阅读说明：本技术 一种化合物及其应用 (Compound and application thereof ) 是由 黄金华 曾礼昌 王志鹏 张维宏 黄鑫鑫 高文正 于 2021-05-10 设计创作，主要内容包括：本发明涉及一种化合物及其应用,所述化合物具有式I所示的结构,在本发明的化合物结构中,萘环1-位引入取代基Ar～(2)不仅能够调节邻位位阻大小,还能有效调控分子的扭曲度以降低分子结晶性；其次,2-位引入芳胺基团,且芳胺基团上三取代结构的引入能够有效调控分子的立体结构,提高分子的堆积致密度,进而使所设计材料能够满足器件对材料的需求。本发明的化合物应用于有机电致发光器件,特别是作为电子阻挡层时,可以提高发光效率、降低启动电压及延长器件的使用寿命。(The invention relates to a compound and application thereof, wherein the compound has a structure shown in formula I, and in the structure of the compound, a substituent Ar is introduced into 1-site of a naphthalene ring 2 Not only can adjust the size of the steric hindrance of the adjacent position, but also can effectively regulate and control the torsion resistance of molecules so as to reduce the molecular crystallizationSex; secondly, 2-site aromatic amine groups are introduced, and the introduction of a trisubstituted structure on the aromatic amine groups can effectively regulate the three-dimensional structure of molecules, so that the accumulation density of the molecules is improved, and the designed material can meet the requirements of devices on the material. The compound of the invention is applied to organic electroluminescent devices, and particularly can improve the luminous efficiency, reduce the starting voltage and prolong the service life of the devices when being used as an electron blocking layer.)

1. A compound having a structure according to formula I;

in the formula I, Ar is¹And Ar²Independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;

in the formula I, L is¹Selected from substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene;

in the formula I, L is²One selected from a single bond, a substituted or unsubstituted C6-C30 arylene, or a substituted or unsubstituted C3-C30 heteroarylene;

in the formula I, R is¹、R²And R³Independently selected from any one of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 chain alkoxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, halogen, cyano, nitro, hydroxyl, C1-C20 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; the R is¹、R²And R³Are connected with each other to form a ring or are not connected to form a ring;

in the formula I, m is an integer of 0-6;

in the formula I, R is⁴Independently selected from one of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 chain alkoxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C20 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl；

Ar¹、Ar²、L¹、L²、R¹、R²、R³And R⁴Wherein the substituted groups are independently selected from one or a combination of at least two of halogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl and C6-C30 fused ring heteroaryl.

2. The compound of claim 1, wherein L is²One selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group, preferably a single bond or a phenylene group.

3. The compound of claim 1, wherein Ar is Ar²Selected from substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl.

4. The compound of claim 1, wherein Ar is Ar²Any one selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl;

preferably, Ar is²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

5. The method of claim 1A compound characterized in that L is²Is a single bond, and Ar²Selected from substituted or unsubstituted C10-C30 fused ring aryl or substituted or unsubstituted C6-C30 fused ring heteroaryl;

preferably, said L²Is a single bond, and Ar²Any one selected from the following substituted or unsubstituted groups: naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl;

preferably, said L²Is a single bond, and Ar²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

6. The compound of claim 1, wherein L is²Is phenylene, and Ar is²Selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;

preferably, said L²Is phenylene, and Ar is²Any one selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl;

preferably, said L²Is phenylene, and Ar is²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

7. A compound according to any one of claims 1 to 6 wherein R is¹、R²And R³Independently selected from one of methyl, ethyl or phenyl.

8. A compound according to any one of claims 1 to 6 wherein R is¹、R²And R³Are all methyl.

9. A compound according to any one of claims 1 to 6 wherein L is¹One selected from the following substituted or unsubstituted groups: one of phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene, dibenzothiophenylene and 9, 9-dimethylfluorenyl;

said L¹Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

10. A compound according to any one of claims 1 to 9, wherein m is 0.

11. The compound of claim 1, wherein the compound has any one of the following structures P1-P818:

12. use of a compound according to any one of claims 1 to 11 in an organic electroluminescent device;

preferably, the compound is used as an electron blocking layer material in the organic electroluminescent device.

13. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, the organic layer containing at least one compound according to any one of claims 1 to 11;

preferably, the organic layer comprises an electron blocking layer comprising at least one compound according to any one of claims 1 to 11.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to a compound and application thereof.

Background

In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them well suited for fabrication on flexible substrates, allowing for the design and production of aesthetically pleasing and crunchy optoelectronic products, with unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have been developed particularly rapidly, and have been commercially successful in the field of information display. The OLED can provide three colors of red, green and blue with high saturation, and a full-color display device manufactured by using the OLED does not need an additional backlight source and has the advantages of colorful, light, thin and soft color and the like.

The core of the OLED device is a thin film structure containing various organic functional materials. Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light.

People have developed various organic materials, and the organic materials are combined with various peculiar device structures, so that the carrier mobility can be improved, the carrier balance can be regulated and controlled, the electroluminescent efficiency can be broken through, and the attenuation of the device can be delayed. For quantum mechanical reasons, common fluorescent luminophores mainly utilize singlet excitons generated when electrons and air are combined to emit light, and are still widely applied to various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet excitons and singlet excitons, which are called phosphorescent emitters, and the energy conversion efficiency can be increased by up to four times as compared with conventional fluorescent emitters. The thermal excitation delayed fluorescence (TADF) technology can still effectively utilize triplet excitons to achieve higher luminous efficiency without using a metal complex by promoting the conversion of triplet excitons to singlet excitons. Thermal excitation sensitized fluorescence (TASF) technology also achieves higher luminous efficiency by sensitizing the emitter by energy transfer using TADF-like materials.

As OLED products gradually enter the market, there are increasingly higher requirements on the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, service life, cost and the like.

Therefore, there is a need in the art to develop an organic electroluminescent material that can improve the light emitting efficiency of the device, reduce the driving voltage, and prolong the lifetime.

Disclosure of Invention

The invention aims to provide a compound which is applied to an organic electroluminescent device and can improve the luminous efficiency of the device, reduce the driving voltage and prolong the service life.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a compound, which has a structure shown in a formula I;

in the formula I, Ar is¹And Ar²Independently selected from substituted or unsubstituted C6-C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) aryl or substituted or unsubstituted C3-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroaryl;

the substituted or unsubstituted C6-C30 aryl groups include C6-C30 monocyclic aryl groups and C10-C30 fused ring aryl groups; the substituted or unsubstituted C3-C30 heteroaryl includes C3-C30 monocyclic heteroaryl and C6-C30 fused ring heteroaryl;

in the formula I, L is¹Is selected from substituted or unsubstituted C6-C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylene or substituted or unsubstituted C3-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroarylene;

in the formula I, L is²One selected from a single bond, a substituted or unsubstituted C6-C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylene group, or a substituted or unsubstituted C3-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroarylene group;

in the formula I, R is¹、R²And R³Independently selected from substituted or unsubstituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, etc.) chain alkyl, substituted or unsubstituted C13-C13 (e.g., C13-C13, C, Substituted or unsubstituted C2-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkynyl, halogen, cyano, nitro, hydroxy, C1-C20 (e.g., C1-C20C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, etc.) silyl, amino, substituted or unsubstituted C6-C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) arylamino, substituted or unsubstituted C3-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, etc.) heteroarylamino, substituted or unsubstituted C23-C23 (e.g., C23, etc.) heteroaryl, etc.; the R is¹、R²And R³Are connected with each other to form a ring or are not connected to form a ring;

in the formula I, m is an integer of 0-6, such as 1, 2, 3,4, 5 and the like; when m is greater than or equal to 2, R⁴The same or different;

in the formula I, R is⁴Independently selected from substituted or unsubstituted C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, etc.) chain alkyl, substituted or unsubstituted C13-C13 (e.g., C13-C13, C, Substituted or unsubstituted C-C (e.g., C, etc.) alkynyl, halogen, cyano, nitro, hydroxy, substituted or unsubstituted C-C (e.g., C, etc.) silyl, amino, substituted or unsubstituted C-C (e.g., C, etc.) arylamino, substituted or unsubstituted C-C (e.g., C, etc.) heteroarylamino, substituted or unsubstituted C-C (e.g., C, etc.), substituted or unsubstituted C-C (e.g., C, etc.) heteroaryl amino, or a substituted or unsubstituted C-C, or a pharmaceutically acceptable salts thereof, or a pharmaceutically acceptable salt thereof, or a pharmaceutically acceptable carrier, or a pharmaceutically acceptable salt thereof, or a pharmaceutically acceptable carrier or a pharmaceutically acceptable salt thereof, or a pharmaceutically acceptable carrier or a carrier or,C12, C14, C16, C18, C20, C26, C28, etc.) aryl, substituted or unsubstituted C3-C30 (e.g., C4, C6, C8, C12, C15, C18, C20, C23, C25, C28, etc.) heteroaryl;

Ar¹、Ar²、L¹、L²、R¹、R²、R³and R⁴In the formula, the substituent is selected from halogen, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) chain alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, C1-C1 (e.g., C1, etc.) thioalkoxy, C1-C1 (e.g., C1, etc.) aryl 1, C1, etc. C1, C1, etc. monocyclic 1, C1, etc. C1, etc. condensed ring (e.g., C1, C1, etc.) condensed ring 1, C1, etc.) condensed ring, C1, etc.) aryl 1, etc. C1, etc. aryl 1, etc. C1, C, C23, C25, C28, etc.), monocyclic heteroaryl, C6-C30 (e.g., C10, C12, C14, C16, C18, C20, C26, C28, etc.) fused ring heteroaryl, or a combination of at least two thereof.

The above "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from different substituents.

In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, for example, hydrogen (H) includes¹H (protium or H),²H (deuterium or D), etc.; carbon (C) then comprises¹²C、¹³C and the like.

In the present invention, the heteroatom of heteroaryl is generally referred to as N, O, S.

In the present invention, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linkage can be formed.

The C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, more preferably a C1-C6 chain alkyl group, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, n-pentyl, isopentyl, neopentyl, n-heptyl, n-nonyl, n-decyl and the like.

The above-mentioned C3-C20 cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The substituted or unsubstituted C6-C30 aryl group, preferably C6-C20 aryl group, is preferably selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,A group of the group consisting of a phenyl group and a tetracenyl group. The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from the group consisting of 1-anthracene group, 2-anthracene group, and 9-anthracene group; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9 '-dimethylfluorene, 9' -spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracene group is selected from the group consisting of 1-tetracene, 2-tetracene, and 9-tetracene.

The substituted or unsubstituted C3-C30 heteroaryl group, preferably C4-C20 heteroaryl group, preferably the heteroaryl group is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl or derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.

In the present invention, the numbers for the substitution sites on the naphthalene ring are as follows:

in the structure of the compound of the invention, a substituent Ar is introduced into the 1-position of a naphthalene ring²Not only can adjust the steric hindrance of 1, but also can effectively adjust and control the twist degree of molecules so as to reduce the crystallinity of the molecules; secondly, 2-substituted arylamine group and trisubstituted structure on arylamine groupThe introduction of the compound can effectively regulate and control the three-dimensional structure of molecules, and the accumulation density of the molecules is improved, so that the designed material can meet the requirements of devices on the material.

In the invention, 1-position and 2-position substituted naphthalene ring parent nucleus structures are matched with Ar¹、Ar²、R¹～R⁴The substituent groups can achieve the best effect, so that the material can be applied to an organic electroluminescent device, and particularly can improve the luminous efficiency, reduce the starting voltage and prolong the service life of the device when being used as an electron blocking layer.

In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.

Preferably, said L²One selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group, preferably a single bond or a phenylene group.

Preferably, Ar is²Selected from substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl.

Preferably, Ar is²Any one selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl.

PreferablyAr is said²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

Preferably, said L²Is a single bond, and Ar²Selected from substituted or unsubstituted C10-C30 fused ring aryl or substituted or unsubstituted C6-C30 fused ring heteroaryl.

Preferably, said L²Is a single bond, and Ar²Any one selected from the following substituted or unsubstituted groups: naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, triphenylenyl, fluoranthenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl.

Preferably, said L²Is a single bond, and Ar²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

In the present invention, the expression pattern of the loop structure marked by the dotted line indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.

Preferably, said L²Is phenylene, and Ar is²Selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl.

Preferably, said L²Is phenylene, and Ar is²Any one selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9-dimethylfluoreneA group, 9-diphenylfluorenyl group, spirofluorenyl group, triphenylene group, fluoranthenyl group, benzo 9, 9-dimethylfluorenyl group, benzospirofluorenyl group.

Preferably, said L²Is phenylene, and Ar is²Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

Preferably, said R is¹、R²And R³Independently selected from one of methyl, ethyl or phenyl.

Preferably, said R is¹、R²And R³Are all methyl.

Preferably, said L¹One selected from the following substituted or unsubstituted groups: phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene, dibenzothiophenylene, and 9, 9-dimethylfluorenyl.

Preferably, said L¹Any one selected from the following substituted or unsubstituted groups:

wherein the dotted line represents the linking bond of the group.

Preferably, m is 0.

Preferably, Ar is¹Any one selected from the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, binaphthyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, benzo 9, 9-dimethylfluorenyl, benzospirofluorenyl, benzo 9, 9-diphenylfluorenyl, naphtho 9, 9-dimethylfluorenyl, naphtho spirofluorenyl, naphtho 9, 9-diphenylfluorenyl, dibenzofuranyl, dibenzothienyl, N-phenylcarbazolyl, spiro (cyclopentyl-1, 9' -fluorene) group, benzonaphtho furoPyranyl, benzonaphthothienyl, spiro (cyclohexyl-1, 9 '-fluorene) and spiro (adamantyl-1, 9' -fluorene) groups.

Preferably, the compound has any one of the structures shown below as P1-P818.

The second purpose of the invention is to provide the application of the compound in the first purpose, and the compound is applied to an organic electroluminescent device.

Preferably, the compound is used as an electron blocking layer material in the organic electroluminescent device.

It is a further object of the present invention to provide an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, the organic layer containing at least one compound according to one of the objects.

The organic electroluminescent device containing the compound of formula I provided by the invention has the brightness of 3000cd/m²When the voltage is low, the driving voltage is 3.8V or less, and the current efficiency is as high as 18.2cd/A or more.

Preferably, the organic layer comprises an electron blocking layer containing at least one compound according to one of the objects.

The compound of the invention can be applied to organic electroluminescent devices, and can also be applied to other types of organic electronic devices, including organic field effect transistors, organic thin-film solar cells, information labels, electronic artificial skin sheets, sheet type scanners or electronic paper.

Specifically, another technical scheme of the present invention provides an organic electroluminescent device, including a substrate, and an anode layer, a plurality of light emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer and an electron transport layer, wherein the electron blocking layer contains at least one of the compounds.

The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.

In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.

The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used₂) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.

The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.

The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may have a multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL) using the compound of formula I according to the present invention.

The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives including compounds shown below as HT-1 to HT-34; or any combination thereof.

The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1 to HI-3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI-1 to HI-3 described below.

The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.

According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.

In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, the combination of one or more of BFH-1 through BFH-17 listed below.

In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent dopant may be selected from, but is not limited to, combinations of one or more of BFD-1 through BFD-12 listed below.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more of GPH-1 to GPH-80.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more of GPD-1 to GPD-47 listed below.

Wherein D is deuterium.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.

In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of YPD-1 to YPD-11 listed below.

In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. The fluorescent dopant of the light emitting layer can be selected from, but is not limited to, the combination of one or more of TDE-1 to TDE-39 listed below.

In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. The host material of the light emitting layer is selected from, but not limited to, one or more of TDH 1-TDH 24.

The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.

An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li₂O、Cs₂CO₃、BaO、Na、Li or Ca.

Compared with the prior art, the invention has the following beneficial effects:

in the structure of the compound of the invention, a substituent Ar is introduced into the 1-position of a naphthalene ring²Not only can adjust the size of steric hindrance at the ortho position, but also can effectively adjust and control the twist degree of molecules so as to reduce the crystallinity of the molecules; secondly, an arylamine group is substituted at the 2-position, and the introduction of a trisubstitution structure on the arylamine group can effectively regulate the three-dimensional structure of molecules, so that the accumulation density of the molecules is improved, and the designed material can meet the requirements of devices on the material.

In the invention, 1-position and 2-position substituted naphthalene ring parent nucleus structures are matched with Ar¹、Ar²、R¹～R⁴The substituent groups can achieve the best effect, so that the material can be applied to an organic electroluminescent device, and particularly can improve the luminous efficiency, reduce the starting voltage and prolong the service life of the device when being used as an electron blocking layer.

In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.

The organic electroluminescent device containing the compound of formula I provided by the invention has the brightness of 3000cd/m²When the voltage is low, the driving voltage is 3.8V or less, and the current efficiency is as high as 18.2cd/A or more.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

A representative synthetic route for the compounds of formula I of the present invention is as follows:

wherein R is₁、R₂、R₃、R₄、L¹、L²、Ar¹And Ar²Are all the same as the symbols in formula I; pd₂(dba)₃Represents tris (dibenzylacetone) dipalladium (0), IPr. HCl represents 1, bis (2, diisopropylphenyl) imidurium chloride, NaOBu-t represents sodium tert-butoxide, (t-Bu)₃P represents tri-tert-butylphosphine.

More specifically, the present invention provides a specific synthesis method of a representative compound as exemplified by the following synthesis examples, and the solvents and reagents used in the following synthesis examples, such as 3-bromo-9, 9-dimethylfluorene, 1, bis (2, diisopropylphenyl) imidazolium chloride, tris (dibenzylacetone) dipalladium (0), toluene, methanol, ethanol, tri-tert-butylphosphine, potassium/sodium tert-butoxide, and other chemical reagents, can be purchased or customized from domestic chemical product markets, such as from national drug group reagent company, Sigma-Aldrich company, warfarin reagent company, and intermediates M1 to M7, which are customized by reagent company. In addition, they can be synthesized by a known method by those skilled in the art.

Synthesis example 1: synthesis of Compound P1

Into a 1000mL single-necked flask were added 13.5g (50mmol) of M1, 13.6g (50mmol) of 3-bromo-9, 9-dimethylfluorene, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-1.

In a 1000mL single neck flask, 23g (50mmol) of M1-1, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P1.

M/Z theoretical value: 593; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 594.

synthesis example 2: synthesis of Compound P2

In a 1000mL single neck flask, 23g (50mmol) of M1-1, 14.4g (50mmol) of 4-bromo-4' -tert-butylbiphenyl, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd2(dba)3), 0.5mL of tri-tert-butylphosphine ((t-Bu)3P), 500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), and the reaction was warmed to 110 ℃ for 5h by changing nitrogen gas under vacuum. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P2.

M/Z theoretical value: 669; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 670.

synthesis example 3: synthesis of Compound P5

In a 1000mL single-necked flask, 23g (50mmol) of M1-1, 14.5g (50mmol) of 2-bromo-5-tert-butylbiphenyl, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P5.

M/Z theoretical value: 669; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 670.

synthesis example 4: synthesis of Compound P6

In a 1000mL single-necked flask, 23g (50mmol) of M1-1, 18.5g (50mmol) of 4-bromo-3-phenyl-4' -tert-butylbiphenyl, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P6.

M/Z theoretical value: 745; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 746.

synthesis example 5: synthesis of Compound P7

In a 1000mL single-necked flask, 13.5g (50mmol) of M1, 20g (50mmol) of 3-bromo-9, 9-diphenylfluorene, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-2.

In a 1000mL single-neck flask, 29g (50mmol) of M1-2, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P7.

M/Z theoretical value: 717; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 718.

synthesis example 6: synthesis of Compound P15

Into a 1000mL single-neck flask were added 13.5g (50mmol) of M1 and 16.5g (50mmol) of 3-bromo- [6,7 ]]-benzo-9, 9-dimethylfluorene, 0.9g (1mmol) tris (dibenzylideneacetone) dipalladium (i.e. Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-3.

In a 1000mL single-neck flask, 25.5g (50mmol) of M1-3, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P15.

M/Z theoretical value: 643; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 644.

synthesis example 7: synthesis of Compound P37

In a 1000mL single-neck flask, 16g (50mmol) of M2, 13.5g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction solution, concentrating the organic phase, adding methanol, stirring for 1h, and vacuum filtering to obtain light yellowPowder M2-1.

In a 1000mL single-neck flask, 26g (50mmol) of M2-1, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P37.

M/Z theoretical value: 649, performing a chemical mechanical polishing; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 650.

synthesis example 8: synthesis of Compound P38

In a 1000mL single-necked flask, 26g (50mmol) of M2-1, 14.5g (50mmol) of 4-bromo-4' -tert-butylbiphenyl, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P38.

M/Z theoretical value: 725 (a); ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 726.

synthesis example 9: synthesis of Compound P74

In a 1000mL single-neck flask, 15.5g (50mmol) of M3, 13.5g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), suctionChanging nitrogen in vacuum for 3 times, and heating the reaction to 90 ℃ for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M3-1.

In a 1000mL single-necked flask, 25g (50mmol) of M3-1, 14.5g (50mmol) of 4-bromo-4' -tert-butylbiphenyl, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P74.

M/Z theoretical value: 709; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 710.

synthesis example 10: synthesis of Compound P253

In a 1000mL single-necked flask, 16.5g (50mmol) of M4, 13.6g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M4-1.

In a 1000mL single-neck flask, 26.5g (50mmol) of M4-1, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P253.

M/Z theoretical value: 659; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 660.

synthesis example 11: synthesis of Compound P284

In a 1000mL single-neck flask, 26.5g (50mmol) of M4-1, 20g (50mmol) of 1- (4-bromophenyl) -1,1, 1-triphenylmethane, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P284.

M/Z theoretical value: 845; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 846.

synthesis example 12: synthesis of Compound P375

In a 1000mL single-neck flask, 15g (50mmol) of M5, 13.5g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M5-1.

In a 1000mL single neck flask, 25g (50mmol) of M5-1, 14.5g (50mmol) of 2-phenyl 4-bromobutyl benzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and heating the reaction to 110 ℃ for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P375.

M/Z theoretical value: 695 parts of; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 696.

synthesis example 13: synthesis of Compound P322

In a 1000mL single-necked flask, 16.5g (50mmol) of M7, 13.5g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M7-1.

In a 1000mL single-neck flask, 26.5g (50mmol) of M7-1, 14g (50mmol) of 1- (4-bromophenyl) -1, 1-dimethyl-1-phenylmethane, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P322.

M/Z theoretical value: 721; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 722.

synthesis example 14: synthesis of Compound P323

In a 1000mL single-necked flask, 16.5g (50mmol) was added) M7, 16.5g (50mmol) of 3-bromo-9, 9-dimethyl-6, 7-benzofluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M7-2.

In a 1000mL single-necked flask, 29g (50mmol) of M7-2, 12.7g (50mmol) of 1- (4-bromophenyl) -1,1, 1-triethylmethane, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P323.

M/Z theoretical value: 751; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 752.

synthesis example 15: synthesis of Compound P20

In a 1000mL single-neck flask, 25.5g (50mmol) of M1-3, 16g (50mmol) of 3-bromo-6-tert-butyldibenzothiophene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and filtering to obtain light yellow powder P20.

M/Z theoretical value: 749; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 750.

synthesis example 16: synthesis of Compound P628

Into a 1000mL single-necked flask were added 13.5g (50mmol) of M1, 16.5g (50mmol) of 3-bromo-9, 9-dimethyl-5, 6-benzofluorene, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-4.

In a 1000mL single-necked flask, 25.5g (50mmol) of M1-4, 14.5g (50mmol) of 2-bromo-5-tert-butylbiphenyl, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P628.

M/Z theoretical value: 719 of a container; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 720.

synthesis example 17: synthesis of Compound P613

Into a 1000mL single-necked flask were added 13.5g (50mmol) of M1, 12.3g (50mmol) of 3-bromo-dibenzofuran, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-5.

In a 1000mL single-neck bottle, add22g (50mmol) M1-5, 11g (50mmol) 4-bromo-tert-butylbenzene, 0.9g (1mmol) tris (dibenzylideneacetone) dipalladium (i.e. Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P613.

M/Z theoretical value: 567. a first step of mixing; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 568.

synthesis example 18: synthesis of Compound P602

In a 1000mL single-necked flask, 21g (50mmol) of M1-5, 14.5g (50mmol) of 4-bromo-4' -tert-butylbiphenyl, and 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P602.

M/Z theoretical value: 629; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 630.

synthesis example 19: synthesis of Compound P784

In a 1000mL single-necked flask, 19.2g (50mmol) of M8, 13.6g (50mmol) of 3-bromo-9, 9-dimethylfluorene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. After the reaction is finished, the reaction is stoppedAnd (4) reacting. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M8-1.

In a 1000mL single-neck flask, 28.8g (50mmol) of M8-1, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd) were added₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P784.

M/Z theoretical value: 708; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 709.

synthesis example 20: synthesis of Compound P797

Into a 1000mL single-neck flask were added 13.5g (50mmol) of M1, 16g (50mmol) of A1, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5g IPr. HCl, 500mL toluene, 14.4g (150mmol) sodium tert-butoxide (NaOBu-t), vacuumized and nitrogen exchanged for 3 times, and the reaction is heated to 90 ℃ for 5 h. And stopping the reaction after the reaction is finished. Cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder M1-6.

In a 1000mL single neck flask, 25g (50mmol) of M1-6, 11g (50mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 14.4g (150mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and raising the temperature of the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P797.

M/Z theoretical value: 633; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 634.

synthesis example 21: synthesis of Compound P807

Into a 1000mL single-necked flask were added 13.5g (50mmol) of M1, 22g (100mmol) of 4-bromo-tert-butylbenzene, 0.9g (1mmol) of tris (dibenzylideneacetone) dipalladium (i.e., Pd)₂(dba)₃) 0.5mL of tri-tert-butylphosphine ((t-Bu)₃P),500mL of toluene, 30g (300mmol) of sodium tert-butoxide (NaOBu-t), vacuumizing and changing nitrogen for 3 times, and heating the reaction to 110 ℃ for reaction for 5 hours. And stopping the reaction after the reaction is finished. And cooling to room temperature, separating the reaction liquid, concentrating the organic phase, adding methanol, stirring for 1h, and performing suction filtration to obtain light yellow powder P807.

M/Z theoretical value: 533; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z measured value: 534.

example 1

The embodiment provides an organic electroluminescent device, which is specifically prepared as follows:

the glass plate coated with the ITO transparent conductive layer (as anode) was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;

placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10^-5Pa, performing vacuum evaporation on the anode layer film to obtain HI-3 serving as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;

evaporating HT-4 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;

and (3) evaporating the compound P1 on the hole transport layer in vacuum to be used as an electron barrier layer material of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm.

A luminescent layer of the device is vacuum evaporated on the electron blocking layer, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material GPH-59 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-8 is 3% of the evaporation rate of the main material, the proportion is set, and the total evaporation film thickness is 30 nm;

vacuum evaporating an electron transport layer material ET-46 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;

LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.

The organic electroluminescent devices provided in examples 2 to 21 and comparative examples 1 to 6 were fabricated in the same manner as in example 1, except that the compound P1 as an electron blocking layer material was replaced with the compounds shown in table 1.

The structures of the electron barrier materials of comparative examples 1 to 6 are as follows:

wherein R-1 and R-2 are described in detail in patent application CN109749735A, and R-3 to R-6 are described in patent application CN 110511151A.

The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:

the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 21 and comparative examples 1 to 6 were measured at the same luminance using a digital source meter (Keithley2400) and a luminance meter (ST-86LA type luminance meter, photoelectric instrument factory, university of beijing) and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 3000cd/m²The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency, and the test results are shown in table 1.

TABLE 1

As can be seen from the data in Table 1, when the compound of the invention is used as an electron barrier material of an organic electroluminescent device, the luminance of the device reaches 3000cd/m²When the material is used, the driving voltage is low below 3.8V, the current efficiency is as high as more than 18.2cd/A, the driving voltage can be effectively improved, the current efficiency can be improved, and the material is an electron barrier layer material with good performance.

When the compound R-1 of comparative example 1, which is different from the compound P602 of example 18 in that the 1-position of naphthalene is unsubstituted and the 4-position is a benzene ring in the structure of the compound R-1, is used as an electron blocking layer material for an organic electroluminescent device, the driving voltage of the device is 5.3V and the current efficiency is 11 cd/A. The turn-on voltage and current efficiency of the compound are inferior to that of P602, which may be attributed to the fact that compound P602 has better space accumulation and thus improves hole transport performance.

The arylamine group of the compound R-2 of comparative example 2 was substituted at the 1-position of the naphthalene ring, the benzene ring was substituted at the 2-position and the 3-position, and no substituent having a tert-butyl structure was contained, and when this compound was used as an electron blocking layer material for an organic electroluminescent device, the driving voltage of the device was 5.8V, the current efficiency was 10.1cd/A, and the effect was significantly inferior to that of examples 1 to 18.

The compound R-3 of comparative example 3 is compared to the compound P1 of example 1, except that the four position of the phenyl group attached to the N is not substituted with a tert-butyl group. When the compound is used as an electron barrier material of an organic electroluminescent device, the driving voltage of the device is 3.3V, and the current efficiency is 19 cd/A. The current efficiency of the compound is inferior to that of P1, which is probably attributed to that the 4-tertiary butyl in the compound P1 can provide stronger electron-supplying capability and improve the molecular space accumulation structure, thereby effectively improving the hole transport performance of the material.

The compound R-4 of comparative example 4 is different from the compound P2 of example 2 in that the terminal of biphenyl attached to N in the molecule has no tert-butyl substitution. When the compound is used as an electron barrier material of an organic electroluminescent device, the driving voltage of the device is 3.1V, and the current efficiency is 19.3 cd/A. The current efficiency of the compound is inferior to that of P2, which is probably attributed to that the 4-tertiary butyl group in the compound P2 can not only provide electron-donating capability, but also improve the structure of molecular space accumulation, thereby effectively improving the hole transport performance of the material.

The compound R-5 of comparative example 5 is different from the compound P5 of example 3 in that the biphenyl group attached to N has no tert-butyl substitution at the 4-position. When the compound is used as an electron barrier material of an organic electroluminescent device, the driving voltage of the device is 3.4V, and the current efficiency is 18.5 cd/A. The current efficiency of the compound is inferior to that of P5, which is probably attributed to that the 4-tertiary butyl in the compound P5 not only can provide stronger electron-donating capability, but also can improve the molecular space accumulation structure, thereby effectively improving the hole transport performance of the material.

The compound R-6 of comparative example 6 is different from the compound P6 of example 4 in that the terminal of 2-phenylbiphenyl group bonded to nitrogen in the molecule is not substituted with a tert-butyl group. When the compound is used as an electron barrier material of an organic electroluminescent device, the driving voltage of the device is 3.5V, and the current efficiency is 17.8 cd/A. The current efficiency of the compound is inferior to that of P6, which is probably attributed to that the tert-butyl in the compound P6 not only can provide electron-donating capability, but also can improve the structure of molecular space accumulation, thereby effectively improving the hole transport performance of the material.

Thus, in the compound provided by the invention, Ar is substituted at the 1-position of the naphthalene ring²The substitution of 2-substituted arylamine and tert-butyl structural substituent is an important factor for enabling the compound to bring excellent performance when being applied to an organic electroluminescent device.

The present invention is illustrated by the above examples of the compounds of the present invention and their application in OLED devices, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention has to be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.