubstituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl 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 alkylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxy, mercapto, sulfonyl, phosphonyl, and combinations thereof;

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

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

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

2. The compound of claim 1, wherein X is selected from O or S; preferably, X is O.

3. The compound of claim 1 or 2, wherein X ₁ -X ₆ Is selected from CR, identically or differently at each occurrence _x The method comprises the steps of carrying out a first treatment on the surface of the And/or Z ₁ -Z ₈ Is selected identically or differently on each occurrence from C or CR _z And Z is ₁ -Z ₄ One of which is selected from C and is with L ₂ Are connected.

4. A compound as claimed in any one of claims 1 to 3, L ₁ The same or different at each occurrence is selected from substituted or unsubstituted arylene groups having 6 to 20 carbon atoms;

preferably L ₁ The same or different at each occurrence is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, or a combination thereof.

5. The compound of any one of claims 1-4, wherein L ₂ Each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms, or a combination thereof;

preferably L ₂ Each occurrence is identically or differently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, or a combination thereof;

More preferably L ₂ And is selected identically or differently on each occurrence from a single bond or a phenylene group.

6. The compound of any one of claims 1-5, wherein 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 groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms, and combinations thereof;

preferably, R _x ，R _y And R is _z Each occurrence is identically or differently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

7. The compound of claim 1, wherein Ar is, identically or differently, selected from the group consisting of substituted or unsubstituted aryl groups having 6-20 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-20 carbon atoms, or a combination thereof;

Preferably, ar is selected identically or differently on each occurrence from the group consisting of: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and combinations thereof.

8. The compound of claim 1, wherein the compound is selected from the group consisting of:

optionally, hydrogen in the above compounds a-1 to a-262 can be partially or fully substituted with deuterium.

9. An organic electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising the compound of any one of claims 1-8.

10. The organic electroluminescent device of claim 9, wherein the organic layer comprising the compound is a light-emitting layer, the compound is a host compound, and the light-emitting layer comprises at least a first metal complex.

11. The organic electroluminescent device of claim 10, wherein the first metal complex has a structure of M (L _a ) _m (L _b ) _n (L _c ) _q Is of the general formula (I);

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

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

ligand L _a Has a structure as shown in formula 2:

ring C ₁ And ring C ₂ Each occurrence of which is identically or differently selected from aromatic rings having 5 to 30 ring atoms, having 5 to 30A heteroaromatic ring of ring atoms, or a combination thereof;

R ₁₁ and R is ₁₂ 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;

ligand L _b And L _c The same or different at each occurrence is selected from monoanionic bidentate ligands;

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

wherein,,

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 heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;

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

12. The organic electroluminescent device of claim 10, wherein the light-emitting layer further comprises a second host compound comprising 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;

preferably, the second host compound comprises at least one chemical group selected from the group consisting of: benzene, carbazole, indolocarbazole, fluorene, silafluorene, and combinations thereof.

13. The organic electroluminescent device of claim 12, wherein the second host compound has a structure represented by formula 3 or formula 4:

wherein,,

R _t 、R _g and is selected, identically or differently, on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstitutedCycloalkyl 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 aryl having 7 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 silyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium group having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium group having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylate, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

Ar ₁ the same or different at each occurrence is selected from substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, or combinations thereof;

Adjacent substituents R _t 、R _g Can optionally be linked to form a ring;

preferably, the second host compound has a structure represented by one of formulas 3-a to 3-j, and formulas 4-a to 4-f:

wherein, in the formulae 3-a to 3-j, T, L _T 、Ar ₁ Has the same definition as in formula 3;

wherein, in the formulae 4-a to 4-f, T, G, L _T 、Ar ₁ Has the same definition as in formula 4.

14. A compound composition comprising a compound of any one of claims 1-8.