CN113683518B

CN113683518B - Aromatic amine derivatives organic electroluminescent materials and devices

Info

Publication number: CN113683518B
Application number: CN202010418571.2A
Authority: CN
Inventors: 田学超; 毕欣; 张少博; 赵春亮; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Xiahe Technology Co Ltd
Priority date: 2020-05-18
Filing date: 2020-05-18
Publication date: 2025-05-06
Anticipated expiration: 2040-05-18
Also published as: CN113683518A

Abstract

Disclosed are aromatic amine derivative organic electroluminescent materials and devices thereof. The compound is an aromatic amine substituted pyrene compound, wherein one aryl group of the aromatic amine in the compound has a substituted six-membered (hetero) aromatic ring and a saturated ring structure, and the other aryl group is a substituted (hetero) aryl group. The compounds are useful as light-emitting materials in organic electroluminescent devices. These novel compounds can provide better device performance, such as narrower half-widths and higher external quantum efficiencies. An electroluminescent device and a compound formulation are also disclosed.

Description

Aromatic amine derivative 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 pyrene compound containing an aromatic amine substitution, and an organic electroluminescent device and a compound formulation containing the same.

Background

Organic electronic devices include, but are not limited to, organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic Light Emitting Transistors (OLETs), 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 Isomangan 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 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.

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 OLED phosphor materials have been successfully commercialized. At present, the phosphorescent blue light OLED has short service life, is difficult to reach deep blue, and has the problems of blue unsaturation, high working voltage and the like. Fluorescent blue OLEDs have longer lifetimes than phosphorescent blue OLEDs, but have low efficiency, and thus, there is a great need to improve the efficiency of fluorescent blue electroluminescent devices.

WO2010013676A1 discloses diaminopyrene derivatives of the formulaWherein an aminopyrene derivative having a benzo-cyclic hydrocarbon substituent in part is disclosed, the specific structure is Etc. However, the patent application does not examine the effect of the introduction of the benzocyclic hydrocarbon on the performance of the device, and does not recognize the advantages of the introduction of the benzocyclic hydrocarbon or the fact that other groups are attached to the benzene ring of the benzocyclic hydrocarbon, and does not recognize the different effects of the change of the substituent position of the benzoalicyclic ring.

CN109678729A discloses a pyrene compound containing benzocyclohexane hydrocarbon structure, the general formula is as followsWherein Ar ₂ is selected fromThe concrete structure is thatEtc. However, this patent application discloses only benzocyclohexane compounds having only a few structures, and does not examine the effect of the introduction of benzocyclohexane on the device performance, nor does it disclose or teach the device effect that further substitution of a benzocyclohexane ring hydrocarbon with a non-six membered ring and a benzene ring of a benzocyclohexane ring hydrocarbon would achieve.

CN107556239A discloses a pyrene compound containing an acridine structure, which has the following general formulaWherein Ar ₁ and Ar ₂ can be heterocyclic groups, and the specific structure is thatAnd the like, but the patent application is mainly aimed at a series of pyrene compounds with acridine substituted aromatic amine, does not pay attention to the improvement of the performance of devices by benzo-heterocyclic hydrocarbon, and does not disclose or teach that better device effects can be obtained by connecting other groups to benzene rings of the benzo-heterocyclic hydrocarbon.

Some pyrene-based fluorescent luminescent materials having an aromatic amine structure are disclosed in these documents. However, further development of fluorescent materials is still needed to obtain higher device performance.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a novel series of pyrene compounds having a substituted six-membered (hetero) aromatic ring and saturated ring and a substituted (hetero) aryl group aromatic amine structure.

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

wherein, in the formula 1,

At least one of the substituents R ₁-R₁₀ has the structure of formula 2:

And the remainder of the substituents R _l-R_l0 are, identically or differently, selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having from 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, cyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, and combinations thereof;

Wherein, in the formula 2,

L is, identically or differently, selected from a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms, or a combination thereof;

X ₁-X₅ is selected identically or differently from C, CR _x1,CR_x2 or N at each occurrence, and at least two of the adjacent groups of X ₁-X₅ are C and are linked to the formula 2, at least one of the groups of X ₁-X₅ is CR _x2;

Y ₁-Y₅ is selected identically or differently from CR _y1,CR_y2 or N at each occurrence, and at least one of Y ₁-Y₅ is CR _y2;

Z is selected identically or differently for each occurrence from C (R _z)₂,NR_z, O, S or Se;

R _x1 and R _y1 are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, carbonyl, carboxylate, ester, cyano, mercapto, sulfonyl, phosphonyl, and combinations thereof;

R _x2 and R _y2 are each independently selected from the group consisting of deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylate, cyano, isothioyl, sulfonyl, phosphonyl, and combinations thereof;

* Represents the position at which the substituent having the structure of formula 2 is attached to formula 1;

n is 0,1,2,3,4 or 5;

R _z is the same or different at each occurrence and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryloxy having 6-30 carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl having 3-20 carbon atoms, substituted or unsubstituted arylsilyl having 6-20 carbon atoms, and combinations thereof;

Adjacent substituents R _x1,R_x2,R_y1,R_y2 can optionally be linked to form a ring.

According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising the compound having the structure of formula 1. The specific structure of the compounds is described in the previous examples.

According to another embodiment of the present invention, a compound formulation is also disclosed, comprising the compound having the structure of formula 1. The specific structure of the compounds is described in the previous examples.

The novel pyrene compounds with substituted six-membered (hetero) aromatic ring, saturated ring and substituted (hetero) aryl aromatic amine structure can be used as luminescent materials in organic electroluminescent devices. These novel compounds can provide better device performance such as narrower half-widths and higher external quantum efficiencies.

Drawings

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

Fig. 2 is a schematic diagram of another organic light emitting device that may contain the compounds and compound formulations 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 various layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2 at 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 m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, 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 rate of reverse intersystem crossing (IRISC) 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 yields 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-includes straight and branched alkyl groups. 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. In addition, the alkyl group may be optionally substituted. The carbon in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.

Cycloalkyl-as used herein, includes cyclic alkyl. Preferred cycloalkyl groups are cycloalkyl groups containing 4 to 10 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, cycloalkyl groups may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.

Alkenyl-as used herein, covers both straight chain and branched alkene groups. Preferred alkenyl groups are alkenyl groups containing 2 to 15 carbon atoms. Examples of alkenyl groups include vinyl, allyl, 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 and 3-phenyl-1-butenyl. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, covers both straight and branched chain alkynyl groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.

Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chicory, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-triphenyl-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.

Heterocyclyl or heterocycle-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl-as used herein, non-fused and fused heteroaromatic groups are contemplated that may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 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, indenazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzothiophene pyridine, thienodipyridine, benzothiophene bipyridine, benzoselenophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-1, 3-aza-borane, 1-borane, 4-borane, and the like. In addition, heteroaryl groups may be optionally substituted.

Alkoxy-is represented by-O-alkyl. Examples of alkyl groups and preferred examples are the same as described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy groups. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

Aryloxy-is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy and diphenoxy.

Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, aralkyl groups may be optionally substituted. 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, o-cyanobenzyl, 1-chlorophenyl, 1-isopropyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl.

The term "aza" in azafluorene, azaspirobifluorene ring, azadibenzofuran, aza-dibenzothiophene, etc. means that one or more 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 aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, refers to alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, any one of which may be substituted with one or more groups selected from deuterium, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, 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, sulfinyl groups, sulfonyl groups, phosphino 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, a deuterated substituent, such as deuterated methyl, means that at least one hydrogen atom in the substituent (methyl) is replaced by deuterium.

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 may be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to further distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

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

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

wherein, in the formula 1,

At least one of the substituents R ₁-R₁₀ has the structure of formula 2:

And the remainder of the substituents R ₁-R₁₀ are, identically or differently, selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having from 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, cyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, and combinations thereof;

Wherein, in the formula 2,

n is 0,1,2,3,4 or 5;

R _z is, identically or differently, selected 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 heteroalkyl groups having 1 to 20 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 alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;

Adjacent substituents R _x1,R_x2,R_y1,R_y2 can optionally be linked to form a ring;

the substituents R _z can optionally be linked to form a ring.

In this embodiment, the "adjacent substituents R _x1,R_x2,R_y1,R_y2 can optionally be linked to form a ring" can include any one or more of the cases where there is a link between adjacent substituents to form a ring, such as, for example, where there is a link between any one or more of adjacent substituents R _x1 and R _x1, adjacent substituents R _x1 and R _x2, adjacent substituents R _x2 and R _x2, adjacent substituents R _y1 and R _y1, adjacent substituents R _y1 and R _y2, and adjacent substituents R _y2 and R _y2. In another case, no ring may be formed between adjacent substituents.

In this embodiment, the "substituent R _z can optionally be linked to form a ring" can comprise any one or more of the following, one of which is the case for the presence of a link between substituents R _z to form a ring, such as when two or more R _z are present together, there is a link between these R _z to form a ring, such as when R _z is linked to form a spiro or bridged ring structure. In another case, the substituents R _z may not be bonded to each other to form a ring.

In this embodiment, at least one of the substituents R ₁ to R ₁₀ in formula 1 has the structure of formula 2, and the remainder of R ₁ to R ₁₀, for each occurrence, are identically or differently selected from the group consisting of the substituents described above. For example, when substituent R ₁ has the structure of formula 2, the remainder of R ₁ to R ₁₀, i.e., R ₂ to R ₁₀, are identically or differently selected from the group consisting of the substituents described above at each occurrence. When the substituents R ₁ and R ₆ have the structure of formula 2, the remainder of R ₁ to R ₁₀, i.e., R ₂ to R ₅ and R ₇ to R ₁₀, are identically or differently selected from the group consisting of the substituents described above for each occurrence.

According to an embodiment of the present invention, wherein the substituent having formula 2 further has a structure of formula 3 or formula 4:

wherein, in the formulas 3 and 4,

X ₁-X₃ in formula 3 is selected identically or differently from CR _x1,CR_x2 or N at each occurrence, and at least one is CR _x2;

X ₁-X₂ and X ₅ in formula 4 are, identically or differently, selected from CR _x1,CR_x2 or N, and at least one is CR _x2;

n is 0,1,2,3,4 or 5;

the substituents R _z can optionally be linked to form a ring;

* Represents the position at which the substituent having the structures represented by formula 3 and formula 4 is linked to formula 1.

According to one embodiment of the invention, n is 0, 1,2, 3.

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

According to one embodiment of the invention, wherein the substituents R ₁ and R ₆ in formula 1 have the structure represented by formula 2, formula 3 or formula 4 and R ₁ and R ₆ are the same or different, R ₂ to R ₅,R₇ to R ₁₀ are the same or different at each occurrence and are selected 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 heteroalkyl groups having 1 to 20 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 alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 6 to 20 carbon atoms, carbonyl groups, substituted or unsubstituted silyl groups having 0 carbon atoms, cyano groups, substituted or unsubstituted silyl groups having 6 to 20 carbon atoms, carbonyl groups, cyano groups, carbonyl groups having 0.

According to one embodiment of the invention, the substituents R ₁ and R ₆ in formula 1 have the structure represented by formula 2, formula 3 or formula 4 and R ₁ and R ₆ are identical or different, R ₂,R₄-R₅,R₇ and R ₉-R₁₀ are hydrogen, R ₃ and R ₈ are, identically or differently, selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms.

According to one embodiment of the invention, wherein L 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.

According to one embodiment of the invention, wherein L is, identically or differently, selected from a single bond, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 12 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein L is selected from single bonds.

According to one embodiment of the invention, wherein R _x1 and R _y1 are identically or differently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-6 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-6 carbon atoms, substituted or unsubstituted aryl groups having 6-12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-12 carbon atoms, substituted or unsubstituted silyl groups having 3-6 carbon atoms, substituted or unsubstituted arylsilyl groups having 6-12 carbon atoms, and combinations thereof.

According to one embodiment of the invention, wherein R _x1 and R _y1 are identically or differently selected from the group consisting of hydrogen, deuterium, halogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, trimethylsilyl, and combinations thereof, at each occurrence.

According to one embodiment of the invention, wherein R _x1 and R _y1 are hydrogen.

According to one embodiment of the invention, wherein X ₁-X₅ is selected identically or differently for each occurrence from C, CR _x1 or CR _x2, and at least one of X ₁-X₅ is selected identically or differently for each occurrence from CR _x2;Y₁-Y₅ from CR _y1 or CR _y2, and at least one of Y ₁-Y₅ is selected from CR _y2.

According to one embodiment of the invention, wherein at least one of X ₁-X₅ is CR _x2 and R _x2 is, identically or differently, selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein at least one of X ₁-X₅ is CR _x2 and R _x2 is, identically or differently, selected from substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 18 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein at least one of X ₁-X₅ is CR _x2 and R _x2 is, identically or differently, selected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein X ₁-X₅ is CR _x2 except for the ring-forming atom, and R _x2 is selected, identically or differently, from the group consisting of phenyl, biphenyl, terphenyl, tetrabiphenyl, triphenylene, tetraphenylene, 2-naphthyl, phenanthryl, anthracenyl, indenyl, fluorenyl, indolyl, carbazolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothianyl, benzothiophenyl, dibenzoselenophenyl, and combinations thereof, at least one of which is a CR _x2.

According to one embodiment of the invention, wherein at least one of Y ₂ to Y ₄ is CR _y2 and R _y2 is, identically or differently, selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms.

According to one embodiment of the invention, wherein at least one of Y ₂ to Y ₄ is CR _y2 and R _y2 is, identically or differently, selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 18 carbon atoms.

According to one embodiment of the invention, wherein at least one of Y ₂ to Y ₄ is CR _y2 and R _y2 is, identically or differently, selected from the group consisting of phenyl, biphenyl, terphenyl, tetrabiphenyl, triphenylene, tetraphenylene, 2-naphthyl, phenanthryl, anthracenyl, indenyl, fluorenyl, indolyl, carbazolyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiazyl, benzothiophenyl, dibenzoselenophenyl, and combinations thereof, at each occurrence.

According to one embodiment of the invention, wherein Y ₁ and/or Y ₅ are CR _y2 and R _y2, identically or differently, is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or a combination thereof.

According to one embodiment of the invention, wherein Y ₁ and/or Y ₅ are CR _y2, and R _y2, identically or differently, is selected from the group consisting of methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, cyclopropyl, deuterated cyclopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, and deuterated cyclohexyl at each occurrence.

According to one embodiment of the invention, wherein Z is C (R _z)₂, and R _z is the same or different at each occurrence selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 ring carbon atoms, substituted or unsubstituted aryl groups having 6-30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3-30 carbon atoms, substituted or unsubstituted silyl groups having 3-20 carbon atoms, and combinations thereof.

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

According to an embodiment of the invention, the compound is selected from the group consisting of compound BD1 to compound BD810, the specific structure of compound BD1 to compound BD810 being shown in claim 12.

According to an embodiment of the present invention, there is also disclosed an electroluminescent device including:

An anode is provided with a cathode,

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

And an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having a structure of formula 1:

wherein, in the formula 1,

At least one substituent in the substituent R ₁-R₁₀ has a structure represented by formula 2;

Wherein, in the formula 2,

R _x1 and R _y1 are each occurrence identically or differently selected 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 heteroalkyl groups having 1 to 20 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 alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylate groups, cyano groups, isothioyl groups, sulfinyl groups, phosphonyl groups, and combinations thereof;

* Represents the position where the substituent having the structure represented by formula 2 is attached to formula 1;

n is 0,1,2,3,4 or 5;

the substituents R _z can optionally be linked to form a ring.

According to one embodiment of the invention, wherein the organic layer comprises a light emitting layer, wherein the light emitting layer comprises a compound having the structure of formula 1.

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

According to one embodiment of the invention, wherein the host material comprises a compound having the structure of formula 5:

Wherein, in the formula 5,

R _g1 to R _g8 are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted 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 amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, mercapto, sulfonyl, phosphonyl, and combinations thereof;

r _g9 and R _g10 are each independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms.

According to one embodiment of the present invention, there is also disclosed a compound formulation comprising a compound having the structure of formula 1, the specific structure of which is shown in any of the foregoing 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 luminescent dopants disclosed herein may be used in combination with a variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.

In the examples of material synthesis, all reactions were carried out under nitrogen protection, unless otherwise indicated. All reaction solvents were anhydrous and used as received from commercial sources. The synthetic products were subjected to structural confirmation and characterization testing using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai's optical technique fluorescence spectrophotometer, wuhan Koste's electrochemical workstation, anhui Bei Yi g sublimator, etc.), in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, the evaporator manufactured by Angstrom Engineering, the optical test system manufactured by Frieda, st. O. F. And the lifetime test system, 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 BD176

First step

2-Bromo-4-iodo-1-methylbenzene (100 g,337 mmol), phenylboronic acid (49 g,404 mmol), pd (PPh ₃)₄(7.8g,6.8mmol),K₂CO₃ (116 g,843 mmol) were placed in a 1000mL three-necked flask, toluene 340mL, THF110mL, H ₂ O110mL were added, N ₂ was displaced, and the reaction was heated to 78 ℃ C. Until the starting material was complete, and column chromatography was performed to give intermediate 1 (80 g,325mmol, 97% yield) as a colorless oily liquid.

Second step

Intermediate 1 (81 g,329 mmol), NBS (61 g,345 mmol) was placed in a 2L two-necked flask, 1.3L acetonitrile was added to replace N ₂, heated to 80℃and the reaction was stirred. Benzoyl peroxide (BPO, 8g,33 mmol) was added in portions. The reaction was completed, and the white solid intermediate 2 (82 g, 255 mmol, 77% yield) was obtained by column chromatography.

Third step

LDA (130 mL,260 mmol) was placed in a 500mL three-necked flask, stirred under dry ice-ethanol for half an hour, methyl isobutyrate (30 mL,260 mmol) was added and stirring was continued for half an hour. Intermediate 2 (80 g,130 mmol) was added. The reaction was completed, and column chromatography was performed to give intermediate 3 (50 g,145mmol, 98% yield) as a pale yellow oil.

Fourth step

Intermediate 3 (78 g,227 mmol), KOH (88 g,1.57 mol) was mixed, H ₂ O230 mL, methanol 23mL was added, and the reaction was heated to 100℃until TLC detection was complete. Cooled, and after the reaction was restored to room temperature, the pH of the system was adjusted to acidity by adding concentrated HCl, and the intermediate (71 g,227 mmol) was obtained by filtration.

The intermediate (20 g,60 mmol) was dissolved in 200mL of dichloromethane, N ₂ was added to the solution, oxalyl chloride (30 mL,60 mmol) was gradually added dropwise, after the system had no more bubbles, the reaction was stirred for half an hour under an ice water bath, aluminum trichloride (8 g,60 mmol) was added in portions, and TLC monitoring was carried out until the reaction was completed. The mixture was filtered through celite and concentrated. Column chromatography (PE as eluent) afforded intermediate 4 (6 g,18.8mmol, 31% yield) as a white solid.

Fifth step

Intermediate 4 (18 g,57 mmol) was dissolved in 180mL methanol and stirred for half an hour in an ice-water bath, naBH ₄ was added in portions until the reaction was complete, filtered through celite and the filtrate concentrated.

The above product was dissolved in methylene chloride, et ₃ SiH (12.7 g,111 mmol) was added, stirred for half an hour under ice-water bath, TFA (18 g,155 mmol) was gradually added dropwise, and the reaction was allowed to proceed to completion, and purification by column chromatography afforded intermediate 5 (12 g,39.9mmol, yield 70%) as a colorless oil.

Sixth step

Pd ₂(dba)₃ (910 mg,0.99 mmol), BINAP (1.18 g,1.99 mmol), intermediate 5 (6 g,19.9 mmol), 4-methyl- [1,1' -biphenyl ] -3-amine (5.5 g,30 mmol) and t-Buona (3.8 g,39.8 mmol) were added to toluene (100 mL) at room temperature under nitrogen and the system heated to 120℃for 2h. After the completion of the reaction, intermediate 6 (6.7 g,16.4mmol, yield 82.7%) was obtained as a white solid by column chromatography.

Seventh step

1, 6-Dibromopyrene (2.38 g,6.6 mmol), intermediate 6 (6.2 g,15.2 mmol), pd (OAc) ₂(74mg,0.33mmol),t-Bu₃P·HBF₄ (191 mg,0.66 mmol) and t-Buona (1.46 g,15.2 mmol) were added under nitrogen at room temperature, and the system was heated to 95 ℃. After the completion of the reaction, the product compound BD176 (6 g,5.97mmol, yield 90%) was obtained by column chromatography purification. The product was identified as the target product and had a molecular weight of 1004.5.

Synthesis example 2 Synthesis of Compound BD109

The first step:

Pd ₂(dba)₃ (910 mg,0.99 mmol), BINAP (1.18 g,1.99 mmol), intermediate 5 (6 g,19.9 mmol), [1,1' -biphenyl ] -3-amine (5.5 g,30 mmol) and t-Buona (3.8 g,39.8 mmol) were added to toluene (100 mL) at room temperature under nitrogen and the system heated to 120℃for 2h. After the completion of the reaction, purification by column chromatography gave intermediate 7 (6.7 g,16.4mmol, yield 83%) as a colorless oil.

And a second step of:

1, 6-Dibromopyrene (2.2 g,6.1 mmol), intermediate 7(5.5g,14mmol),Pd(OAc)₂(68mg,0.3mmol),tBu₃PH⁺BF₄ ^-(174mg,0.6mmol) and t-Buona (1.3 g,14 mmol) were added to xylene (30 mL) at room temperature under nitrogen and the system heated to 95 ℃. After the completion of the reaction, purification by column chromatography gave BD109 (5 g,5.1mmol, yield 84%) as a yellow-green solid. The product was identified as the target product and had a molecular weight of 976.5.

Synthesis comparative example 1 Synthesis of comparative Compound A

The first step:

Pd (OAc) ₂(52mg,0.23mmol),tBu₃PH⁺BF₄ ^- (134 mg,0.46 mmol) was charged into a 250mL two-necked flask and xylene (100 mL) was added. To this solution was added N ₂ min until the color was no longer changed, followed by 1, 6-dibromopyrene (2.77 g,7.68 mmol), the compound bis (4-methyl- [1,1' -biphenyl ] -3-yl) amine (5.9 g,16.9 mmol), sodium t-butoxide (3.69 g,38.4 mmol). The N ₂ min was continued and the system was heated to 90℃until the starting material was completely reacted. After the completion of the reaction, the product was purified by column chromatography to give comparative compound a (2.4 g,2.68mmol, yield 34.9%). The product was identified as the target product and had a molecular weight of 896.4.

Synthesis comparative example 2 Synthesis of comparative Compound B

The first step:

LDA (100 mL,200 mmol) was placed in a 250mL three-necked flask, stirred under dry ice-ethanol for half an hour, methyl isobutyrate (23 mL,200 mmol) was added and stirring was continued for half an hour. Benzyl bromide (25 g,100 mmol) was added thereto and filtered through celite. After concentration, crude intermediate 8 was obtained and was directly subjected to the next reaction.

And a second step of:

Intermediate 8 (27 g,100 mmol), potassium hydroxide (56 g,1 mol) were mixed, 100mL of water, 10mL of methanol were added, and the reaction was heated to 100℃until the TLC detection reaction was complete. Cooling, adding concentrated hydrochloric acid to adjust pH to acidity after the reaction returns to room temperature, extracting organic phase with ethyl acetate, mixing organic phases, and concentrating.

The above product (27 g,100 mmol) was dissolved in 200mL of dichloromethane, N ₂ was bubbled with a drop of DMF and gradually added dropwise oxalyl chloride (12.8 mL,120 mmol) after the system had no longer generated bubbles, the reaction was moved to ice water bath and stirred for half an hour, aluminum trichloride (14.3 g,108 mmol) was added in portions and TLC monitoring was carried out until the reaction was complete. Elution by column chromatography using PE afforded intermediate 9 (22 g,91.6mmol, 85% yield) as a white solid.

And a third step of:

Intermediate 9 (22 g,99 mmol) was dissolved using 300mL methanol and placed under stirring for half an hour in an ice-water bath, naBH ₄ was added in portions until the reaction was complete, filtered through celite and the filtrate concentrated.

The above product was dissolved in methylene chloride, et ₃ SiH (22.5 g, 39 mmol) was added, stirred under ice-water bath for half an hour, TFA (34 g, 294 mmol) was gradually added dropwise, and concentrated, and purified by column chromatography to give intermediate 10 (7.7 g,34.4mmol, yield 35%) as a colorless oil.

Fourth step:

Pd ₂(dba₃) (1 g,1.1 mmol), intermediate 10 (5.1 g,22.7 mmol), 4-methyl- [1,1' -biphenyl ] -3-amine (5 g,27.2 mmol), BINAP (1.4 g,2.2 mmol) and t-Buona (4.7 g,49.6 mmol) were added to xylene (100 mL) at room temperature under nitrogen and the system heated to 90℃overnight. After the completion of the reaction, purification by column chromatography gave intermediate 11 (5.7 g,17.4mmol, yield 76%) as a white solid.

Fifth step:

1, 6-Dibromopyrene (2.6 g,7.2 mmol), 2-dimethyl-N- (4-methyl- [1,1' -biphenyl ] -3-yl) -2, 3-dihydro-1H-indan-4-amine (5.7 g,17.4 mmol), pd (OAc) ₂(161mg,0.72mmol),t-Bu₃P·BF₄ (406 mg,1.4 mmol) and t-Buona (2.7 g,28.2 mmol) were added to xylene (20 mL) at room temperature under nitrogen and the system heated to 100℃until the reaction was complete. And purified by column chromatography to give comparative compound B (1.2 g,1.41mmol, yield 20%) as a yellow-green solid. The product was identified as the target product and had a molecular weight of 852.4.

Synthesis comparative example 3 Synthesis of comparative Compound C

The first step:

Pd ₂(dba)₃ (910 mg,0.99 mmol), BINAP (1.18 g,1.99 mmol), intermediate 5 (6 g,19.9 mmol), aniline (2.79 g,30 mmol) and t-Buona (3.8 g,39.8 mmol) were reacted at room temperature under nitrogen, toluene (100 mL) was added and the system heated to 120℃for 3h. After the completion of the reaction, purification by column chromatography gave intermediate 12 (5.3 g,16.9mmol, yield 85%) as a colorless oil.

And a second step of:

1, 6-Dibromopyrene (2.38 g,6.6 mmol), intermediate 12 (4.76 g,15.2 mmol), pd (OAc) ₂(74mg,0.33mmol),t-Bu₃P·HBF₄ (191 mg,0.66 mmol) and t-Buona (1.46 g,15.2 mmol) were added to xylene (30 mL) at room temperature under nitrogen and the system heated to 95 ℃. After the completion of the reaction, the mixture was separated and purified by column chromatography to give comparative compound C (4.68 g,5.67mmol, yield 86%) as a yellow-green solid. The product was identified as the target product and had a molecular weight of 824.4.

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 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 layers specified below were evaporated sequentially on the ITO anode by thermal vacuum evaporation at a rate of 0.2-2 Angstrom/second with a vacuum of about 10 ^-8 Torr. The compound HI is used as a Hole Injection Layer (HIL). The compound HT serves as a Hole Transport Layer (HTL). Compound EB acts as an Electron Blocking Layer (EBL). Compound BD176 was then doped into compound BH and co-evaporated to serve as the light emitting layer (EML). Compound HB 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 encapsulated with a glass cover and a moisture absorbent to complete the device.

Device example 2

The embodiment of device example 2 is the same as device example 1 except that compound BD109 is used in place of compound BD176 in the light emitting layer (EML).

Device comparative example 1

The embodiment of device comparative example 1 is the same as device example 1 except that compound a is used in place of compound BD176 in the light emitting layer (EML).

Device comparative example 2

The embodiment of device comparative example 2 is the same as device example 1 except that compound C is used in place of compound BD176 in the light emitting layer (EML).

Device comparative example 3

The embodiment of device comparative example 3 is the same as device example 1 except that compound B is used in place of compound BD176 in the light emitting layer (EML).

The detailed device layer portion structure and thickness are shown in table 1. 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 and comparative examples

The material structure used in the device is as follows:

IVL was measured for all example and comparative example devices at different current densities and voltages. External Quantum Efficiency (EQE), maximum emission wavelength (λ _max), full width at half maximum (FWHM) and CIE data were measured at a constant current of 1000cd/m ².

Table 2 device data for example 1, comparative example 1 and comparative example 3

Device numbering	CIE(x,y)	λmax(nm)	FWHM(nm)	EQE(%)
					Example 1	0.135,0.118	461	29.70	9.12
Comparative example 1	0.140,0.098	456	32.20	8.88
					Comparative example 3	0.135,0.118	461	30.10	9.05

Discussion:

The device data of example 1, comparative example 1 and comparative example 3 are shown in Table 2, and it can be seen that the device example 1 has an External Quantum Efficiency (EQE) of 9.12%, a maximum emission wavelength of 460 nm, a CIE of (0.135,0.118), a half-width of 29.7nm, and the comparative example 1 has an External Quantum Efficiency (EQE) of 8.88%, a maximum emission wavelength of 266 nm, a CIE of (0.140,0.098), and a half-width of 32.2nm. Example 1 has an EQE increased by 2.7% with a narrowing of the half-width by 3.5nm compared to comparative example 1. From the result of example 1, compared with the result of comparative example 1, since a specific benzo-saturated ring substituent is introduced into one aryl group in the aromatic amine, there is a higher EQE and a narrower half-peak width in the device result, effectively increasing the blue light emission performance.

Comparative example 3 has an External Quantum Efficiency (EQE) of 9.05%, a maximum emission wavelength of 460 nm, a cie (0.135,0.118), and a half-width of 30.1nm. In example 1, compared with the result of comparative example 3, the EQE was increased by 0.77% and the half-width was narrowed by 0.4nm due to further introduction of aryl group on the benzo-saturated ring, effectively increasing the blue light emitting property.

Table 3 example 2 and comparative example 2 device data

Discussion:

The device data for example 2 and comparative example 2 are shown in Table 3, and it can be seen that example 2 has an External Quantum Efficiency (EQE) of 9.02%, a maximum emission wavelength of 463nm, a CIE of (0.133,0.129), a half-width of 30.5nm, and comparative example 2 has an External Quantum Efficiency (EQE) of 8.65%, a maximum emission wavelength of 463nm, a CIE of (0.133), and a half-width of 30.5nm. Example 2 has an EQE increased by 4.27% compared to comparative example 2, with both the half-peak width and the maximum emission wavelength remaining unchanged. Example 2 it can be seen that an improvement in EQE can be achieved by reintroducing a phenyl substituent into another aryl group of the aromatic amine, as compared to comparative example 2.

In summary, the novel compound obtained by introducing a substituted six-membered (hetero) aromatic ring and saturated ring structure into one aryl group of the aromatic amine substituted pyrene compound and introducing a substituted (hetero) aryl group into the other aryl group is applied to the organic electroluminescent device, and finally, blue emission wavelength in the device is realized, and the novel compound has higher EQE and narrower half-peak width, so that the comprehensive performance of the device is improved.

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

Claims

1. A compound, wherein the compound is selected from the following structures:

BD176:

2. An electroluminescent device, comprising:

anode,

cathode,

and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

3. The electroluminescent device of claim 2, wherein the organic layer comprises a light-emitting layer, wherein the light-emitting layer comprises the compound of claim 1.

The electroluminescent device according to claim 3 , wherein the light-emitting layer further comprises a host material.

5. The electroluminescent device according to claim 4, wherein the host material comprises a compound having a structure of Formula 5:

Among them, in formula 5,

_Rg1 to _Rg8 are each identically or differently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted 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 alkyl having 2 to 20 carbon atoms, alkenyl, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl having 3-20 carbon atoms, substituted or unsubstituted arylsilyl having 6-20 carbon atoms, substituted or unsubstituted amino having 0-20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;

_Rg9 and _Rg10 are each independently selected from 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.

A composition comprising the compound of claim 1.