CN112430189B

CN112430189B - Pyrene organic electroluminescent material containing aromatic amine substitution

Info

Publication number: CN112430189B
Application number: CN201910787989.8A
Authority: CN
Inventors: 赵春亮; 王峥; 叶丹; 张少博; 邝志远; 夏传军
Original assignee: Beijing Summer Sprout Technology Co Ltd
Current assignee: Beijing Summer Sprout Technology Co Ltd
Priority date: 2019-08-26
Filing date: 2019-08-26
Publication date: 2024-03-29
Anticipated expiration: 2039-08-26
Also published as: CN112430189A

Abstract

Disclosed is a pyrene organic electroluminescent material containing aromatic amine substitution. The material is prepared by introducing asymmetric structural factors into an aromatic amine structure taking pyrene as a core, and simultaneously introducing a group with specific ortho-position substitution and a fluorenyl group into the aromatic amine structure. These novel aromatic amine pyrene compounds provide better device performance when used as luminescent materials in organic light emitting devices. An electroluminescent device and a compound formulation are also disclosed.

Description

Pyrene organic electroluminescent material containing aromatic amine substitution

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. And more particularly, to a 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, 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.

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. Although fluorescent blue OLEDs have a longer lifetime than phosphorescent blue OLEDs, lifetime and efficiency are also improved to meet increasing demands in the display field, and thus improving lifetime and efficiency of fluorescent blue devices is a very important item.

WO2018095382A1 discloses compounds having the general structure:wherein Ar is ₁ To Ar ₄ At least one of which has the following general structure:/>the pyrene compound disclosed by the method has the following general structure: />Specific examples are:. The compounds disclosed in this application must incorporate naphthalene ring structures, whereby the desired effect is obtained, and do not disclose or teach the use of other aryl/heteroaryl groups with ortho-substitution in such compounds, nor do they contemplate the particular advantages of using other aryl/heteroaryl groups with ortho-substitution and fluorenyl groups simultaneously.

In US20130234118A1 the following general structure is disclosed:wherein Ar is ₁ To Ar ₄ At least one of them may be a 4-position fluorene/spirobifluorene structure as shown below: />Specific examples are: />This application discloses only triarylamine compounds having a 4-position fluorene/spirobifluorene structure, but does not disclose or teach the use of other position substituted fluorene structure groups.

In US20150255736a, triarylamine compounds with a silafluorene substituent with pyrene as core are disclosed:wherein Ar is ₁ To Ar ₄ At least one of which has the general structure>Specific examples are: />The compounds disclosed in this application must have a silafluorene structural unit, but they do not disclose or teach the simultaneous introduction of a group having a specific ortho substitution and a fluorene structural unit in such pyrene-containing triarylamine compounds, nor do they notice the particular advantage of using a fluorenyl group.

Compounds of the general structure are disclosed in TW201925161 a:wherein Ar is ⁴ The general structure of (a) is as follows: />Wherein G is pyrene, (-) -A>Anthracene and other fluorescent material core segments, n is 0 or 1, r is 0-2, s and p are 0-10, m and q are 1-10. Specific examples are: />The application relates to the research of blue light materials with fluorene ring type triarylamine structures. However, the structure disclosed in this application must contain an Ar structure fragment having 2 or more fluorene ring structural units, and since this application is an OLED device manufactured by a solution method, the multiple fluorene ring structures and long alkyl chains in the disclosed compound are all intended to be more advantageously applied to the device manufactured by the solution method. Meanwhile, due to the introduction of a plurality of fluorene ring structural units and long alkyl chains, the compound disclosed in the application is not beneficial to being applied to the preparation of OLED devices by a vacuum evaporation method. Thus, there is no disclosure or teaching in this application that only 1 fluorene ring structural unit is contained in a single Ar group, nor is there any particular advantage of groups having specific ortho-substitution noted.

Numerous fluorescent luminescent materials with an aromatic amine structure, which are core in pyrene, are disclosed in these documents. However, further developments are still needed for fluorescent materials to achieve higher device efficiencies, longer device lifetimes, etc. The inventor of the present invention has found through intensive research that, in an aromatic amine structure with pyrene as a core, asymmetric structural factors are introduced, and simultaneously, a group with specific ortho-substitution and a fluorenyl group are introduced into the aromatic amine structure, so that when novel aromatic amine pyrene compounds are obtained and used as luminescent materials in organic luminescent devices, the novel compounds provide better device performance.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of novel pyrene compounds having an aromatic amine structure. The compounds are useful as light emitting materials in organic electroluminescent devices. These novel compounds can provide better device performance.

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

in the formula 1, the components are mixed,

substituent R ₁ To R ₁₀ At least one substituent has a structure represented by formula 2:

and substituent R ₁ To R ₁₀ At least one substituent of the formula 3:

And R is ₁ To R ₁₀ Each of the remainder of (a) is independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted having 3 to 20 ring carbonsCycloalkyl of atoms, substituted or unsubstituted heteroalkyl of 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl of 7 to 30 carbon atoms, substituted or unsubstituted alkoxy of 1 to 20 carbon atoms, substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl of 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl of 6 to 20 carbon atoms, substituted or unsubstituted amine of 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

in the formula 2, the components are mixed,

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

R _c independently 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;

Ar ₁ Has a structure represented by formula 4 or formula 5, and Ar is ₁ Comprises only one fluorene ring structure, an azafluorene ring structure, a spirobifluorene ring structure, or an azaspirobifluorene ring structure:

in the formulae 4 and 5,

* Represents the Ar ₁ The position of N shown in connection formula 2;

X ₁ -X ₄ each independently selected from CR or N, X ₅ -X ₈ Each independently selected from CR' or N;

L ₁ independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms;

R，R'，R _a and R is _b 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 amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid groups, ester groups, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

In formula 4 or formula 5, the substituent R _a And R is _b Can optionally be linked to form a ring;

in formula 4 or formula 5, two adjacent substituents R can be optionally linked to form a ring, and two adjacent substituents R' can be optionally linked to form a ring;

in the formula 3, the components are mixed,

* Represents the position where the substituent having the structure represented by formula 3 is attached to the pyrene ring in formula 1;

L ₂ independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms;

R _d independently 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;

ring Ar is an aryl group having 6 to 30 ring carbon atoms or a heteroaryl group having 3 to 30 ring atoms; and when ring Ar is an aryl group, ring Ar is not a naphthalene ring structure;

R _e represents ortho-substitution of the position of N in formula 3 to which the ring Ar is attached, R _f Can represent a single fetchSubstituted, polysubstituted, or unsubstituted;

R _e independently selected from the group consisting of: substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having from 7 to 30 carbon atoms, substituted or unsubstituted amine groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, nitrile groups, isonitrile groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof;

R _f 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 amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid groups, ester groups, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

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

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 compound is shown in the foregoing.

The novel pyrene compound with the aromatic amine structure disclosed by the invention can be used as a luminescent material in an electroluminescent device. These novel compounds can provide better device performance, such as higher efficiency, more blue luminescence, longer lifetime, etc.

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 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 a cathode having a thin layer of metal such as Mg: ag and an overlying transparent layerA composite cathode of an bright, 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-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, 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 silyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, refers to any one or more groups selected from alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, silyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups that 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 aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms or preferably unsubstituted aryl having 6 to 12 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms or preferably unsubstituted heteroaryl having 3 to 12 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, the carboxylic acid group, ester group, nitrile group, isonitrile group, thio group, sulfinyl group, sulfonyl group, phosphine group, 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:

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

in the formula 1, the components are mixed,

and substituent R ₁ To R ₁₀ At least one substituent of the formula 3:

and R is ₁ To R ₁₀ Each of the remainder of (a) is 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 Substituted 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 amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, nitrile groups, isonitrile groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

in the formula 2, the components are mixed,

in the formulae 4 and 5,

* Represents the Ar ₁ The position of N shown in connection formula 2;

X ₁ -X ₄ Each independently selected from CR or N (X for formula 4 ₁ ，X ₃ And X ₄ Each independently selected from CR or N, X for formula 5 ₁ ，X ₂ And X ₄ Each independently selected from CR or N), X ₅ -X ₈ Each independently selected from CR' or N;

in the formula 3, the components are mixed,

R _e represents ortho-substitution of the position of N in formula 3 to which the ring Ar is attached, R _f Can represent mono-substituted, poly-substituted, or unsubstituted;

In this embodiment, in formula 4 or formula 5, only the substituents R _a And R is _b Can optionally be linked to form a ring, two adjacent substituents R 'can optionally be linked to form a ring, and the other substituents are not linked to form a ring, e.g., adjacent substituents R' and R are not linked to form a ring. In some cases, none of the substituents in formula 4 may be linked to form a ring. In some cases, none of the substituents in formula 5 may be linked to form a ring.

In this embodiment, the substituent R in formula 1 ₁ To R ₁₀ At least one substituent has the structure represented by formula 2, and substituent R ₁ To R ₁₀ At least one substituent of the formula 3, and R ₁ To R ₁₀ The remainder of (2) are each independently selected from the group consisting of the foregoing. For example, when the substituent R ₁ Has a structure represented by formula 2, substituent R ₆ When having the structure represented by formula 3, R ₁ To R ₁₀ The remainder of (a), R ₂ To R ₅ And R is ₇ To R ₁₀ Each independently selected from the group consisting of the foregoing.

In this embodiment, the ring Ar in formula 3 refers to a ring structure consisting only of ring atoms (which may all be ring carbon atoms and may also contain ring heteroatoms). All substituents which have to be present and which may be present on the ring Ar are exclusively represented by R in formula 3 _e And R is _f The representation is performed. When ring Ar is an aryl group having 6 to 30 ring carbon atoms or a heteroaryl group having 3 to 30 ring atoms, it means that ring Ar is an aryl ring structure having 6 to 30 ring carbon atoms or a heteroaryl ring structure having 3 to 30 ring atoms. Thus, ring Ar is not a naphthalene ring structure, meaning that ring Ar is not a structure of formula I or formula II: formula I or formula II represents the position of the ring Ar to which N has been shown in formula 3. Partial Structure relating to Ring Ar in formula 3 +. >Which is not a structure represented by any of formula III, formula IV or formula V:in the structure of formula III, formula IV or formula V, R _f Can be monosubstituted, polysubstituted or unsubstituted, and is applicable to substituents R in the structures of the formulae III, IV or V _e And R is _f Is not particularly limited in scope. In some cases, the substituent R in the structures of formula III, formula IV or formula V _e Can be in the range of R in this embodiment _e The scope of the definition being the same, a substituent R in the structures of formula III, formula IV or formula V _f Can be in the range of R in this embodiment _f The defined ranges are the same.

Also in this embodiment, the Ar ₁ Comprises only one fluorene ring structure, an azafluorene ring structure, a spirobifluorene ring structure, or an azaspirobifluorene ring structure, meaning that only one of the four ring structures of formula 4 or formula 5 is contained for the sum of the numbers of fluorene ring structures, azafluorene ring structures, spirobifluorene ring structures, and azaspirobifluorene ring structures. The only one ring structure is that comprising X ₁ ，X ₄ ，X ₅ To X ₈ The ring structure including these atoms or groups. It will be appreciated that in formula 4 or formula 5 above, L ₁ Neither R' nor R contains a fluorene ring structure, an azafluorene ring structure, a spirobifluorene ring structure, or an azaspirobifluorene ring structure. It is noted that even if one or more optional substituents are present on the fluorene ring structure, the azafluorene ring structure, the spirobifluorene ring structure, or the azaspirobifluorene ring structure, such a structure is still accounted for in the Ar ₁ Including the number of ring structures.

In certain embodiments, R in formula 2 _c At most, comprises a fluorene ring structure, an azafluorene ring structure, a spirobifluorene ring structure, or an azaspirobifluorene ring structure. Even if one or more optional substituents are present on the fluorene ring structure, azafluorene ring structure, spirobifluorene ring structure, or azaspirobifluorene ring structure, such a structure will still be counted into the R _c Including the number of ring structures. In this case, R _c Contains no more than one of the above ring structures.

According to one embodiment of the invention, wherein the substituents R ₁ -R ₁₀ Wherein one substituent is a structure represented by formula 2, and substituent R ₁ -R ₁₀ Still another substituent of (a) is a structure represented by formula 3.

According to one embodiment of the invention, wherein the substituents R ₁ The substituent R is a structure represented by formula 2 ₆ Is a structure represented by formula 3.

According to one embodiment of the invention, wherein the substituents R ₂ ，R ₄ -R ₅ ，R ₇ ，R ₉ -R ₁₀ Is a hydrogen atom, substituent R ₃ And R is ₈ Each independently selected from hydrogen, 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 said compound, wherein said L ₁ And L ₂ Each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 12 carbon atoms; preferably, L ₁ And L ₂ Each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

According to one embodiment of the invention, wherein X ₁ To X ₄ Each independently selected from CR, X ₅ -X ₈ Each independently selected from CR' or N; wherein R and R' are each independently 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 3-10 ring 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 amine groups having 0-6 carbon atoms, nitriles, isonitriles, and combinations thereof; preferably, R and R' are each independently selected from hydrogen, deuterium, fluoro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, phenyl, or cyano. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, cyclohexyl, phenyl, cyano.

According to an embodiment of the present invention, the substituent represented by formula 2 and the substituent represented by formula 3 may be the same or different structures.

According to one embodiment of the present invention, wherein the substituent R in formula 2 _c And/or substituents R in the formula 3 _d When selected from substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, it may not be of the structure represented by formula VI:in the structure of formula VI, R represents the position of N shown in the connection formula 2 or 3 _s Can represent mono-substituted, poly-substituted, or unsubstituted. In the structure of formula VI, the substituent R _s 、R _s1 And R is _s2 The range of (2) is not particularly limited. In some cases, substituent R in the structure of formula VI _s 、R _s1 And R is _s2 Can be in the range of R in formula 3 _f The range of the defined categories is the same.

According to one embodiment of the invention, wherein the compound, wherein R is _a ，R _b Each independently selected from substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, or substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, and R _a ，R _b Are not connected to form a ring.

According to one embodiment of the invention, wherein the compound, wherein R _a ，R _b Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and R _a ，R _b Are not connected to form a ring.

According to one embodiment of the invention, wherein the compound, wherein the ring Ar is selected from any one of the following ring structures: benzene ring, triphenylene ring, tetra-phenylene ring, phenanthrene ring, anthracene ring, indene ring, fluorene ring,A ring, indole ring, carbazole ring, benzofuran ring, dibenzofuran ring, benzothiophene ring, dibenzothiophene ring, benzoselenophene ring, dibenzoselenophene ring, or aza ring structures of any of the above. In this embodiment, for example, when ring Ar is selected from benzene rings, the corresponding partial structure of formula 3 involving ring Ar is +.>Namely +.>Wherein R is _e And R is _f Is defined as in formula 3. When ring Ar is selected from other ring structures, the situation is similar to the examples of benzene rings. For another example, when ring Ar is selected from an azabenzene ring, meaning that one or more C-H groups in the benzene ring are replaced with nitrogen atoms, corresponding formula 3 relates to the partial structure of ring Ar>Namely, isAnd the like. When ring Ar is selected from other ring structures of aza, the situation is similar to the example of an aza benzene ring.

According to one embodiment of the invention, wherein the compound, wherein R _e 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.

According to one embodiment of the invention, wherein R _f Represents no substitution, or R _f Represents monosubstituted and R _f Selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted silyl having 3 to 6 carbon atoms, substituted or unsubstituted amine having 0 to 6 carbon atoms, nitrile, isonitrile, and combinations thereof; preferably, R _f Selected from phenyl, biphenyl, terphenyl.

According to one embodiment of the invention, wherein R _c And R is _d Each independently selected from a substituted or unsubstituted aryl group having from 6 to 12 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 3 to 12 carbon atoms; preferably, R _c And R is _d Each independently selected from substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups.

According to one embodiment of the invention, wherein the compound is selected from the group consisting of compound 1-1 to compound 1-256, compound 2-1 to compound 2-140, compound 3-1 to compound 3-268, compound 4-1 to compound 4-140, and compound 5-1 to compound 5-96. The specific structures of the compounds 1-1 to 1-256, the compounds 2-1 to 2-140, the compounds 3-1 to 3-268, the compounds 4-1 to 4-140 and the compounds 5-1 to 5-96 are shown in claim 11.

According to one embodiment of the present invention, hydrogen in any one of compounds 1-1 to 1-256, 2-1 to 2-140, 3-1 to 3-268, 4-1 to 4-140, and 5-1 to 5-96 can be partially or completely substituted with deuterium.

According to one embodiment of the invention, wherein the molecular weight of the compound is less than 1800; further, or molecular weight is less than 1500.

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 formula 1. The specific structure of the compound is shown in any one of the previous embodiments.

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

According to one embodiment of the invention, the device, the light emitting layer further comprises at least one host material, wherein the host material is a compound having formula 6:

R _f1 to R _f8 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 amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid groups, ester groups, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

R _f9 And R is _f10 Independently selected from substituted or unsubstituted aryl or heteroaryl groups having 5 to 30 ring atoms.

According to another embodiment of the present invention, a compound formulation comprising a compound represented by formula 1 is also disclosed. The specific structure of the compound is shown in any one of the previous embodiments.

Combined with other materials

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

Materials described herein as useful for specific layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the 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, a vapor deposition machine manufactured by Angstrom Engineering, an optical test system manufactured by Frieda, st. John's, an ellipsometer manufactured by Beijing, etc.), in a manner well known to those skilled in the art. Since those skilled in the art are aware of the relevant contents of the device usage and the testing method, and can obtain the intrinsic data of the sample certainly and uninfluenced, the relevant contents are not further described in this patent.

Material synthesis examples:

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

material synthesis examples:

synthesis example 1: synthesis of Compound 3-141

Step 1: synthesis of 9, 9-dimethyl-N-phenyl-9H-fluoren-3-amine

Pd is added at room temperature under the protection of nitrogen ₂ (dba) ₃ (2.1 g,2.2 mmol) was added to toluene (200 mL), and after stirring for 10min BINAP (3.0 g,4.5 mmol) was added and stirring continued for 20min. 3-bromo-9, 9-dimethyl-9H-fluorene (11.9 g,44.1 mmol) was added to the reaction solution, after stirring until it was completely dissolved, aniline (6.1 g,66.0 mmol) was added, after stirring for 5min, sodium t-butoxide (12.9 g,134.0 mmol) was added, and the reaction solution was heated to 110℃for 3H. After the completion of the reaction, the solvent was removed by rotary evaporation under reduced pressure and purified by column chromatography to give 9, 9-dimethyl-N-phenyl-9H-fluoren-3-amine (11.5 g, yield 93%) as a white solid.

Step 2: synthesis of 6-bromo-N, N-bis (4-methyl- [1,1' -biphenyl ] -3-yl) pyrene-1-amine

Bis (4-methyl- [1,1 '-biphenyl ] -3-yl) amine (5.0 g,14.3 mmol), 1, 6-dibromopyrene (10.3 g,28.6 mmol), palladium acetate (96 mg,0.43 mmol), 1' -bis (diphenylphosphine) ferrocene (470 mg,0.86 mmol) and sodium t-butoxide (3.4 g,35.82 mmol) were sequentially added to a dry 500mL two-necked flask under nitrogen protection, after replacing nitrogen three times, xylene (200 mL) was added and nitrogen was introduced into the flask for 5min, and the flask was heated to 100℃until the starting materials were reacted completely. Purification by column chromatography gave the compound 6-bromo-N, N-bis (4-methyl- [1,1' -biphenyl ] -3-yl) pyrene-1-amine (2.5 g,3.98mmol, 28% yield) as a pale yellow solid.

Step 3: synthesis of Compound 3-141

Palladium acetate (22 mg,0.095 mmol), t-Bu, was reacted at room temperature under nitrogen ₃ P·HBF ₄ Xylene (45 mL) was added (55 mg,0.19 mmol). N is introduced into the solution ₂ For 20 minutes, 6-bromo-N, N-bis (4-methyl- [1,1' -biphenyl) was added successively]-3-yl) pyrene-1-amine (2 g,3.18 mmol), 9-dimethyl-N-phenyl-9H-fluoren-3-amine (1.4 g,4.77 mmol), sodium t-butoxide (0.76 g,7.95 mmol). Continuing to feed N ₂ 10 minutes, the system was heated to 100deg.C until 6-bromo-N, N-bis (4-methyl- [1,1' -biphenyl)]-3-yl) pyrene-1-amine is fully reacted. Column chromatography purification gave the product compound 3-141 (1.8 g,2.16mmol, 68% yield) which was identified as the target product, molecular weight 832.4.

Synthesis example 2: synthesis of Compounds 5-17

Step 1: synthesis of 6-bromo-N- (9, 9-dimethyl-9H-fluoren-3-yl) -N-phenylpyrene-1-amine

9, 9-dimethyl-N-phenyl-9H-fluoren-3-amine (2.5 g,8.7 mmol), 1, 6-dibromopyrene (6.3 g,17.4 mmol), palladium acetate (58 mg,0.26 mmol), 1' -bis (diphenylphosphine) ferrocene (288 mg,0.52 mmol) and sodium t-butoxide (2.1 g,21.7 mmol) were sequentially added to a dry 500mL two-necked flask under the protection of nitrogen, after replacing nitrogen three times, xylene (100 mL) was added and nitrogen was introduced into the flask for 5min, and the flask was heated to 100℃until the reaction was complete. After the completion of the reaction, the compound 6-bromo-N- (9, 9-dimethyl-9H-fluoren-3-yl) -N-phenylpyrene-1-amine (2.6 g,4.6mmol, yield 53%) was obtained by purification by column chromatography.

Step 2: synthesis of Compounds 5-17

Palladium acetate (20.3 mg,0.906 mmol), t-Bu, was reacted at room temperature under nitrogen ₃ P·HBF ₄ Xylene (60 mL) was added (52.6 mg,0.18 mmol). N is introduced into the solution ₂ 6-bromo-N- (9, 9-dimethyl-9H-fluoren-3-yl) -N-phenylpyrene-1-amine (1.7 g,3.02 mmol), 9-dimethyl-N- (o-methylphenyl) -9H-fluoren-3-amine (1.35 g,4.53 mmol), sodium t-butoxide (0.726 g,7.55 mmol) were added sequentially over 20 min. Continuing to feed N ₂ The system was heated to 100deg.C for 10 minutes until the reaction was complete, and purified by column chromatography to give compound 5-17 (1.4 g,1.79mmol, 59% yield) as a yellowish green solid. The product was identified as the target product, molecular weight 782.4.

Synthesis example 3: synthesis of Compounds 1-141

Step 1: synthesis of 6-bromo-N- (9, 9-dimethyl-9H-fluoren-2-yl) -N-phenylpyrene-1-amine

Pd (OAc) ₂ (118 mg,0.52 mmol), dppf (583 mg,1.05 mmol) was put into a 100mL two-necked flask, and xylene (50 mL) was added. N is introduced into the solution ₂ 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine (3 g,10.51 mmol), 1, 6-dibromopyrene (7.57 g,21.02 mmol), sodium t-butoxide (2.02 g,21.02 mmol) were added sequentially after 10 minutes until the color was no longer changed. Continuing to feed N ₂ For 10 minutes, the system was heated to 90 ℃ until the starting materials were completely reacted. Column chromatography (PE: tol=10:1 to 5:1) afforded the compound 6-bromo-N- (9, 9-dimethyl-9H-fluoren-2-yl) -N-phenylpyrene-1-amine (3 g,5.31mmol, yield=50.5%).

Step 2: synthesis of Compounds 1-141

Pd (OAc) ₂ (24mg，0.11mmol)，t-Bu ₃ P·HBF ₄ (62 mg,0.21 mmol) was placed in a 100mL two-necked flask, and xylene (45 mL) was added. N is introduced into the solution ₂ For 10 minutes until the color6-bromo-N- (9, 9-dimethyl-9H-fluoren-2-yl) -N-phenyl-pyrene-1-amine (2 g,3.54 mmol) was added successively, without further change, compound 2 (4-methyl- [1,1' -biphenyl]3-yl) amine (1.48 g,4.25 mmol), sodium t-butoxide (850 mg,8.85 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 90 ℃ until the starting materials were completely reacted. After the completion of the reaction, the compound 1-141 (1.3 g,1.56mmol, yield 44.1%) was obtained by column chromatography purification. The product was identified as the target product, molecular weight 832.4.

Synthesis example 4: synthesis of Compound 3-131

Step 1: synthesis of 6-bromo-N- (4-methyl- [1,1' -biphenyl ] -3-yl) -N-phenylpyrene-1-amine

4-methyl-N-phenyl- [1,1' -biphenyl ] -3-amine (4.5 g,17.3 mmol), 1, 6-dibromopyrene (12.5 g,34.7 mmol), palladium acetate (116 mg,0.52 mmol), 1' -bis (diphenylphosphine) ferrocene (576 mg,1.04 mmol) and sodium tert-butoxide (3.65 g,38.06 mmol) were sequentially added to a dry 500mL two-necked flask under nitrogen protection, after three times of nitrogen substitution, xylene (350 mL) was added and nitrogen was introduced into the flask, heated to 95℃for reaction until the starting materials were complete, and purified by column chromatography to give 6-bromo-N- (4-methyl- [1,1' -biphenyl ] -3-yl) -N-phenylpyrene-1-amine (5.1 g,9.5mmol, 55% yield) as a pale yellow solid.

Step 2: synthesis of Compound 3-131

Palladium acetate (40 mg,0.18 mmol), tri-tert-butylphosphine tetrafluoroborate (104.5 mg,0.36 mmol) and xylene (120 mL) were successively added to a dry 500mL two-necked flask under nitrogen at room temperature. To this solution was added nitrogen gas for 15 minutes with stirring, and 6-bromo-N- (4-methyl- [1,1' -biphenyl ] -3-yl) -N-phenylpyrene-1-amine (3.2 g,5.96 mmol), 9-dimethyl-N- (2-methylphenyl) -9H-fluoren-3-amine (2.32 g,7.75 mmol), and sodium t-butoxide (1.26 g,13.11 mmol) were added. Nitrogen was continued to be introduced for 10 minutes and the system was heated to 95 ℃ until the reaction was complete. Column chromatography gave compound 3-131 (3.4 g,4.5mmol, 76% yield) as a yellow-green solid. The product was identified as the target product, molecular weight 756.4.

Synthetic comparative example 1: synthesis of comparative Compound 1

Step 1: synthesis of N- ([ 1,1' -biphenyl ] -4-phenyl) -6-bromo-N-phenyl-pyrene-1-amine

N-phenyl- [1,1' -biphenyl ] -4-amine (30.0 g,122.3 mmol), 1, 6-dibromopyrene (88 g,244.6 mmol), palladium acetate (1.37 g,6.1 mmol) and dppf (6.78 g,12.23 mmol) were sequentially added to a dry 1000mL two-necked flask under the protection of nitrogen, after replacing nitrogen three times with sodium tert-butoxide (23.5 g,244.6 mmol), xylene (600 mL) was added and nitrogen was introduced into the flask for 5min, and the flask was heated to 90℃until the reaction was complete. After the reaction was completed, column chromatography was performed to obtain a yellowish green solid compound, N- ([ 1,1' -biphenyl ] -4-phenyl) -6-bromo-N-phenyl-pyrene-1-amine (20 g,38.13mmol, yield 31.2%).

Step 2: comparative Synthesis of Compound 1

Pd (OAc) ₂ (52mg，0.23mmol)，tBu ₃ P·HBF ₄ (134 mg,0.46 mmol) was placed in a 250mL two-necked flask and xylene (60 mL) was added. N is introduced into the solution ₂ After 20 minutes until the color is no longer changed, N- ([ 1,1' -biphenyl) is added in sequence]-4-phenyl) -6-bromo-N-phenylpyrene-1-amine (2.5 g,4.77 mmol), compound bis (4-methyl- [1,1' -biphenyl)]-3-yl) -amine (2.0 g,5.73 mmol), sodium t-butoxide (1.15 g,11.93 mmol). Continuing to feed N ₂ For 10 minutes, the system was heated to 90 ℃ until the starting materials were completely reacted. After the completion of the reaction, column chromatography gave comparative compound 1 (1.18 g,1.49mmol, yield 31.2%). Product identification as targetProduct, molecular weight 792.4.

Synthetic comparative example 2: synthesis of comparative Compound 2

Step 1: comparative Synthesis of Compound 2

Pd (OAc) was taken at room temperature under nitrogen blanket ₂ (60.0 mg,0.25 mmol) was added to xylene (50 mL) and after stirring for 10min, t-Bu was added ₃ P·HBF ₄ (145.0 mg,0.5 mmol) was stirred for an additional 20min. 1, 6-dibromopyrene (1.8 g,5.0 mmol) was added to the reaction system and after stirring to complete dissolution, 9-dimethyl-N-phenyl-9H-fluoren-3-amine (4.2 g,15.0 mmol) was added to the reaction solution, sodium t-butoxide (2.0 g,20.0 mmol) was added after stirring to complete dissolution, the reaction solution was warmed to 95℃and after completion of the reaction the solvent was removed by spin-drying under reduced pressure and purified by column chromatography to give comparative compound 2 (3.0 g, yield 78%). The product was identified as the target product and had a molecular weight of 768.4.

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 embodiment

Device example 1

First, a glass substrate having an 80nm thick Indium Tin Oxide (ITO) anode was cleaned, and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was baked in a glove box to remove moisture. The substrate is then mounted on a substrate support and loaded into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 ^-8 The deposition was performed sequentially on the ITO anode by thermal vacuum deposition at a rate of 0.2 to 2 a/s in the case of a tray. 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 BH was then co-evaporated with inventive compound 3-141 (96:4) to serve as a 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

Device example 2 was prepared in the same manner as device example 1 except that inventive compounds 5-17 were used in place of inventive compounds 3-141.

Device comparative example 1

Device comparative example 1 was prepared in the same manner as device example 1 except that comparative compound 1 was used in place of inventive compounds 3-141.

Device comparative example 2

Device comparative example 2 was prepared in the same manner as device example 1 except that comparative compound 2 was used in place of inventive compounds 3-141.

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 partial device structures of device examples and comparative examples

The material structure used in the device is as follows:

IVL of the device was measured at different current densities and voltages. At a constant current of 10mA/cm ² Lower test lifetime LT97, external Quantum Efficiency (EQE), maximum emission wavelength (λ _max ) Half width of peak (FWHM) and CIE data. LT97 represents the decay of device brightness to initial brightness97% life.

Discussion:

device example 1 has an External Quantum Efficiency (EQE) of 8.99%, LT97 of 325 hours, maximum emission wavelength of 466nm, cie (0.129,0.153), half-width of 34.5nm; comparative example 1 has an External Quantum Efficiency (EQE) of 8.33%, LT97 of 119 hours, maximum emission wavelength of 467nm, cie (0.130,0.168), and half-width of 35.1nm. Example 1 has an EQE increased by 7.9% and an LT97 increased by 173% compared to comparative example 1, while narrowing the half-width by 0.6nm and blue shifting the maximum emission wavelength by 1nm. From the results of example 1, there were higher EQE, LT97 and smaller CIE y values in the device results due to the introduction of specific fluorene ring substituents, effectively increasing blue emission performance, compared to the results of comparative example 1.

In addition, example 2 had an External Quantum Efficiency (EQE) of 8.60%, a maximum emission wavelength of 469nm, cie (0.128,0.179), and a half-width of 33.0nm; comparative example 2 has an External Quantum Efficiency (EQE) of 7.92%, a maximum emission wavelength of 471nm, cie (0.125,0.204), and a half-width of 36.4nm. Example 2 has an EQE increased by 8.5% compared to comparative example 2, a narrowing of the half-width by 3.4nm, and a blue shift of 2nm in the maximum emission wavelength. Example 2 it can be seen that by introducing ortho-substitution R at the ring Ar group as compared to comparative example 2 _e An asymmetric structure is introduced, so that the EQE can be improved, the maximum emission wavelength can be moved to the deep blue direction, and the blue light-emitting performance can be effectively improved. Taken together, by introducing R having ortho-substitution _e The structural design of the compound of the groups and fluorenyl groups finally realizes very good device effect.

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 formula 1:

in the formula 1, the components are mixed,

wherein the substituents R ₁ -R ₁₀ Wherein one substituent has the structure represented by formula 2, and substituent R ₁ Is a structure represented by formula 2:

substituent R ₁ -R ₁₀ Still another substituent has the structure represented by formula 3, and substituent R ₆ Is a structure represented by formula 3:

R ₂ -R ₅ and R is ₇ -R ₁₀ Each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

in the formula 2, the components are mixed,

R _c independently selected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms;

Ar ₁ has a structure represented by formula 5, and Ar is ₁ Comprises only one fluorene ring structure:

in the formula 5, the components are,

* Represents the Ar ₁ The position of N shown in connection formula 2;

X ₁ ，X ₂ ，X ₄ each independently selected from CR, X ₅ -X ₈ Each independently selected from CR';

L ₁ independently selected from single bonds;

R，R'，R _a and R is _b Each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and combinations thereof;

in the formula 3, the components are mixed,

L ₂ independently selected from single bonds;

R _d Independently selected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms;

ring Ar is an aryl group having 6 to 12 ring carbon atoms; and when ring Ar is an aryl group, ring Ar is not a naphthalene ring structure;

R _e independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms;

R _f independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aryl groups having 6-12 carbon atoms, and combinations thereof;

substituted alkyl and substituted aryl, the substitution being by one or more groups selected from deuterium, unsubstituted alkyl groups having 1-20 carbon atoms, unsubstituted aryl groups having 6-12 carbon atoms, and combinations thereof.

2. The compound of claim 1 wherein the substituent R ₂ ，R ₄ -R ₅ ，R ₇ ，R ₉ -R ₁₀ Is a hydrogen atom, substituent R ₃ And R is ₈ Each independently selected from hydrogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

3. The compound of claim 1, wherein X ₁ ，X ₂ ，X ₄ Each independently selected from CR, X ₅ To X ₈ Each independently selected from CR'; wherein R and R' are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, and combinations thereof.

4. The compound of claim 1, wherein X ₁ ，X ₂ ，X ₄ Each independently selected from CR, X ₅ To X ₈ Each independently selected from CR'; wherein R and R' are each independently selected from hydrogen, deuterium, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

5. The compound of claim 1, wherein R _a ，R _b Each independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and R _a ，R _b Are not connected to form a ring.

6. The compound of claim 1, wherein R _a ，R _b Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

7. The compound of claim 1, wherein ring Ar is selected from benzene rings.

8. The compound of claim 7, wherein R _e Selected from the group consisting of: methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, tert-butyl, and deuterated tert-butyl; wherein R is _f Represents no substitution, or R _f Represents monosubstituted and R _f Each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aryl groups having 6-12 carbon atoms, and combinations thereof 。

9. The compound of claim 8, wherein R _f Each independently selected from hydrogen, fluorine, phenyl, or biphenyl.

10. The compound of claim 1, wherein R _c And R is _d Each independently selected from substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, R _e Independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

11. The compound of claim 1, wherein R _c And R is _d Each independently selected from substituted or unsubstituted phenyl.

12. A compound, wherein the compound is selected from the group consisting of:

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13. the compound of claim 12, wherein/>

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The hydrogen in any of the compounds contained in (a) can be partially or completely substituted with deuterium.

14. An 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 claim 1.

15. The device of claim 14, wherein the organic layer is a light emitting layer and the compound is a light emitting material.

16. The device of claim 15, wherein the light emitting layer further comprises at least one host material, wherein the host material is a compound having formula 6:

Wherein R is _f1 To R _f8 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 amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid groups, ester groups, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

R _f9 and R is _f10 Each independently selected from a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 3 to 30 carbon atoms;

The substituted refers to being substituted with one or more groups selected from deuterium, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted aralkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

17. A composition comprising the compound of claim 1.