CN116178298A

CN116178298A - Novel organic electroluminescent material and device thereof

Info

Publication number: CN116178298A
Application number: CN202111411226.7A
Authority: CN
Inventors: 丁华龙; 郑仁杰; 胡俊涛; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2021-11-25
Filing date: 2021-11-25
Publication date: 2023-05-30

Abstract

Disclosed are a novel organic electroluminescent material and a device thereof. The novel organic electroluminescent material is a conjugated system compound containing two N-containing five-membered heterocycles, which is represented by a formula 1, and can be used as a charge transport material and a charge injection material in an organic electroluminescent device, so that the balance of electrons and holes in the device is improved, the performance of the organic electroluminescent device can be greatly improved, excellent device effects are brought, such as reduction of device voltage, and improvement of device efficiency and service life are realized. Also disclosed are organic electroluminescent devices and compound compositions comprising the organic electroluminescent materials.

Description

Novel organic electroluminescent material and device thereof

Technical Field

The invention relates to a novel organic electroluminescent material and a device thereof. And more particularly, to an organic electroluminescent material having the structure of formula 1, and an organic electroluminescent device and a compound composition including the material.

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 organic electroluminescent device converts electric energy into light by applying a voltage across the device. In general, an organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layers of the organic electroluminescent device include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including a host material and a light emitting material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The materials constituting the organic layer may be classified into a hole injecting material, a hole transporting material, an electron blocking material, a host material, a light emitting material, an electron buffer material, a hole blocking material, an electron transporting material, an electron injecting material, and the like according to the functions of the materials. When a bias is applied to the device, holes are injected from the anode to the light emitting layer and electrons are injected from the cathode to the light emitting layer. The holes and electrons meet to form excitons, which recombine to emit light. The hole injection layer is one of important functional layers affecting the performance of the organic electroluminescent device, and the selection and collocation of materials can have important influence on the performance of the organic electroluminescent device, such as driving voltage, efficiency, service life and the like. Since organic electroluminescent devices having characteristics such as low driving voltage, high efficiency, and long service life are commercially desired, the development of a novel hole injection layer is a very critical research area.

In the early OLED device, most of the organic material is only arranged between the anode and the light-emitting layer, and the functions of hole injection, hole transmission and even electron blocking are considered, and the structure of the device is limited by a single hole transmission material, so that the energy level cannot be matched more ideally, and therefore, the very ideal performance is difficult to obtain; with the increasing demands of the industry for device performance, the demands for performance of a hole transport region between an anode and a light emitting layer are also increasing, and then the hole transport material is further subdivided into a hole injection layer and a hole transport layer, at this time, a single triarylamine material is generally used as the hole injection layer, and the following triarylamine materials are common:

in the most advanced device structure in the current industry, a plurality of organic layers are generally disposed between an anode and a light emitting layer to respectively realize a hole injection function, a hole transport function and an electron blocking function. In order to obtain a better hole injection effect, a certain proportion of p-type doping materials are often doped in a hole transport material (for example, arylamine compounds) in the hole injection layer, and common p-type doping materials are:

most of p-type doping materials commonly used at present have various problems, and have the characteristics of excellent hole injection capability, high stability, high film forming property and the like. For example, F4TCNQ and F6TCNNQ, while having good hole injection capability, vapor deposition temperatures are too low to affect deposition control and production performance reproducibility and device thermal stability. Therefore, research and development of novel p-type doping materials to solve the above problems is not trivial.

K.Suzuki, M.Tomura, S.Tanaka, Y.Yamashita, tetrahedron Letter,2000,41,8359-8364 discloses a compound having the structures bithiophene and bithiazole, wherein the structure of a particular compound is:

however, the compound has a different framework structure from the compound claimed in the application, and the document does not disclose or teach the application of any such compound in an organic electroluminescent device.

K.Yui, Y.Aso, T.Otsubo, F.Ogura, J.Chem.Soc., chem.Commun.,1987,24,1816-1817; K.Yui, Y.Aso, T.Otsubo, F.Ogura, bull.Chem.Soc.Jpn.,1989,62,1539-1846; H.Ishida, K.Yui, Y.Aso, T.Otsubo, F.Ogura, bull.Chem.Soc.Jpn.,1990,63,2828-2835; a series of compounds having thiophene, bithiophene type structures are disclosed, wherein examples of specific compounds are:

the above compounds are structurally different from the compounds claimed herein and these documents do not disclose or teach the use of any such compounds.

How to further improve the performance of the organic electroluminescent device, obtain higher device efficiency, such as higher external quantum efficiency and longer service life, meet the increasing device performance requirement, and is a problem to be solved by researchers in the industry. The properties of the charge transport materials have a critical influence on the performance of the device, so research and development of novel compounds with stronger charge transfer capability and more possibilities for selection of the transport materials are a work with wide industrial prospect and application value.

Disclosure of Invention

The present invention aims to provide a series of novel organic electroluminescent materials and devices to solve at least part of the above problems. The compound is a compound having a structure of formula 1 and comprising two conjugated systems containing N five-membered heterocyclic rings, which is useful as a charge transport material, a charge injection material and the like in an organic electroluminescent device. The novel compounds have strong charge transfer capability, can provide low-voltage, high-efficiency and long-service-life organic electroluminescent devices, greatly improve the performance of the organic electroluminescent devices, and have wider application prospects.

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

wherein,,

y is selected identically or differently at each occurrence from the group consisting of O, S, se and NR _N A group of;

ring Z is, identically or differently, selected from the group consisting of: an aromatic ring having 6-30 carbon atoms, a heteroaromatic ring having 3-30 carbon atoms, and combinations thereof;

r represents identically or differently for each occurrence a single, multiple or no substitution;

R，R _N and is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic groups having 3 to 20 ring atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

R ', R' are selected identically or differently on each occurrence from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Borane, sulfinyl, sulfonyl, phosphinyloxy, azaAryl radicals and substituted by halogen, nitroso, nitro, acyl, carbonyl, carboxyl, ester, cyano, isocyano, SCN, OCN, SF radicals ₅ Any of the following substituted with one or more of borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl groups: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

adjacent substituents R, R _N R ', R' can optionally be linked to form a ring.

According to another embodiment of the present invention, there is also disclosed an organic electroluminescent device comprising the compound according to the above embodiment.

According to another embodiment of the present invention, there is also disclosed a compound composition comprising the compound of the above embodiment.

The invention discloses a series of conjugated system compounds with a structure of formula 1, which contain two N-containing five-membered heterocycles, and the compounds can be used as charge transport materials and charge injection materials in organic electroluminescent devices, so that the balance of electrons and holes in the devices is improved, the performance of the organic electroluminescent devices can be greatly improved, excellent device effects are brought, such as reducing the voltage of the devices, and improving the efficiency and the service life of the devices are realized.

Drawings

Fig. 1 is a schematic diagram of an organic light emitting device that may contain a compound and a compound composition as 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. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

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

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

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

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

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

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

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

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

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

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

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

Definition of terms for substituents

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present disclosure, when any one of the terms from the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanium, substituted arylgermanium, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, which may be substituted with one or more groups selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted cycloalkyl having 1 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, unsubstituted arylgermanium groups having 6 to 20 carbon atoms, unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof.

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

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

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

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

In the present invention, the number of ring atoms means the number of atoms constituting the ring itself of a compound having a ring-shaped structure to which atoms are bonded (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound). When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the number of ring atoms. The "number of ring atoms" described herein is the same as defined above unless otherwise specified.

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

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

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

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

wherein,,

r ', R' are selected identically or differently at each occurrence from the group consisting ofThe group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boranyl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any of the following substituted with one or more of borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl groups: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

adjacent substituents R, R _N R ', R' can optionally be linked to form a ring.

Herein, "adjacent substituents R, R _N R ', R ' can optionally be linked to form a ring ' is intended to mean wherein adjacent groups of substituents, e.g. between two substituents R, substituents R and R _N Between the substituents R' and R ", any one or more of these groups of substituents 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 when ring Z is selected from the group consisting of heteroaromatic rings having from 3 to 30 carbon atoms, the heteroaromatic rings do not include pyridine, pyridazine, pyrimidine, thiazole, oxazole, imidazole, pyrazine, triazine, 1, 2-azaborane, 1, 3-azaborane, 1, 4-azaborane, borazole and aza analogues thereof.

According to one embodiment of the invention, wherein, when ring Z is selected from heteroaromatic rings having 3 to 30 carbon atoms, the heteroaromatic ring is preferably: thiophene, furan, selenophene, pyrrole, benzothiophene, benzofuran, benzoselenophene, dibenzothiophene, dibenzofuran, dibenzoselenophene, indole, carbazole.

According to one embodiment of the invention, wherein, when R, R _N When selected from the group consisting of substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, the heteroaryl groups do not include pyridine, pyridazine, pyrimidine, thiazole, oxazole, imidazole, pyrazine, triazine, 1, 2-azaborane, 1, 3-azaborane, 1, 4-azaborane, borazole, and aza analogues thereof.

According to one embodiment of the invention, wherein, when R, R _N When selected from substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, the heteroaryl group is preferably: thiophene, furan, selenophene, pyrrole, benzothiophene, benzofuran, benzoselenophene, dibenzothiophene, dibenzofuran, dibenzoselenophene, indole, carbazole.

According to one embodiment of the invention, wherein R, R _N The same or different at each occurrence is selected from groups that do not contain electron withdrawing groups.

According to one embodiment of the invention, wherein R, R _N Is not selected from electron withdrawing groups.

According to one embodiment of the invention, wherein the Hammett constant of the electron withdrawing group is not less than 0.05, preferably not less than 0.3, more preferably not less than 0.5.

According to one embodiment of the invention, wherein the electron withdrawing group is selected from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boranyl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Any of the following substituted with one or more of borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl groups: alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 ring carbon atoms, heteroalkyl having 1 to 20 carbon atoms, heterocyclyl having 3 to 20 ring atoms, aralkyl having 7 to 30 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryloxy having 6 to 30 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 3 to 20 carbon atoms Alkylsilyl groups, arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein Y is selected identically or differently for each occurrence from O, S or Se.

According to one embodiment of the invention, wherein Y is selected identically or differently on each occurrence from O or S.

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

According to one embodiment of the invention, wherein Y is chosen, identically or differently, for each occurrence, from NR _N And R is _N And is selected identically or differently on each occurrence from the group consisting of: 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 aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R _N And is selected identically or differently on each occurrence from the group consisting of: substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl groups having from 7 to 30 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein the ring Z is selected identically or differently on each occurrence from the group consisting of: aromatic rings having 6-20 carbon atoms, heteroaromatic rings having 6-20 carbon atoms, and combinations thereof.

According to one embodiment of the invention, the rings Z are selected identically or differently on each occurrence from aromatic rings having 6 to 20 carbon atoms.

According to one embodiment of the invention, wherein ring Z is selected, identically or differently, for each occurrence, from the group consisting of benzene rings, biphenyl rings, terphenyl rings, triphenyleneRing, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrene ring,

rings and perylene rings.

According to one embodiment of the present invention, wherein at least one of R is selected from the group consisting of 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 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 aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a combination thereof.

According to one embodiment of the present invention, wherein at least one of R is selected from the group consisting of substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 ring carbon atoms, substituted or unsubstituted aralkyl groups having 7-30 carbon atoms, substituted or unsubstituted aryl groups having 6-30 carbon atoms, or combinations thereof.

According to one embodiment of the invention, R is selected identically or differently from hydrogen or an electron donating group for each occurrence.

According to one embodiment of the invention, wherein R is selected identically or differently on each occurrence from hydrogen, deuterium, unsubstituted or substituted with at least one electron donating group: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein the Hammett constant of the electron donating group is <0.05, preferably <0.03, more preferably <0.

The Hammett substituent constant value includes a Hammett substituent para-position constant and/or meta-position constant, and any value of either the para-position constant or the meta-position constant may be used as the preferred electron donating group of the present invention if one of the para-position constant and the meta-position constant is less than 0.05, more preferably less than 0.03, and still more preferably less than 0.

According to one embodiment of the invention, wherein the electron donating groups are the same or different at each occurrence selected from the group consisting of: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms containing only at least one of an O atom, an S atom, a Se atom, and combinations thereof.

According to one embodiment of the invention, wherein the electron donating groups are the same or different at each occurrence selected from the group consisting of: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, aralkyl groups having 7 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein at least one of R ', R' is a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein R ', R' are each a group having at least one electron withdrawing group.

According to one embodiment of the invention, wherein R', R "are, identically or differently, selected from the group consisting of: halogen, nitro, ester, cyano, isocyano, SCN, OCN, sulfinyl, sulfonyl, phosphinoxy, azaaromatic ring groups, and any of the following substituted with one or more of halogen, nitro, ester, cyano, isocyano, SCN, OCN, sulfinyl, sulfonyl, phosphinoxy, azaaromatic ring groups: alkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R', R "are, for each occurrence, identically or differently selected from the group consisting of: halogen, cyano, SCN, and any of the following substituted with one or more of halogen, cyano, SCN: alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R', R "are, for each occurrence, identically or differently selected from the group consisting of: fluoro, cyano, SCN, trifluoromethyl, 2,3,5, 6-tetrafluoro-4-cyanophenyl, 2,3,5, 6-tetrafluoropyridyl, cyanophenyl, fluorophenyl, and combinations thereof.

According to one embodiment of the invention, wherein R', R "are, identically or differently, selected from the group consisting of:

", represents the position of connection of R', R" having the above structure to formula 1.

According to one embodiment of the invention, wherein R ', R' are selected from

According to one embodiment of the invention, wherein R _N And in 1

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

/>

In the above structure, ph represents phenyl;

represents +.>

The position of the N-containing five-membered conjugated heterocyclic ring in formula 1->

And also represents when Y is selected from NR _N When the R has the structure _N Connection to N.

According to one embodiment of the present invention, wherein in one compound represented by formula 1, two rings Z are the same and two R are the same.

According to one embodiment of the invention, wherein the compound is selected from the group consisting of compound I-1 to compound I-204; the specific structure of said compounds I-1 to I-204 is seen in claim 11.

According to an embodiment of the present invention, an organic electroluminescent device is disclosed, which includes:

an anode is provided with a cathode,

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

an organic layer disposed between the anode and cathode, the organic layer comprising a compound according to any of the preceding embodiments.

According to one embodiment of the present invention, wherein the organic layer is a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer is formed separately from the compound.

According to one embodiment of the present invention, wherein the organic layer is a hole injection layer or a hole transport layer, the hole injection layer or the hole transport layer further comprising at least one hole transport material; wherein the molar doping ratio of the compound to the hole transport material is from 10000:1 to 1:10000.

According to one embodiment of the present invention, wherein the organic layer is a hole injection layer or a hole transport layer, the hole injection layer or the hole transport layer further comprising at least one hole transport material; the molar doping ratio of the compound to the hole transport material is from 10:1 to 1:100.

According to one embodiment of the present invention, wherein the organic electroluminescent device comprises at least two light emitting cells, the organic layer is a charge generating layer and is disposed between the at least two light emitting cells, wherein the charge generating layer comprises a p-type charge generating layer and an n-type charge generating layer; preferably, the p-type charge generation layer comprises the compound.

According to one embodiment of the present invention, wherein the p-type charge generation layer further comprises at least one hole transport material, wherein the molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000.

according to one embodiment of the present invention, wherein the p-type charge generation layer further comprises at least one hole transport material, wherein the molar doping ratio of the compound to the hole transport material is 10:1 to 1:100.

According to one embodiment of the invention, wherein the hole transport material is selected from the group consisting of: compounds having triarylamine units, spirobifluorene compounds, pentacene compounds, oligothiophenes compounds, oligophenyl compounds, oligophenylenevinylene compounds, oligofluorene compounds, porphyrin complexes, metal phthalocyanine complexes, and combinations thereof.

According to one embodiment of the present invention, wherein the charge generation layer further comprises a buffer layer disposed between the p-type charge generation layer and the n-type charge generation layer, the buffer layer comprising the compound.

According to one embodiment of the invention, the organic electroluminescent device is prepared by a vacuum evaporation method.

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

Combined with other materials

The materials described herein for specific layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

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

In the device of the present invention, charge injection, transport layers, such as hole injection layers, hole transport layers, electron transport layers, and electron injection layers, may be included; may also comprise a light-emitting layer comprising at least one light-emitting dopant, which may be a fluorescent light-emitting dopant and/or a phosphorescent light-emitting dopant, and at least one host compound; barrier layers, such as hole blocking layers, electron blocking layers, may also be included.

The method of manufacturing the organic electroluminescent device is not limited, and the method of manufacturing the following examples is only one example and should not be construed as limiting. Those skilled in the art will be able to make reasonable modifications to the preparation methods of the following examples in light of the prior art. Illustratively, the proportions of the various materials in the organic layers are not particularly limited, and can be reasonably selected within a certain range by those skilled in the art according to the prior 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.

The measured LUMO energy level obtained herein is the electrochemical property of the compound measured by Cyclic Voltammetry (CV). The electrochemical workstation model CorrTest CS120, manufactured by Wuhan Koste instruments Co., ltd, was used. Three electrode working system: platinum disk electrode as working electrode, ag/AgNO ₃ The electrode is a reference electrode, and the platinum wire electrode is an auxiliary electrode. The target compound was prepared to 10 using anhydrous DCM as a solvent and tetrabutylammonium hexafluorophosphate at 0.1mol/L as a supporting electrolyte ^-3 And (3) introducing nitrogen into the solution in mol/L for 10min to deoxidize before testing. Instrument parameter setting: the scan rate was 100mV/s, the potential spacing was 0.5mV, and the test window was 1V to-0.5V.

The calculated LUMO level obtained herein is obtained by the DFT calculation [ GAUSS-09, B3LYP/6-311G (d) ] method.

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.

Examples of materials synthesis

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

Synthesis example 1: synthesis of Compound I-1

Step 1: synthesis of intermediate 1-b

1-a (2.2 g,7.6 mmol) was added to THF (50 mL) under nitrogen, cooled to-72℃and LiHMDS solution (1.0M, 35 mL) was slowly added dropwise followed by a slow rise to-30℃and reaction for 0.5h. ZnCl is added dropwise at-30 DEG C ₂ (2.0M, 17 mL) was slowly warmed to 0deg.C and reacted for 10min, elemental solid iodine (7.8 g,31 mmol) was added to the reaction solution and reacted at 0deg.C for 2h. The reaction is completed by saturated NH ₄ The reaction was quenched with Cl solution, washed with saturated sodium thiosulfate solution, extracted with DCM, and dried Na ₂ SO ₄ Drying, filtering and concentrating. Silica gel column chromatography (DCM/pe=1/2 as eluent) afforded product 1-b as a white solid (4.0 g,97% yield).

Step 2: synthesis of intermediate 1-c

Malononitrile (4.52 g,68.4 mmol) was added to anhydrous DMF (160 mL), 0, under a nitrogen atmosphereNaH (2.80 g,70.0mmol,60% content) was added in portions at C, stirred for 30 minutes, after which 1-b (8.8 g,16.3 mmol) and Pd (PPh) were added ₄ ) ₃ (1.88 g,1.63 mmol) was reacted at 90℃for 24 hours. After complete conversion, the mixture is poured into ice water, and the pH value is regulated by 2N dilute hydrochloric acid <1, a large amount of yellow solid precipitated, filtered, the filter cake washed with a large amount of water and petroleum ether, the solid product eluted with acetone, concentrated, filtered to give a yellow solid, washed three times with dichloromethane, and finally filtered to give yellow solid 1-c (4.4 g,65% yield).

Step 3: synthesis of Compound I-1

1-c (4.4 g,10.6 mmol) was added to DCM (600 mL) under nitrogen, cooled to 0deg.C, PIFA ([ bis (trifluoroacetoxy) iodo ] benzene) (9.3 g,21.6 mmol) was added in portions and the solution stirred at room temperature for 3 days in the dark purple color. The solution was concentrated and filtered, washed twice successively with DCM/pe=1:1 (50 mL) to finally give compound I-1 as a black solid (2.9 g,66% yield). The product was identified as the target product and had a molecular weight of 414.1.

Lumo= -4.70eV of compound I-1 was measured by cyclic voltammetry in DCM, and the dft calculation gave lumo= -4.83eV of compound I-1. At 6.8 x 10 ^-4 Heating and sublimating under the vacuum condition of Pa and the constant temperature of 300 ℃ for 2 hours to obtain the black solid compound I-1.

Synthesis example 2: synthesis of Compound I-2

Step 1: synthesis of intermediate 2-b

2-a (4.7 g,14.9 mmol) was added to THF (500 mL) under nitrogen, the temperature was reduced to-72℃and LiHMDS solution (1.0M, 32 mL) was slowly added dropwise followed by a slow increase to-30℃and reaction continued for 2h. Elemental solid iodine (15.1 g,59.4 mmol) was added to the reaction solution and allowed to react at room temperature for 1h. The reaction is completed, With saturated NH ₄ The reaction was quenched with Cl solution, washed with saturated sodium thiosulfate solution, extracted with DCM, and dried Na ₂ SO ₄ Drying, filtering, and concentrating. Silica gel column chromatography (DCM/pe=2/1 as eluent) afforded product 2-b as a white solid (6.5 g,77% yield).

Step 2: synthesis of intermediate 2-c

Malononitrile (4.57 g,68.6 mmol) was added to anhydrous DMF (300 mL) under nitrogen, naH (2.75 g,68.6mmol,60% content) was added in portions at 0deg.C, and stirred for 30 min. 2-b (6.5 g,11.4 mmol) and Pd (PPh) were added ₄ ) ₃ (1.32 g,1.14 mmol) was reacted at 90℃for 24 hours. After complete conversion, the mixture is poured into ice water, and pH is adjusted by 2N diluted hydrochloric acid<1, a large amount of yellow solid is precipitated, filtered and the filter cake is washed with a small amount of water and petroleum ether. The solid product was dissolved in acetone, the solvent was removed by rotary evaporation and dried, washed twice with acetonitrile and dichloromethane, filtered, and washed three times with dichloromethane (20 mL) to give 2-c as an off-white solid (3.5 g,69% yield).

Step 3: synthesis of Compound I-2

2-c (3.5 g,7.88 mmol) was added to DCM (1000 mL) under nitrogen, cooled to 0deg.C, PIFA (6.77 g,15.75 mmol) was added in portions and stirred at room temperature for 2 days, the solution being purple black. The solution was concentrated and filtered to give a black solid. Washed twice with DCM/pe=1:1 (20 mL) and finally dried to give black solid I-2 (2.6 g,74% yield). The product was identified as the target product and had a molecular weight of 442.1. Lumo= -4.70eV for compound I-2 was measured by cyclic voltammetry in DCM and calculated by dft to give lumo= -4.70eV for compound I-2.

Synthesis example 3: synthesis of Compound I-3

Step 1: synthesis of intermediate 3-b

3-a (13.8 g,34.5 mmol) was added to THF (350 mL) under nitrogen, cooled to-72 ℃ (ethanol/dry ice), liHMDS solution (1.0M, 140 mL) was slowly added dropwise, followed by a slow rise to-30℃and reaction for 0.5h. ZnCl is added dropwise at-30 DEG C ₂ (2.0M, 70 mL) was slowly warmed to 0deg.C and reacted for 10min, elemental solid iodine (35.5 g,140 mmol) was added to the reaction solution and reacted at 0deg.C for 2h. The reaction is completed by saturated NH ₄ The reaction was quenched with Cl solution, washed with saturated sodium thiosulfate solution, extracted with DCM, and dried Na ₂ SO ₄ Drying and filtering the spin-dried solvent. Silica gel column chromatography (DCM/pe=2/1 as eluent) afforded the product as a white solid 3-b (21.3 g,95% yield).

Step 2: synthesis of intermediate 3-c

Malononitrile (11.6 g,176 mmol) was added to anhydrous DMF (260 mL) under nitrogen, and K was added in portions at 0deg.C ₂ CO ₃ (15.6 g,113 mmol) was stirred for 30 min, after which 3-b (18.7 g,28.7 mmol) and Pd (PPh) were added ₄ ) ₃ (3.44 g,2.98 mmol) was reacted at 90℃for 24 hours. After complete conversion, the mixture is poured into ice water, and the pH value is regulated by 2N dilute hydrochloric acid<1, a large amount of yellow solid is separated out, filtered and the filter cake is washed with a large amount of water and petroleum ether. The solid product was dissolved in acetone, the solvent was removed by rotary evaporation and dried, washed with acetonitrile and dichloromethane respectively, filtered, washed three times with dichloromethane (20 mL) and finally filtered to give 3-c as a yellow solid (8.9 g,59% yield).

Step 3: synthesis of Compound I-3

3-c (8.9 g,16.9 mmol) was added to DCM (100)0 mL), the temperature was lowered to 0 ℃, PIFA (14.5 g,33.7 mmol) was added after batch, and the solution was stirred at room temperature for 3 days, and the solution was purple black. Most of the solvent was removed by rotary evaporation, filtered, washed twice consecutively with DCM/pe=1:1 (100 mL) and finally dried to give black solid I-3 (6.8 g,77% yield). The product was identified as the target product and had a molecular weight of 526.2. Lumo= -4.71eV for compound I-3 was measured by cyclic voltammetry in DCM and calculated by dft to give lumo= -4.72eV for compound I-3. At 4.9 x 10 ^-4 Heating and sublimating under the vacuum condition of Pa and the constant temperature of 280 ℃ for 3 hours to obtain the black solid compound I-3.

Synthesis example 4: synthesis of Compound I-7

Step 1: synthesis of [ intermediate 4-b ]

4-a (11.5 g,33.0 mmol) was added to THF (220 mL) under nitrogen, the temperature was reduced to-72℃and LiHMDS solution (1.0M, 150 mL) was slowly added dropwise followed by a slow increase to-30℃and reaction continued for 0.5h. ZnCl is added dropwise at-30 DEG C ₂ (2.0M, 75 mL) solution was slowly warmed to 0deg.C for 10min, elemental solid iodine (33.6 g,132 mmol) was added to the reaction solution, the temperature of the reaction solution was returned to room temperature, and the reaction was carried out at room temperature for 2h. The reaction is completed by saturated NH ₄ The reaction was quenched with Cl solution, washed with saturated sodium thiosulfate solution, extracted with DCM, and dried Na ₂ SO ₄ After drying, the spin-dried solvent was filtered. Silica gel column chromatography (DCM/pe=1/2 as eluent) afforded the product as a white solid 4-b (17.0 g,86% yield).

Step 2: synthesis of intermediate 4-c

Malononitrile (11.9 g,180 mmol) was added to anhydrous DMF (300 mL) under nitrogen, and K was added in portions at 0deg.C ₂ CO ₃ (24.8 g,180 mmol) and stirred for 20 minutes. 5-b (18.0 g, 3)0.0 mmol) and Pd (PPh ₄ ) ₃ (3.50 g,3.03 mmol) was reacted at 90℃for 24 hours. After complete conversion, the mixture is poured into ice water, and pH is adjusted by 2N diluted hydrochloric acid<1, a large amount of yellow solid is precipitated, filtered and the filter cake is washed with a small amount of water and petroleum ether. The solid product was dissolved in THF, the solvent removed by rotary evaporation and dried, washed with acetonitrile and tetrahydrofuran, filtered, and washed three times with dichloromethane (20 mL) to afford 4-c as a yellow solid (7.0 g,50% yield).

Step 3: synthesis of Compound I-7

4-c (7.0 g,14.7 mmol) was added to DCM (800 mL) under nitrogen, the temperature was reduced to 0deg.C, PIFA (12.6 g,19.4 mmol) was added in portions and the solution stirred at room temperature for 2 days in the form of a purple black. After most of the solvent was removed by rotary evaporation, a black solid was obtained by filtration. Washing twice with DCM/pe=1:1 (20 mL) and finally drying gave I-7 as a black solid (6.6 g,94% yield). The product was identified as the target product and had a molecular weight of 474.1. Lumo= -4.73eV for compound I-7 was measured by cyclic voltammetry in DCM and calculated by dft to give lumo= -4.72eV for compound I-7.

Synthetic comparative example 1: synthesis of Compound S

Step 1: synthesis of [ intermediate 5-b ]

5-a (15.0 g,47.2 mmol) was added to ethanol (400 mL), p-toluenesulfonic acid monohydrate (2.06 g,10.8 mmol) was added, NIS (N-iodosuccinimide) (32.5 g,14.4 mmol) was then reacted at room temperature for 12h. The reaction was complete and the solid product was directly obtained, dissolved in DCM and concentrated. Silica gel column chromatography (DCM/pe=1/5 as eluent) afforded the product as a white solid 5-b (15.8 g,59% yield).

Step 2: synthesis of Compound S

Malononitrile (8.7 g,132 mmol) was added to anhydrous DMF (120 mL) under nitrogen, naH (4.95 g,123mmol,60% content) was added in portions at 0deg.C, stirred for 30 min, after which 5-b (7.5 g,13.2 mmol) and Pd (PPh) ₄ ) ₃ (1.8 g,1.5 mmol) was reacted at 90℃for 36h. After complete conversion, the mixture is poured into ice water, and the pH value is regulated by 2N dilute hydrochloric acid<1, a large amount of solid precipitated, filtered, the solid product was washed with DCM, washed with water, extracted with DCM, dried over anhydrous sodium sulfate, and the filtered filtrate was added with PIFA (10.2 g,23.7 mmol) and the reaction was stirred at room temperature for 3h. The reaction gave a dark purple solution, the solvent was removed by rotary evaporation, and column chromatography on silica gel (DCM/pe=1/1 as eluent) gave the product as a black solid compound S (2.0 g,34% yield). The product was identified as the target product and had a molecular weight of 444.1. Lumo= -4.29eV for compound S was measured by cyclic voltammetry in DCM and dft calculation gave lumo= -4.33eV for compound S. At 6.8 x 10 ^-4 Heating and sublimating under the vacuum condition of Pa at the constant temperature of 270 ℃ for 2 hours to obtain the black solid compound S.

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: an organic electroluminescent device 100 was prepared as shown in fig. 1.

First, a glass substrate 101 having a thickness of 0.7mm and having a pre-patterned thereon was used

A thick Indium Tin Oxide (ITO) was used as the anode 110, and the ITO surface was treated with oxygen plasma and UV ozone after washing the substrate with deionized water and a detergent. Subsequently, the substrate was baked in a glove box to remove moisture, and loaded onto a holder into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 ^-6 In case of Torr +.>

Sequentially evaporating on the anode layer by vacuum thermal evaporation: first, compound HT and compound I-1 were simultaneously evaporated as hole injection layers (HIL, 80:20,

) 120, vapor deposition compound HT is used as hole transport layer (HTL, < >>

) 130, evaporation compound EB is used as electron blocking layer (EBL, ">

) 140, then, compound BH and compound BD were simultaneously evaporated as light emitting layers (EML, 96:4, " >

) 150, evaporation of the compound HB as hole blocking layer (HBL, -/->

) 160, the compounds ET and Liq were co-deposited as electron transport layers (ETL, 40:60,/for>

) 170, vapor plating->

Liq of thickness acts as an Electron Injection Layer (EIL) 180. Finally, metallic aluminum was evaporated as Cathode (Cathiode,>

) 190. The device was then transferred back to the glove box and packaged with a glass cover slip to complete the device.

Example 2: the same procedure as in example 1 was followed, except that compound HT and compound I-3 were evaporated as hole injection layers (HIL, 80:20,

)。

comparative example 1: the same preparation as in example 1 was carried out, except that the evaporation of compound HT and compound S was carried out as a hole injection layer (HIL, 80:20,

)。

the detailed device layer structure and thickness are shown in table 1 below. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.

TABLE 1 device structures of organic layer portions of examples 1-2 and comparative example 1

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

/>

table 2 summarises the device performance of examples 1, 2 and comparative example 1. Wherein the color Coordinates (CIE), voltage (V), current Efficiency (CE), external Quantum Efficiency (EQE) and lifetime LT95 (h) are measured at a current density of 10mA/cm ² And (3) measuring the following.

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

Table 2 shows the test results of the organic electroluminescent device comprising different p-type conductivity doping materials and hole transport material compounds HT used in combination, and it can be seen from the color coordinates that the illustrated examples are substantially identical to the color coordinates of the comparative examples.

Compared with comparative example 1, the voltage of example 1 was reduced by 5.58V, and the amplitude reduction reached 55%; compared with comparative example 1, the current efficiency and the external quantum efficiency of example 1 are both greatly improved, wherein the current efficiency is improved by 48%, and the external quantum efficiency is improved by 53%; the life of example 1 was also significantly improved by 167% over comparative example 1.

Compared with comparative example 1, the voltage of example 2 was reduced by 4.08V, and the reduction was 40%; compared with comparative example 1, the current efficiency and external quantum efficiency of example 2 are both greatly improved, wherein the current efficiency is improved by 51%, and the external quantum efficiency is improved by 55%. The lifetime of example 2 was significantly improved by a factor of 27 compared to comparative example 1. It can be seen that the compound I-3 used in example 2 is further substituted on the ring Z based on the compound I-1 used in example 1, which shows more excellent charge transfer capability, and the organic electroluminescent device prepared therefrom achieves a significant improvement in overall performance, in particular, a significant improvement in device lifetime.

As can be seen from the above comparison, the conjugated system compound having the structure of formula 1 disclosed in the present invention, which contains two N-containing five-membered heterocycles, has more excellent charge transfer ability than the compound having the conjugated dithiophene-type structure selected in comparative example 1, and the organic electroluminescent device prepared therefrom achieves a reduction in voltage and a substantial improvement in efficiency, and has excellent device lifetime. Therefore, the compound has incomparable advantages in hole transmission, has wide commercial prospect, can be used for preparing organic semiconductor devices, and is suitable for different types of organic electronic devices, including but not limited to fluorescent OLED, phosphorescent OLED, white OLED, laminated layer OLED, OTFT, OPV and the like.

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 a structure represented by formula 1:

wherein,,

r ', R' are selected identically or differently on each occurrence from the group consisting of: halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN, SF ₅ Boranyl, sulfinyl, sulfonyl, phosphinoxy, azaaryl, and substituted with halogen, nitroso, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, SCN, OCN、SF ₅ Any of the following substituted with one or more of borane, sulfinyl, sulfonyl, phosphinoxy, azaaryl groups: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

adjacent substituents R, R _N R ', R' can optionally be linked to form a ring.

2. The compound of claim 1, wherein Y is selected identically or differently at each occurrence from O, S, or Se; preferably, Y is selected identically or differently on each occurrence from O or S; more preferably, Y is O.

3. The compound of claim 1, wherein Y is selected identically or differently at each occurrence from NR _N And R is _N And is selected identically or differently on each occurrence from the group consisting of: 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 aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

Preferably, R _N And is selected identically or differently on each occurrence from the group consisting of: substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl groups having from 7 to 30 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, and combinations thereof.

4. A compound according to claims 1-3, wherein ring Z is, identically or differently, selected from the group consisting of: an aromatic ring having 6-20 carbon atoms, a heteroaromatic ring having 6-20 carbon atoms, and combinations thereof;

preferably, ring Z is, identically or differently, selected for each occurrence from aromatic rings having 6 to 20 carbon atoms;

more preferably, the rings Z are selected identically or differently on each occurrence from benzene rings, biphenyl rings, terphenyl rings, triphenylene rings, naphthalene rings, anthracene rings, phenanthrene rings, fluorene rings, pyrene rings,

rings and perylene rings.

5. The compound of any one of claims 1-4, wherein at least one of R is selected from a substituted or unsubstituted alkyl group having 1-20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7-30 carbon atoms, a substituted or unsubstituted alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted aryloxy group having 6-30 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, or a combination thereof;

Preferably, at least one of R is selected from the group consisting of 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 aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof.

6. The compound as recited in any of claims 1-4, wherein R, identically or differently for each occurrence, is selected from hydrogen, deuterium, unsubstituted or substituted with at least one electron donating group: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.

7. The compound of any one of claims 1-4, wherein R is selected identically or differently on each occurrence from hydrogen or an electron donating group.

8. The compound of claim 6 or 7, wherein the electron donating groups are the same or different at each occurrence selected from the group consisting of: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, aralkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and combinations thereof;

Preferably, the electron donating groups are the same or different at each occurrence selected from the group consisting of: alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 ring carbon atoms, aralkyl groups having 7 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and combinations thereof.

9. The compound of any one of claims 1-8, wherein R', R "are, identically or differently, selected from the group consisting of: halogen, nitro, ester, cyano, isocyano, SCN, OCN, sulfinyl, sulfonyl, phosphinoxy, azaaromatic ring groups, and any of the following substituted with one or more of halogen, nitro, ester, cyano, isocyano, SCN, OCN, sulfinyl, sulfonyl, phosphinoxy, azaaromatic ring groups: alkyl groups having 1 to 20 carbon atoms, heterocyclic groups having 3 to 20 ring atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;

preferably, wherein R', R "are, identically or differently, selected from the group consisting of:

/>

preferably, wherein R ', R' is selected from

10. The compound of claim 1 or 9, wherein R _N And in 1

/>

wherein "﹋" represents a compound having the above-mentioned structure

The connection position of the N-containing five-membered conjugated heterocyclic ring in the formula 1; "﹋" also represents that when Y is selected from NR _N R having the above-mentioned structure _N Connection to N.

11. The compound of claim 1 or 10, wherein the compound is selected from any one of the structures shown by compounds I-1 to I-204, wherein compounds I-1 to I-204 have the structure of formula 1-1:

in the formula 1-1, two Y's are the same, and B represents a structure

And two B are identical and R', R ", Y and B each correspond to an atom or group selected from the following table:

/>

/>

12. an organic electroluminescent device, comprising:

an anode is provided with a cathode,

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

an organic layer disposed between the anode and cathode, the organic layer comprising the compound of any one of claims 1 to 11.

13. The organic electroluminescent device of claim 12, wherein the organic layer is a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer is formed separately from the compound.

14. The organic electroluminescent device of claim 12, wherein the organic layer is a hole injection layer or a hole transport layer, the hole injection layer or the hole transport layer further comprising at least one hole transport material; wherein the molar doping ratio of the compound to the hole transport material is from 10000:1 to 1:10000;

preferably, the molar doping ratio of the compound to the hole transport material is from 10:1 to 1:100.

15. The organic electroluminescent device of claim 12, wherein the organic electroluminescent device comprises at least two light emitting cells, the organic layer being a charge generating layer and disposed between the at least two light emitting cells, wherein the charge generating layer comprises a p-type charge generating layer and an n-type charge generating layer; preferably, the p-type charge generation layer comprises the compound;

more preferably, the p-type charge generation layer further comprises at least one hole transport material, wherein the molar doping ratio of the compound to the hole transport material is 10000:1 to 1:10000; most preferably, the molar doping ratio of the compound to the hole transport material is from 10:1 to 1:100.

16. The organic electroluminescent device of claim 14 or 15, wherein the hole transport material is selected from the group consisting of: compounds having triarylamine units, spirobifluorene compounds, pentacene compounds, oligothiophenes compounds, oligophenyl compounds, oligophenylenevinylene compounds, oligofluorene compounds, porphyrin complexes, metal phthalocyanine complexes, and combinations thereof.

17. The organic electroluminescent device of claim 15, wherein the charge generation layer further comprises a buffer layer disposed between the p-type charge generation layer and the n-type charge generation layer, the buffer layer comprising the compound.

18. A compound composition comprising a compound of any one of claims 1-11.