阅读说明：本技术 含氘原子的电子传输材料及其应用 (Electronic transmission material containing deuterium atom and its application ) 是由 张晗 陈晓 邝志远 夏传军 于 2020-05-08 设计创作，主要内容包括：公开了含氘原子的电子传输材料及其应用。所述含氘原子的电子传输材料是一种具有氘代的取代基的苯并咪唑化合物,可用作电致发光器件中的电子传输材料。这些新型化合物能使有机电致发光器件效率有所提升的同时获得更长的器件寿命,能提供更好的器件性能。还公开了一种电致发光器件和化合物配方。(Electronic transport materials containing deuterium atoms and uses thereof are disclosed. The electron transport material containing deuterium atoms is a benzimidazole compound having a deuterated substituent, and can be used as an electron transport material in an electroluminescent device. The novel compounds can improve the efficiency of the organic electroluminescent device, simultaneously obtain longer device life and provide better device performance. An electroluminescent device and compound formulation are also disclosed.)

1. A compound having a structure represented by formula 1:

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr N;

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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 aralkyl, or aralkyl, and others, aralkyl, and others, aralkyl, and othersAn alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Each occurrence, the same or different, is selected from the group consisting of: a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

2. The compound of claim 1, wherein ring X and ring Y are each independently selected from an aromatic ring having 6-18 ring atoms or a heteroaromatic ring having 5-18 ring atoms;

preferably, ring X and ring Y are each independently selected from a benzene, naphthalene, phenanthrene, anthracene, fluoranthene, pyridine or pyrazine ring;

more preferably, ring X and ring Y are each independently selected from benzene rings.

3. The compound of claim 1 or 2, wherein Ar is selected from substituted or unsubstituted aryl having 6 to 18 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms;

preferably, Ar is selected from the group consisting of: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, pyrenyl, fluoranthenyl, 9, 9-dimethylfluorenyl, spirobifluorenyl, pyridyl, quinolinyl, phenanthrolinyl, 9, 9-dimethylazafluorenyl, dibenzofuranyl, dibenzothiophenyl, and combinations thereof.

4. The compound of claim 3, wherein Ar is selected from any one of the group consisting of the following structures:

5. the compound of any one of claims 1-4, wherein L₁And L₂Each independently selected from a single bond or any of the group consisting of:

wherein R is_aThe same or different at each occurrence denotes mono-, poly-or unsubstituted;

R_aeach occurrence, the same or different, is 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 cycloalkyl having 1 to 20 carbon atomsA heteroalkyl group of a subgroup, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R_aCan optionally be linked to form a ring;

preferably, L₁And L₂Each independently selected from a single bond or phenylene.

6. The compound of any one of claims 1-5, wherein R is selected from substituted alkyl having 1-20 carbon atoms, substituted cycloalkyl having 3-20 carbon atoms, substituted aryl having 6-25 carbon atoms, substituted heteroaryl having 3-25 carbon atoms, or a combination thereof; and said R comprises at least one of D, CD₂Or CD₃；

Preferably, R is selected from the group consisting of: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated butyl, deuterated isobutyl, deuterated tert-butyl, deuterated pentyl, deuterated hexyl, deuterated heptyl, deuterated octyl, deuterated nonyl, deuterated cyclopropyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated phenyl, deuterated naphthyl, deuterated pyridyl, deuterated fluorenyl, deuterated spirobifluorenyl, deuterated dibenzofuranyl, deuterated dibenzothiophenyl, deuterated carbazolyl, and combinations thereof.

7. The compound of claim 6, wherein R is selected from any one of the group consisting of R1 through R100:

8. the compound of any one of claims 1-7, wherein Z is₁-Z₄Each independently selected from CR_z，R_zEach occurrence, identically or differently, is selected from: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a combination thereof;

preferably, R_zSelected from hydrogen or deuterium, the same or different at each occurrence.

9. The compound of claim 1, wherein the compound is selected from the group consisting of compound 1 to compound 217:

10. an electroluminescent device, comprising:

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

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

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr the number of N is greater than the number of N,

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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 amine groups having 0-20 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;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Each occurrence, the same or different, is selected from the group consisting of: single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atomsA substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

11. The device of claim 10, wherein the organic layer is an electron transport layer and the compound is an electron transport material.

12. The device of claim 11, wherein the electron transport layer further comprises at least one material;

preferably, wherein the electron transport layer further comprises at least one metal complex;

more preferably, wherein the metal complex comprises a ligand L represented by formula 2_a：

Wherein Q₁To Q₆Each independently selected from CR_qOr N; r_qEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, substituted or unsubstituted silyl having 3 to 20 carbon atoms, cyano, substituted or unsubstituted aryl having 6 to 30 carbon atoms and substituted or unsubstitutedSubstituted heteroaryl having 3 to 30 carbon atoms;

wherein W is selected from NR_NO, S or Se;

R_Neach occurrence, the same or different, is 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 amine groups having 0-20 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;

most preferably wherein the metal complex is selected from 8-hydroxyquinoline-lithium, 8-hydroxyquinoline-sodium, 8-hydroxyquinoline-potassium, bis (8-hydroxyquinoline) -beryllium, bis (8-hydroxyquinoline) -magnesium, bis (8-hydroxyquinoline) -calcium, tris (8-hydroxyquinoline) -boron, tris (8-hydroxyquinoline) -aluminum, or tris (8-hydroxyquinoline) -gallium.

13. A compound formulation comprising a compound of any one of claims 1-9.

Technical Field

The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. More particularly, it relates to a benzimidazole compound having a deuterated substituent, and an organic electroluminescent device and a compound formulation comprising the same.

Background

Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), Organic Light Emitting Transistors (OLETs), Organic Photovoltaics (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 plasma light emitting devices.

In 1987, Tang and Van Slyke of Islamic Kodak reported a two-layer 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). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). The most advanced OLEDs may comprise 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. Since OLEDs are a self-emissive solid state device, it offers 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 the fabrication of flexible substrates.

OLEDs can be classified into three different types according to their light emitting mechanisms. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes to the commercialization of active matrix OLEDs (amoleds). Recently, Adachi has achieved high efficiency through 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 are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.

OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.

Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.

In general, an organic electroluminescent device has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Electric charges are injected into an organic layer formed between an anode and a cathode to form electron and hole pairs, causing an organic compound having fluorescent or phosphorescent characteristics to generate light emission. The organic layers may be formed of a multilayer structure composed of different substances due to the difference in the moving speed of holes and electrons, such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

To achieve better device performance, such as higher device efficiency, longer device lifetime, etc., it is a solution to develop new electron transport materials.

A series of compounds having a benzimidazole structure are disclosed in KR20170107140 (a):wherein R is₁Is imidazolyl, phenyl or pyridyl, R₂Deuterated alkyl or aryl, specific examples are:the compounds disclosed in this application must have a structure in which the benzimidazole is linked to the anthracene at the 2-position via a phenylene group, which does not disclose or teach the use of benzimidazole to link to other sites of anthracene or other fused structures.

KR101460365(B1) discloses a series of compounds having phenanthro [9,10 ]]Compound of imidazole structure:specific examples areThe compounds disclosed in this patent must have phenanthro [9,10 ]]Imidazole structures, and does not disclose or teach the use of benzimidazole structures with deuterated substituents to link fused structures.

In order to obtain better performance of the organic light emitting device, one idea is to develop a more excellent electron transport material to improve electron transport efficiency, so that holes and electrons in the device reach a more balanced state, thereby improving light emitting efficiency and/or lifetime. Although there have been many studies on electron transport materials, the properties of the materials have shortcomings, and the development of new high-performance electron transport materials is still in need.

Disclosure of Invention

The present invention aims to solve at least part of the above problems by providing a series of benzimidazole compounds having deuterated substituents. The compounds are useful as electron transport materials in organic electroluminescent devices. The novel compounds can improve the efficiency of the organic electroluminescent device, simultaneously obtain longer device life and provide better device performance.

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

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr N;

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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 amine groups having 0-20 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;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Each occurrence, the same or different, is selected from the group consisting of: a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

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 a structure represented by formula 1:

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr N;

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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 alkylsilicon having 3 to 20 carbon atomsA group, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Each occurrence, the same or different, is selected from the group consisting of: a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

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

The novel benzimidazole compound with the deuterated substituent can be used as an electron transport material in an electroluminescent device. The novel compounds can improve the efficiency of the organic electroluminescent device, simultaneously obtain longer device life and provide better device performance.

Drawings

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

Fig. 2 is a schematic view of another organic light emitting device that can contain compounds and compound formulations disclosed herein.

Figure 3 is structural formula 1 showing compounds as disclosed herein.

Detailed Description

OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures 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, an emissive 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 described layers. The nature and function of the layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.

There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. 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 at a molar ratio of 50:1₄TCNQ m-MTDATA 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. patent 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 at 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. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: Ag and an overlying layer of transparent, conductive, sputter-deposited ITO. 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 injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. Which can be incorporated by reference in its entiretyA description of protective layers is found in U.S. patent application publication No. 2004/0174116.

The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some 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 sub-layers. 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, as shown in fig. 2, which is an exemplary, non-limiting illustration of an organic light emitting device 200, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to protect against 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 a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is 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 various 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, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.

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

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "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 "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.

It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can generally be divided into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).

On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch between energy states. Thermal energy can activate the 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 retardation component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, then the fraction of backfill singlet excited states may reach 75%. The total singlet fraction may be 100%, far exceeding 25% of the spin statistics of the electrogenerated excitons.

The delayed fluorescence of type E can be characterized by excitation of complex systems or single compoundsIn (1). Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small mono-triplet energy gap (Δ Ε)_S-T). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ E_S-T. These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).

Definitions for substituent terms

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

Alkyl-comprises both straight and branched chain 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 carbons 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 preferable.

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

Alkenyl-as used herein, encompasses both straight and branched chain olefinic groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group and a 3-phenyl-1-butenyl group. In addition, alkenyl groups may be optionally substituted.

Alkynyl-as used herein, straight and branched alkynyl groups are contemplated. 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,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 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-quaterphenyl.

Heterocyclyl or heterocyclic-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 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 which may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 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, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, cinnolino, benzoselenophenopyridine, selenobenzene, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.

Alkoxy-is represented by-O-alkyl. Examples and preferred examples of the alkyl group are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. 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 a phenoxy group and a biphenyloxy group.

Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally substituted. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 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-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable.

The term "aza" in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives may be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed within the terms described herein.

In this disclosure, unless otherwise defined, when any one of the terms in 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 amine, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino, any of which groups may be substituted with one or more moieties selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, unsubstituted aralkyl groups having 7 to 30 carbon atoms, unsubstituted alkoxy groups having 1 to 20 carbon atoms, unsubstituted aryloxy groups having 6 to 30 carbon atoms, unsubstituted alkenyl groups having 2 to 20 carbon atoms, unsubstituted aryl groups having 6 to 30 carbon atoms, unsubstituted heteroaryl groups having 3 to 30 carbon atoms, unsubstituted silyl groups having 3 to 20 carbon atoms, unsubstituted arylsilyl groups having 6 to 20 carbon atoms, 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.

It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on 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 to be equivalent.

In the compounds mentioned in the present disclosure, a hydrogen atom 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 it enhances the efficiency and stability of the device.

In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.

In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. 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 carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.

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

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

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

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

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr N;

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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 amine groups having 0-20 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;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Identical or different at each occurrenceSelected from the group consisting of: a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

As used herein, the adjacent substituent R_x，R_yCan optionally be linked to form a ring, intended to denote when a plurality of substituents R are present_xWhen adjacent substituent R_xCan optionally be linked to form a ring, when a plurality of substituents R are present_yWhen adjacent substituent R_yCan optionally be linked to form a ring. Obviously, when a plurality of substituents R are present_xA plurality of substituents R_yWhen adjacent substituent R_x，R_yOr may be both unconnected to form a ring.

According to one embodiment of the invention, wherein ring X and ring Y are each independently selected from an aromatic ring having 6 to 18 ring atoms or a heteroaromatic ring having 5 to 18 ring atoms.

According to one embodiment of the invention, wherein ring X and ring Y are each independently selected from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, a pyridine ring or a pyrazine ring.

According to one embodiment of the invention, ring X and ring Y are each independently selected from benzene rings.

According to an embodiment of the present invention, wherein in the formula 1, Ar is selected from a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms.

According to an embodiment of the present invention, wherein in formula 1, Ar is selected from the group consisting of: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, pyrenyl, fluoranthenyl, 9, 9-dimethylfluorenyl, spirobifluorenyl, pyridyl, quinolinyl, phenanthrolinyl, 9, 9-dimethylazafluorenyl, dibenzofuranyl, dibenzothiophenyl, and combinations thereof.

According to an embodiment of the present invention, wherein in formula 1, Ar is selected from any one of the group consisting of the following structures:

in this embodiment, the dotted bond represents the structure and L in formula 1₁The location of the connection.

According to an embodiment of the present invention, wherein in said formula 1, L₁And L₂Each independently selected from a single bond or any of the group consisting of:

wherein R is_aThe same or different at each occurrence denotes mono-, poly-or unsubstituted;

R_aeach occurrence, the same or different, is 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 alkyl having 6 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 carbon atomsAn arylsilyl group of carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile, an isonitrile, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

adjacent substituents R_aCan optionally be linked to form a ring.

In this embodiment, the dotted bond represents the position where the structures are connected in equation 1.

In this example, the adjacent substituents R_aCan optionally be linked to form a ring, intended to denote when a plurality of substituents R are present_aWhen there is any adjacent R_aCan be linked to form a ring. Obviously, when a plurality of substituents R are present_aWhen the substituents R are_aOr may be both unconnected to form a ring.

According to an embodiment of the present invention, wherein in said formula 1, L₁And L₂Each independently selected from a single bond or phenylene.

According to an embodiment of the present invention, wherein in the formula 1, R is selected from a substituted alkyl group having 1 to 20 carbon atoms, a substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted aryl group having 6 to 25 carbon atoms, a substituted heteroaryl group having 3 to 25 carbon atoms, or a combination thereof; and said R comprises at least one of D, CD₂Or CD₃。

According to an embodiment of the present invention, wherein in formula 1, R is selected from the group consisting of: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated butyl, deuterated isobutyl, deuterated tert-butyl, deuterated pentyl, deuterated hexyl, deuterated heptyl, deuterated octyl, deuterated nonyl, deuterated cyclopropyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated phenyl, deuterated naphthyl, deuterated pyridyl, deuterated fluorenyl, deuterated spirobifluorenyl, deuterated dibenzofuranyl, deuterated dibenzothiophenyl, deuterated carbazolyl, and combinations thereof.

In this example, R is selected from the group of deuterated substituents, which is intended to mean that the deuterated substituents can be partially deuterated substituted substituents or completely deuterated substituted substituents. For example, when R is selected from deuterated methyl, it means that R can be selected from partially deuterated substituted methyl (mono-deuterated methyl or di-deuterated methyl), and R can also be selected from fully deuterated substituted methyl (tri-deuterated methyl). The same is true when R is selected from other deuterated groups.

According to an embodiment of the present invention, wherein in formula 1, R is selected from any one of the group consisting of R1 to R100 below:

in this example, the dotted bonds represent the positions where the R1 to R100 are attached to the imidazole ring in formula 1.

According to an embodiment of the present invention, wherein in said formula 1, Z₁-Z₄Each independently selected from CR_z，R_zEach occurrence, identically or differently, is selected from: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 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, or combinations thereof.

According to an embodiment of the present invention, wherein in said formula 1, Z₁-Z₄Each independently selected from CR_z，R_zSelected from hydrogen or deuterium, the same or different at each occurrence.

According to an embodiment of the present invention, wherein the compound is selected from the group consisting of compound 1 to compound 217:

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

an anode, a cathode, a anode and a cathode,

a cathode electrode, which is provided with a cathode,

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

wherein the content of the first and second substances,

ring X and ring Y are each independently selected from an aromatic ring having 5 to 30 ring atoms or a heteroaromatic ring having 5 to 30 ring atoms;

Z₁-Z₄each independently selected from CR_zOr N;

R_xand R_yThe same or different at each occurrence denotes mono-, poly-or no-substitution;

R_x、R_yand R_zEach occurrence, the same or different, is 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, getSubstituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;

adjacent substituents R_x，R_yCan optionally be linked to form a ring;

L₁and L₂Each occurrence, the same or different, is selected from the group consisting of: a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and combinations thereof;

ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

r is selected from substituted alkyl having 1 to 20 carbon atoms, substituted cycloalkyl having 3 to 20 carbon atoms, substituted aryl having 6 to 30 carbon atoms, substituted heteroaryl having 3 to 30 carbon atoms, or combinations thereof; and said R contains at least one deuterium atom.

According to one embodiment of the invention, in the device, the organic layer is an electron transport layer and the compound is an electron transport material.

According to an embodiment of the invention, in the device, the electron transport layer further comprises at least one material.

According to one embodiment of the invention, in the device, the electron transport layer further comprises at least one metal complex.

According to one embodiment of the present invention, in the device, the metal complex includes a ligand L represented by formula 2_a：

Wherein Q₁To Q₆Each independently selected from CR_qOr N; r_qEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, substituted or unsubstituted silyl having 3 to 20 carbon atoms, cyano, substituted or unsubstituted aryl having 6 to 30 carbon atoms and substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

wherein W is selected from NR_NO, S or Se;

R_Neach occurrence, the same or different, is 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 amine groups having 0-20 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.

According to one embodiment of the invention, the device wherein the metal complex is selected from the group consisting of 8-hydroxyquinoline-lithium, 8-hydroxyquinoline-sodium, 8-hydroxyquinoline-potassium, bis (8-hydroxyquinoline) -beryllium, bis (8-hydroxyquinoline) -magnesium, bis (8-hydroxyquinoline) -calcium, tris (8-hydroxyquinoline) -boron, tris (8-hydroxyquinoline) -aluminum, and tris (8-hydroxyquinoline) -gallium.

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

In combination with other materials

The materials described herein for use in particular 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 Ser. No. 0132-0161 of U.S. 2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced 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 being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. US2015/0349273A1, paragraph 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced 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 unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product is subjected to structural validation and characterization using one or more equipment conventional in the art (including, but not limited to, Bruker's nuclear magnetic resonance apparatus, Shimadzu's liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, Shanghai prism-based fluorescence spectrophotometer, Wuhan Corset's electrochemical workstation, Anhui Beidek's 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, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, Suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.

Materials synthesis example:

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

synthesis example 1: synthesis of Compound 2

Step 1. Synthesis of [ intermediate 1-a ]

1-fluoro-2-nitrobenzene (10.0g, 71mmol), 4-bromoaniline (24.2g, 142mmol) were charged to a 100mL two-necked round bottom flask, followed by 30mL of dimethyl sulfoxide. The reaction flask was warmed to 100 ℃ and stirred under nitrogen for 48 hours. After the reaction is finished, the reaction system is cooled to room temperature, 200mL of water is added, dichloromethane is used for extraction for three times, and the organic phase is dried and concentrated to obtain a brownish red solid. The resulting solid was added to 500mL of ethanol and stirred under nitrogen for 2 hours, cooled and filtered to give a red solid [ intermediate 1-a ] (17.3g,59.0mmol, 83.2%).

Step 2. Synthesis of [ intermediate 1-b ]

[ intermediate 1-a ] (15g, 51mmol), stannous chloride (48.5g, 255.0mmol) were charged into a 500mL three-necked round-bottomed flask, followed by 150mL of anhydrous ethanol. The reaction flask was heated to 75 ℃ and refluxed, and stirred under nitrogen atmosphere for 4 hours, and the reaction solution turned from red suspension to colorless and clear. After the reaction is finished, cooling the reaction system to room temperature, removing the solvent under reduced pressure, dissolving the ethyl acetate, and then dropwise adding a potassium hydroxide aqueous solution (2M) to adjust the pH to 8-9. After three extractions with ethyl acetate, the organic phase was concentrated by drying to give a pale yellow solid. The resulting solid was added to 500mL of n-hexane and stirred under nitrogen for 2 hours, cooled and filtered to give a white solid [ intermediate 1-b ] (10.5g, 39.8mmol, 78%).

Step 3. Synthesis of [ intermediate 1-c ]

[ intermediate 1-b ] (7.0g, 26.6mmol) was charged into a 250mL three-necked round-bottomed flask, 60mL of tetrahydrofuran was added to dissolve the intermediate, and then deuterated acetyl chloride (2.2g, 26.6mmol) and N, N-diisopropylethylamine (3mL) were sequentially added to the mixture, so that the reaction solution became red, the reaction flask was stirred under nitrogen atmosphere at room temperature for 24 hours, and then 150mL of water was added to stop the reaction, and the reaction was further stirred to precipitate a solid. The solid was filtered, dissolved in 60mL of glacial acetic acid, heated to 140 ℃ under reflux, and stirred under nitrogen for 24 hours, with the reaction solution being wine-red. After the reaction was completed, it was cooled to room temperature, the pH was adjusted to 6-8 with an aqueous solution of sodium hydroxide (2M) at 0 ℃ in ice bath, and extracted with ethyl acetate, and the organic phase was concentrated by dryness and then isolated by column chromatography to give a purple solid [ intermediate 1-c ] (5.0g, 17.3mmol, 65.0%).

Step 4. Synthesis of Compound 2

[ intermediate 1-c ] (2.5g, 8.6mmol), 10- ([1,1' -biphenyl ] -4-yl) anthracen-9-ylboronic acid (3.24g, 8.6mmol), palladium tetratriphenylphosphine (520mg, 0.46mmol), and potassium carbonate (2.50g, 18.7mmol) were charged into a 250mL three-necked round-bottomed flask, followed by 45mL of tetrahydrofuran and 5mL of water. The reaction flask was warmed to 85 ℃ under reflux and stirred under nitrogen for 10 hours. After completion of the reaction, the reaction system was cooled to room temperature and extracted with dichloromethane, and the organic phase was concentrated by drying and then isolated by column chromatography to obtain Compound 2(1.7g,3.2mmol, 37.2%) as a pale yellow solid. The product was identified as the target product, molecular weight 539.2.

It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other structures of the compounds of the present invention.

Device example 1

First, a glass substrate, having an Indium Tin Oxide (ITO) anode 80nm thick, was cleaned and then treated with oxygen plasma and UV ozone. After treatment, the substrate was dried in a glove box to remove moisture. The substrate is then mounted on a substrate holder and loaded into a vacuum chamber. The organic layer specified below was in a vacuum of about 10 degrees^-8In the case of torr, the evaporation was performed by thermal vacuum evaporation at a rate of 0.2 to 2 angstroms/second in turn on an ITO anode. Compound HIUsed as a Hole Injection Layer (HIL). Compound HTUsed as a Hole Transport Layer (HTL). Compound EBUsed as an Electron Blocking Layer (EBL). The compound GD was then doped in the compound EB and the compound HB as a light emitting layer (EML,compound EB compound HB: compound GD ═ 46:46: 8). On the light-emitting layer, a compound HBThe Hole Blocking Layer (HBL) was formed by evaporation. Compound 2 of the present invention and 8-hydroxyquinoline-lithium (Liq) were then co-evaporated as an Electron Transport Layer (ETL). Finally, Liq of 10 angstroms in thickness was evaporated as an electron injection layer, and 1200 angstroms of aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.

Device comparative example 1

Device comparative example 1 was prepared in the same manner as device example 1 except that comparative compound ET1 was used in place of compound 2 of the present invention in the Electron Transport Layer (ETL).

Device comparative example 2

Device comparative example 2 was prepared in the same manner as device example 1 except that the inventive compound 2 was replaced by comparative compound ET2 in the Electron Transport Layer (ETL).

The detailed device layer structure and thickness are shown in the table below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.

TABLE 1 Electron transport layer structures of device examples and comparative examples

The material structure used in the device is as follows:

for the organic light emitting devices manufactured using the methods of the above examples and comparative examples, at 10mA/cm²The maximum wavelength λ max and the External Quantum Efficiency (EQE) were measured at a current density of 80mA/cm²The lifetime was measured at the current density of (LT 97). To more clearly show the comparison of the data, the EQE data and LT97 data of comparative example 1 were set to 100%, while the EQE and LT97 data of examples 1 and 2 were scaled with respect to the corresponding data of comparative example 1, and the related data and scaling results are shown in table 2.

TABLE 2 device data

Discussion:

as can be seen from the data in table 2, the examples exhibited improved efficiency and life as compared with comparative example 1 and comparative example 2, and particularly exhibited excellent characteristics in terms of life, which were 12.3% higher than comparative example 1 and 9.1% higher than comparative example 2. The above data demonstrate the advantages of the disclosed compounds containing deuterium atoms having the structure of formula 1 compared to compounds that do not contain deuterium atoms for use in the electron transport layer of an organic light emitting device.

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