CN113666963A

CN113666963A - Compound, display panel and display device

Info

Publication number: CN113666963A
Application number: CN202111001448.1A
Authority: CN
Inventors: 高威; 翟露; 张磊; 代文朋; 冉佺; 卢艳; 匡立莲
Original assignee: Wuhan Tianma Microelectronics Co Ltd
Current assignee: Wuhan Tianma Microelectronics Co Ltd
Priority date: 2021-08-30
Filing date: 2021-08-30
Publication date: 2021-11-19

Abstract

The application discloses a compound, a display panel and a display device. The compound has a structure shown in a formula I, wherein Ar is₁、Ar₂Each independently represents at least one of a hydrogen atom, a substituted or unsubstituted aryl group having C6 to C30, a substituted or unsubstituted heteroaryl group having C2 to C20, a substituted or unsubstituted arylamine group having C12 to C40, a substituted or unsubstituted carbazolyl group having C12 to C40, and a substituted or unsubstituted acridine group having C18 to C40; d₁And D₂Each independently represents at least one of a substituted or unsubstituted arylamine group having C12 to C40, a substituted or unsubstituted carbazolyl group having C12 to C40, and a substituted or unsubstituted acridine group having C18 to C40; l is₁、L₂Each independently represents a substituted or unsubstituted aryl group having C6 to C30, or a substituted or unsubstituted heteroaryl group having C2 to C20;m and n are each independently selected from 0, 1 or 2.

Description

Compound, display panel and display device

Technical Field

The application relates to the technical field of organic electroluminescent materials, in particular to a compound, a display panel and a display device.

Background

An Organic Light Emitting Diode (OLED) display device directly converts electrical energy into optical energy by using the photoelectric functional characteristics of a compound. The OLED display device belongs to carrier injection type light emission, and holes injected through an anode and electrons injected from a cathode are recombined in a light emitting layer to form excitons, and are emitted in the form of light energy.

The compounds can be classified into fluorescent materials derived from a singlet excited state of electrons and phosphorescent materials derived from a triplet excited state of electrons according to a light-emitting host. The quantum efficiency of the fluorescent material is not more than 25%, and the rest energy is converted into heat energy to be released. The quantum efficiency theory of the phosphorescent material can reach 100%, and the energy of the fluorescent material converted into heat energy can be converted into light energy, so that the luminous efficiency of the OLED display device can be improved.

However, at high current density, the phosphorescent material may cause triplet-triplet annihilation and concentration quenching, resulting in the degradation of the OLED display device performance.

Disclosure of Invention

The application provides a compound, a display panel and a display device.

In a first aspect, the present application provides a compound having the structure shown in formula I:

wherein Ar is₁、Ar₂Each independently represents at least one of a hydrogen atom, a substituted or unsubstituted aryl group having C6 to C30, a substituted or unsubstituted heteroaryl group having C2 to C20, a substituted or unsubstituted arylamine group having C12 to C40, a substituted or unsubstituted carbazolyl group having C12 to C40, and a substituted or unsubstituted acridine group having C18 to C40;

D₁and D₂Each independently represents at least one of a substituted or unsubstituted arylamine group having C12 to C40, a substituted or unsubstituted carbazolyl group having C12 to C40, and a substituted or unsubstituted acridine group having C18 to C40;

L₁、L₂each independently represents a substituted or unsubstituted aryl group having C6 to C30, or a substituted or unsubstituted heteroaryl group having C2 to C20;

m and n are each independently selected from 0, 1 or 2.

A second aspect of the present application provides a display panel comprising an organic light emitting device comprising an anode, a cathode, a light emitting layer between the anode and the cathode, wherein the light emitting layer comprises a host material and a guest material, the host material or the guest material of the light emitting layer comprising one or more of the compounds as described in the first aspect of the present application.

A third aspect of the present application provides a display device comprising the display panel as in the second aspect.

According to the compound of the embodiment, a spiro structure containing a phosphine-oxygen group is taken as a core of the compound, a nitrogen-containing group is introduced to be taken as an electron donor group, and charge transfer is easily carried out in a molecule to form a bipolar compound; the compound has a proper HOMO energy level and a lower LUMO energy level, so that the electron injection and transmission capability are improved, a lower working voltage is obtained, and holes can be effectively blocked; and the compound has higher triplet state energy level, can block exciton diffusion of a light emitting layer, and achieves higher exciton utilization rate. In addition, the spiro structure reduces molecular action, enables the spiro structure to have proper space distortion, can reduce intermolecular stacking, prevents crystallization, and has good modeling and film stability, thereby inhibiting reduction of electron transport performance and exciton formation efficiency caused by material crystallization, and being beneficial to improvement of luminous efficiency and service life of devices. By modifying different sites of the spiro structure with functional groups, the carrier transmission performance can be adjusted, and the triplet state energy level can be improved; and has good thermodynamic stability.

The display panel and the display device of the present application include the compound, and thus can have a lower driving voltage, a higher light emitting efficiency, and a longer service life.

Drawings

Other features, objects, and advantages of the present application will become apparent from the following detailed description of non-limiting embodiments thereof, when read in conjunction with the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures thereof, and which are not to scale.

Fig. 1 is a schematic structural diagram of an organic light emitting device provided according to an embodiment of the present application;

fig. 2 is a schematic structural diagram of a display device according to an embodiment of the present application.

Detailed Description

In order to make the application purpose, technical solution and beneficial technical effects of the present application clearer, the present application is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.

The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.

In the description herein, unless otherwise specified, "above" and "below" are inclusive of the present numbers, and "one or more", "one or more" and "plural" mean two or more.

The terms "a", "an", "the" each refer to one or more molecules of the compound, and are not limited to a single molecule of the compound. Furthermore, one or more molecules may or may not be the same, provided they fall within the category of the chemical compound.

The term "comprises" and its variants do not have a limiting meaning when presented in the description and claims.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be employed and claimed individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or deleted from the group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is considered herein to contain the modified group and thus satisfy the written description of all markush groups used in the claims.

When a compound or a chemical structural feature (e.g., aryl) is referred to as "substituted," the feature may have one or more substituents, unless otherwise specified. The term "substituent" has the broadest meaning known to those of ordinary skill in the art and includes such fragments (moieity): which occupies the position normally occupied by one or more hydrogen atoms attached to the parent compound or chemical structural feature.

The term "alkyl" includes not only straight-chain or branched-chain saturated hydrocarbon groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl) and the like, but also alkyl substituents bearing other substituents known in the art, such as hydroxyl, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl and the like. Thus, "alkyl" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like. In various embodiments, the C1-C20 alkyl groups, i.e., alkyl groups, can contain 1-20 carbon atoms.

The term "alkoxy" refers to-O-alkyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy, isopropoxy), butoxy (e.g., n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), and the like.

The term "aryl" refers to a closed aromatic ring or ring system. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, triphenylene, pyrenyl, spirobifluorenyl, and the like,

Perylene, indenyl and azulenyl. In various embodiments, the 6-to 30-membered aryl group, i.e., aryl group, can contain 6 to 30 carbon atoms for forming a ring.

The term "heteroaryl" refers to an aryl group in which one or more of the atoms in the ring is an element other than carbon (e.g., N, O, S, etc.). In some embodiments, the 2-20 heteroaryl groups, taken as a whole, can contain 1-6 or 1-3 ring heteroatoms (e.g., N, O, S, etc.). Examples of heteroaryl groups include, but are not limited to, pyrrolyl, furanyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, isoquinolyl, acridinyl, purinyl, pteridinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzothiazolyl, cinnoline, quinoxalinyl, dibenzofuranyl, dibenzothienyl, and phenanthrolinyl. In various embodiments, the 2-20 membered aryl group, i.e., aryl group, can contain 2-20 atoms (including carbon and heteroatoms) for forming a ring.

The term "arylamino" refers to an aromatic ring in which a hydrogen is replaced with an amino group. Examples of arylamine groups include, but are not limited to, cyano arylamine groups, alkyl arylamine groups, alkoxy arylamine groups, aryl arylamine groups, heteroaryl arylamine groups.

The term "acridinyl" refers to a nitrogen-containing heterocycle having two benzene rings and a pyridine structure. Examples of acridinyl groups include, but are not limited to, cyanoacridinyl, alkylazaridinyl (such as methylazaridinyl, ethylazaridinyl, propylacridinyl, and butylazaridinyl), alkoxyacridinyl, arylcarbazolyl, heteroarylcarbazolyl, arylaminocarbonylcarbazolyl.

The term "carbazolyl" refers to a nitrogen-containing aromatic heterocycle. Examples of carbazolyl groups include, but are not limited to, cyanocarbazolyl, alkylcarbazolyl (e.g., methylcarbazolyl, ethylcarbazolyl, propylcarbazolyl, butylcarbazolyl), alkoxycarbazolyl, arylcarbazolyl, heteroarylcarbazolyl, arylaminocarbonylcarbazolyl.

The term "hydrogen" refers to 1H (protium, H), 2H (deuterium, D) or 3H (tritium, T). In various embodiments, "hydrogen" may be 1H (protium, H).

Throughout this specification, substituents of compounds are disclosed in groups or ranges. It is expressly intended that such description include each individual sub-combination of members of these groups and ranges. For example, the term "C1 to C8 alkyl" is specifically contemplated to disclose C1, C2, C3, C4, C5, C6, C7, C8, C1 to C8, C1 to C7, C1 to C6, C1 to C5, C1 to C4, C1 to C3, C1 to C2, C2 to C8, C2 to C7, C2 to C6, C2 to C5, C2 to C4, C4 to C4, and C4 to C4. As other examples, integers ranging from 5 to 40 are expressly contemplated to disclose individually 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40; integers in the range of 1 to 20 are expressly contemplated to disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 individually. Accordingly, other groups or ranges are expressly contemplated.

Herein, the expression that a single bond crosses a single ring or multiple ring system means that a single bond may be attached at any accessible position of the single ring or multiple ring system.

In an embodiment of the first aspect of the present application, there is provided a compound having the structure shown in formula I,

m and n are each independently selected from 0, 1 or 2.

According to the embodiment of the application, the compound takes a spiro structure containing a phosphine-oxygen group as a core of the compound, and a nitrogen-containing group is introduced as an electron donor group, so that charge transfer is easily carried out in a molecule to form a bipolar compound; the compound has a proper HOMO energy level and a lower LUMO energy level, so that the electron injection and transmission capability are improved, a lower working voltage is obtained, and holes can be effectively blocked; and the compound has higher triplet state energy level, can block exciton diffusion of a light emitting layer, and achieves higher exciton utilization rate. In addition, the spiro structure reduces molecular action, enables the spiro structure to have proper space distortion, can reduce intermolecular stacking, prevents crystallization, and has good modeling and film stability, thereby inhibiting reduction of electron transport performance and exciton formation efficiency caused by material crystallization, and being beneficial to improvement of luminous efficiency and service life of devices. By modifying different sites of the spiro structure with functional groups, the carrier transmission performance can be adjusted, and the triplet state energy level can be improved; and has good thermodynamic stability.

In some embodiments, Ar₁And Ar₂Is a substituted or unsubstituted aryl group with C6-C30, and is respectively and independently selected from phenyl, naphthyl, phenanthryl, anthryl, biphenyl, triphenylene, pyrenyl, spirobifluorenyl,

At least one of perylene, indenyl and azulenyl. For example, Ar₁Is phenyl. Ar (Ar)₂Is phenyl.

In some embodiments, Ar₁And Ar₂Is a substituted or unsubstituted heteroaryl group of C2-C20, and is independently selected from at least one of pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, isoquinolyl, acridinyl, purinyl, pteridinyl, benzofuryl, benzothienyl, benzimidazolyl, benzothiazolyl, cinnoline, quinoxalinyl, dibenzofuryl, dibenzothienyl and phenanthrolinyl. Further, Ar₁And Ar₂Each independently selected from at least one of furyl, thienyl, benzofuryl, benzothienyl, dibenzofuryl and dibenzothienyl.

In some embodiments, Ar₁、Ar₂、D₁And D₂Substituted or unsubstituted C12-C40 carbazolyl is adopted, the carbazolyl is easy to form relatively stable positive ions, a large conjugated system and strong intramolecular electron transfer are provided in a molecule, and the thermal stability and the photochemical stability are high; the carbazole ring is easy to carry out structural modification to introduce various functional groups, and the same or different modification groups such as electron transmission modification groups can be introduced at different positions on the carbazole ring, so that electrons and holes are easier to inject, and the balance of the electrons and the holes can be adjusted; and carbazolyl inStrong absorption in the short wavelength range. Ar (Ar)₁、Ar₂、D₁And D₂In (b) is a substituted or unsubstituted C12-C40 carbazolyl group and is respectively and independently selected from at least one of the following groups:

wherein R is^a、R^bAnd R^cEach independently represents a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, or a substituted or unsubstituted C6-C40 aryl group;

R^Aand R^BEach independently represents a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C40 aryl group, a substituted or unsubstituted C4-C40 heteroaryl group, or a substituted or unsubstituted arylamine group;

x represents O, S, N (Z), C (Z)₂、Si(Z)₂Wherein Z represents a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, or a substituted or unsubstituted C6-C40 aryl group;

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

Alternatively, Ar₁、Ar₂、D₁And D₂Each independently selected from at least one of the following groups:

wherein R is^AAnd R^BEach independently represents methyl, isopropyl, tert-butyl, methoxy, phenyl, biphenyl or naphthyl.

In some embodiments, Ar₁、Ar₂、D₁And D₂The aryl amine group is substituted or unsubstituted C12-C40 aryl amine group, and has moderate electron donating property and good hole transport capability; and has good thermal stability and chemical stability; and the compound is easy to chemically modify, and can effectively realize the spatial separation of HOMO and LUMO by combining with an electron acceptor.

Alternatively, Ar₁、Ar₂、D₁And D₂Each independently selected from at least one of the following groups.

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

in some embodiments, Ar₁、Ar₂、D₁And D₂The fluorescent material is a substituted or unsubstituted acridine group of C18-C40, and the acridine group has very strong electron donating capability and shorter fluorescence delay life; the HOMO and LUMO can be better separated; the rigid molecular structure can effectively reduce the non-radiative decay of an excited state; the rigid molecular structure reduces the free rotation vibration in molecules, is beneficial to improving the monochromaticity of the material and reducing the FWHM (full width at half maximum) of the material; furthermore, acridinyl has a high triplet energy level.

x and Y independently represent O, S, N (Z), C (Z)₂、Si(Z)₂Wherein Z independently represents hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, or substituted or unsubstituted C6-C40 aryl;

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

in some embodiments, L₁And L₂Is a substituted or unsubstituted aryl group with C6-C30, and is respectively and independently selected from phenyl, naphthyl, phenanthryl, anthryl, biphenyl, triphenylene, pyrenyl, spirobifluorenyl,

Perylene, indenyl or azulenyl. For example, L₁Is phenyl. L is₂Is phenyl.

In some embodiments, L₁And L₂Is a substituted or unsubstituted heteroaryl group of C2-C20, and is each independently selected from pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, isoquinolyl, acridinyl, purinyl, pteridinyl, benzofuryl, benzothienyl, benzimidazolyl, benzothiazolyl, cinnoline, quinoxalinyl, dibenzofuryl, dibenzothienyl or phenanthrolinyl.

Alternatively, L₁And L₂Each independently selected from furyl, thienyl, benzofuryl, benzothienyl, dibenzofuryl or dibenzothienyl.

In some embodiments, the compound is selected from any one of the following:

the compounds of the present application are useful for display panels and display devices. In some embodiments, the compounds of the present application can have higher solubility in conventional solvents (e.g., dichloromethane, chloroform, toluene, DMF, THF, ethanol, etc.), facilitate the preparation of the compounds, and achieve better film formation uniformity, reducing or avoiding the occurrence of voids.

Another aspect of the present application provides a display panel including an organic light emitting device including an anode, a cathode, and a light emitting layer between the anode and the cathode, the light emitting layer including a host material and a guest material. The host material or guest material comprises one or more of the compounds of embodiments of the first aspect of the present application.

In some embodiments, the host material comprises one or more of the compounds of embodiments of the first aspect of the present application. The guest material is red phosphorescent material and/or green phosphorescent material, e.g. PtOEP and/or Ir (ppy)₃。

In some embodiments, the material used for the anode may include metals (e.g., copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof), metal oxides (e.g., indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.), conductive polymers (e.g., polyaniline, polypyrrole, poly (3-methylthiophene), etc.). Conductive polymers (e.g., polyaniline, polypyrrole, poly (3-methylthiophene), etc.)). In addition to the above materials and combinations thereof that facilitate hole injection, other known materials suitable for use as an anode may be included.

In some embodiments, the cathode can include a metal layer (e.g., aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof), a multi-layer cathode formed by compounding a metal layer and a layer comprising one or more of a metal oxide and a metal halide (e.g., LiF/Al, LiO)₂/Al、BaF₂Al, etc.). In addition to the above materials and combinations thereof that facilitate electron injection, other known materials suitable for use as cathodes are also included.

In some embodiments, the host material of the light emitting layer further includes a dopant material including at least one of a material having an electron transporting function and a material having a hole blocking function. The material having a hole blocking function may be selected from HBMs known in the art, such as BCP, TPBi, TmPyPB, DPEPO, PO-T2T, TAZ, etc., and/or any one or more of the compounds described herein. The material having an electron transport function may be selected from Alq3, TPBi, BCP, TAZ, BPhen, TmPyPB, B3PyPB, ZADN, etc. known in the art, and/or any one or more of the compounds described herein.

In some embodiments, the organic light emitting device further includes one or more of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). The materials of the above-mentioned layers may be selected from the corresponding materials known in the art, respectively.

Fig. 1 shows an organic light emitting device as an example, which includes a substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, and a cathode 9, which are sequentially stacked. The arrows in fig. 1 indicate the light direction.

The display panel may be fabricated using methods known in the art. An exemplary method of fabrication includes: an anode is formed on a transparent or opaque smooth substrate, a light-emitting layer is formed on the anode, and a cathode is formed on the light-emitting layer. The light-emitting layer can be formed by a known film formation method such as vapor deposition, sputtering, spin coating, dipping, ion plating, or the like.

In another embodiment, the present application provides a display device including the display panel described herein. Examples of the display device include, but are not limited to, a mobile phone (e.g., the mobile phone 100 shown in fig. 2), a computer, a television, a smart watch, a smart car, a VR or AR helmet, and the like, which is not particularly limited in this application.

Examples

The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.

The examples show the preparation of exemplary compounds M001, M002, M003, and reference may be made to the synthesis of M001, M002, M003 for the synthesis of other compounds.

Synthesis of intermediates

1. Synthesis of intermediate X003

Under the protection of nitrogen, adding X001(10mmol) and 150mL of anhydrous oxygen-free tetrahydrofuran into a 500mL schlenk reaction bottle, cooling the reaction bottle to-78 ℃ at low temperature, dropwise adding n-butyllithium (10mmol) into the reaction bottle through an injector, reacting at-78 ℃ for 2 hours, dropwise adding X002(10mmol) dissolved in the anhydrous oxygen-free tetrahydrofuran under the protection of nitrogen, continuing to react at-78 ℃ for 2 hours, taking out, slowly heating to room temperature, and stirring overnight. Then with saturated NH₄And (3) quenching the reaction by using a Cl aqueous solution, evaporating out the volatile solvent by using a rotary evaporator, extracting by using dichloromethane, and collecting an organic phase. To the organic phase was added anhydrous sodium sulfate and dried. After the solvent was evaporated by a rotary evaporator, the remaining solid was completely dissolved in acetic acid, and 1mL of concentrated salt was addedHeating and refluxing the acid at 120 ℃, taking out after reacting for 12h, and pouring the solution into ice water to obtain light green solid. Extraction with dichloromethane was performed again, and the solvent was removed by rotary evaporator to obtain a crude product. The crude product was isolated by column chromatography to afford X003(1.75mmol, 35%) as a white solid.

The following results are obtained by liquid chromatography-mass spectrometry combined analysis:

calculated MALDI-TOF MS m/z: C37H24F2P2: 568.1; measurement values: 568.4.

2. synthesis of intermediate X006

Under the protection of nitrogen, adding X004(10mmol) and 150mL of anhydrous oxygen-free tetrahydrofuran into a 500mL schlenk reaction bottle, cooling the reaction bottle to-78 ℃ at low temperature, dropwise adding n-butyl lithium (10mmol) into the reaction bottle through a syringe, reacting at-78 ℃ for 2h, dropwise adding X005(10mmol) dissolved in the anhydrous oxygen-free tetrahydrofuran under the protection of nitrogen, continuing to react at-78 ℃ for 2h, taking out, slowly heating to room temperature, and stirring overnight. Then with saturated NH₄And (3) quenching the reaction by using a Cl aqueous solution, evaporating out the volatile solvent by using a rotary evaporator, extracting by using dichloromethane, and collecting an organic phase. To the organic phase was added anhydrous sodium sulfate and dried. After the solvent was evaporated by a rotary evaporator, the remaining solid was completely dissolved in acetic acid, 1mL of concentrated hydrochloric acid was added, the mixture was heated under reflux at 120 ℃ and reacted for 12 hours, and then taken out, and the solution was poured into ice water to obtain a pale green solid. Extraction with dichloromethane was performed again, and the solvent was removed by rotary evaporator to obtain a crude product. The crude product was isolated by column chromatography to afford X006 as a white solid (1.3mmol, 26%).

calculated MALDI-TOF MS m/z: C37H24F2P2: 568.1; measurement values: 568.3.

3. synthesis of intermediate X009

Under the protection of nitrogen, adding X007(10mmol) and 150mL of anhydrous oxygen-free tetrahydrofuran into a 500mL schlenk reaction bottle, cooling the reaction bottle to-78 ℃ at low temperature, dropwise adding n-butyllithium (10mmol) into the reaction bottle through a syringe, reacting at-78 ℃ for 2h, dropwise adding X008(10mmol) dissolved in the anhydrous oxygen-free tetrahydrofuran under the protection of nitrogen, continuing to react at-78 ℃ for 2h, taking out, slowly heating to room temperature, and stirring overnight. Then with saturated NH₄And (3) quenching the reaction by using a Cl aqueous solution, evaporating out the volatile solvent by using a rotary evaporator, extracting by using dichloromethane, and collecting an organic phase. To the organic phase was added anhydrous sodium sulfate and dried. After the solvent was evaporated by a rotary evaporator, the remaining solid was completely dissolved in acetic acid, 1mL of concentrated hydrochloric acid was added, the mixture was heated under reflux at 120 ℃ and reacted for 12 hours, and then taken out, and the solution was poured into ice water to obtain a pale green solid. Extraction with dichloromethane was performed again, and the solvent was removed by rotary evaporator to obtain a crude product. The crude product was isolated by column chromatography to give X009(1.0mmol, 20%) as a white solid.

calculated MALDI-TOF MS m/z: C37H24F2P2: 568.1; measurement values: 568.4.

example 1

Synthesis of Compound M003

Under nitrogen protection, compound X010(10.5mmol) was weighed into a 500mL two-necked flask, and 80mL of dry, anhydrous tetrahydrofuran was added to dissolve X010. NaH (stored in 60% oil, 11.0mmol) was repeatedly rinsed three times with n-hexane, added to the two-necked flask in portions, and stirred for 1 h. X009(5mmol) was then added to the two-necked flask, and the mixture was reacted at room temperature and stirred overnight. The reaction was quenched with methanol and water, extracted with dichloromethane, the organic phase collected and washed with anhydrous Na₂SO₄And (5) drying. Filtering the dried solutionThe solvent was removed by rotary evaporator to give crude product. The crude product was purified by silica gel chromatography and finally by sublimation to give solid X011(3.1mmol, 62%).

MALDI-TOF MS:m/z calcd for C61H40N2P2:862.3；found:862.4。

x011(2.2mmol) was added to a round bottom flask at room temperature, 50mL of dichloromethane was added, excess hydrogen peroxide (30 wt%, 5mL) was added, and the mixture was vigorously stirred for 30 min. 100mL of H was added₂Extracting with dichloromethane, collecting organic phase, washing with deionized water and saturated saline solution, and adding anhydrous Na₂SO₄Drying, filtration, recrystallization from n-hexane, and purification by sublimation gave the title compound M003(2.1mmol, yield 95%).

MALDI-TOF MS:m/z calcd for C61H40N2O2P2:894.3；found:894.5。

characterization effect of M003:

calculated values of elemental analysis: c, 81.87; h, 4.51; n, 3.13; o, 3.58; p, 6.92; measurement values: c, 81.91; h, 4.54; n, 3.10; o, 3.56; p, 6.90.

The result of the nuclear magnetic resonance hydrogen spectrum of M003 is as follows:

¹H NMR(400MHz,CDCl₃,ppm):8.15-8.16(m,4H),7.84-7.85(m,2H),7.80-7.83(m,6H),7.72-7.74(m,4H),7.67-7.68(m,2H),7.50-7.54(m,10H),7.40-7.41(m,2H),7.32-7.35(m,6H),7.26-7.28(m,4H)。

example 2

Synthesis of Compound M002

Under nitrogen protection, compound X010(10.5mmol) was weighed into a 500mL two-necked flask, and 80mL of dry, anhydrous tetrahydrofuran was added to dissolve X010. NaH (stored in 60% oil, 11.0mmol) was repeatedly rinsed three times with n-hexane, added to the two-necked flask in portions, and stirred for 1 h. Then, X006(5mmol) was added to the two-necked flask, and the mixture was reacted at room temperature and stirred overnight. The reaction was quenched with methanol and water, extracted with dichloromethane, the organic phase collected and washed with anhydrous Na₂SO₄And (5) drying. The dried solution was filtered and the solvent was removed using a rotary evaporator to give the crude product. The crude product was purified by chromatography on a silica gel column and finally by sublimation to give solid X012 (yield 68%).

MALDI-TOF MS:m/z calcd for C61H40N2P2:862.3；found:862.5。

x012(2.2mmol) was added to a round bottom flask at room temperature, 50mL of dichloromethane was added, excess hydrogen peroxide (30 wt%, 5mL) was added, and stirring was performed vigorously for 30 min. 100mL of H was added₂Extracting with dichloromethane, collecting organic phase, washing with deionized water and saturated saline solution, and adding anhydrous Na₂SO₄After drying and filtration, recrystallization was performed using n-hexane, and sublimation purification was performed to obtain the target compound M002 (yield 92%).

MALDI-TOF MS:m/z calcd for C61H40N2O2P2:894.3；found:894.6。

characterization effect of M002:

calculated values of elemental analysis: c, 81.87; h, 4.51; n, 3.13; o, 3.58; p, 6.92; measurement values: c, 81.92; h, 4.53; n, 3.12; o, 3.55; p, 6.89.

The result of the nuclear magnetic resonance hydrogen spectrum of M002 is:

¹H NMR(400MHz,CDCl₃,ppm):8.19-8.21(m,4H),7.86(s,2H),7.80-7.81(m,4H),7.70-7.71(m,6H),7.60-7.61(m,2H),7.50-7.54(m,10H),7.40-7.41(m,2H),7.32-7.34(m,6H),7.26-7.27(m,4H)。

example 3

Synthesis of Compound M001

Under nitrogen protection, compound X010(10.5mmol) was weighed into a 500mL two-necked flask, and 80mL of dry, anhydrous tetrahydrofuran was added to dissolve X010. NaH (stored in 60% oil, 11.0mmol) was repeatedly rinsed three times with n-hexane, added to the two-necked flask in portions, and stirred for 1 h. Then, X003(5mmol) was added to the two-necked flask, and the mixture was reacted at room temperature and stirred overnight. The reaction was quenched with methanol and water, extracted with dichloromethane, and the organic phase was collected and dried over anhydrous Na2SO 4. The dried solution was filtered and the solvent was removed using a rotary evaporator to give the crude product. The crude product was purified by silica gel chromatography and finally by sublimation to give X013 as a solid (yield 74%).

MALDI-TOF MS:m/z calcd for C61H40N2O2P2:894.3；found:894.5。

x013(2.2mmol), 50mL of dichloromethane, excess hydrogen peroxide (30 wt%, 5mL) were added to the round bottom flask at room temperature and stirred vigorously for 30 min. 100mL of H was added₂Extracting with dichloromethane, collecting organic phase, washing with deionized water and saturated saline solution, and adding anhydrous Na₂SO₄After drying and filtration, recrystallization was performed using n-hexane, and sublimation purification was performed to obtain the target compound M001 (yield 94%).

MALDI-TOF MS:m/z calcd for C61H40N2O2P2:894.3；found:894.3。

characterization effect of M002:

calculated values of elemental analysis: c, 81.87; h, 4.51; n, 3.13; o, 3.58; p, 6.92; measurement values: c, 81.89; h, 4.54; n, 3.11; o, 3.56; p, 6.91.

The result of the nuclear magnetic resonance hydrogen spectrum of M001 is as follows:

¹H NMR(400MHz,CDCl₃,ppm):8.18-8.19(m,4H),7.87-7.89(m,4H),7.80-7.81(m,4H),7.70-7.71(m,4H),7.63-7.64(m,4H),7.50-7.52(m,8H),7.40-7.41(m,2H),7.32-7.34(m,6H),7.26-7.27(m,4H)。

testing the performance of the compound:

simulated calculation of energy levels of compounds

The energy levels of the compounds of the examples and comparative examples were calculated by simulation using the Density Functional Theory (DFT). The distribution of the molecular front line orbitals HOMO and LUMO of the compounds of the present application were optimized and calculated using the Gaussian 09 package (Guassian Inc.) at the B3LYP/6-31G (d) calculation level, as shown in Table 1; meanwhile, based on the time-density functional theory (TD-DFT), the singlet state energy level S of each compound molecule is calculated in a simulation mode₁And triplet state energy level T₁The results are shown in Table 2, where Δ E_ST＝S₁-T₁，E_g＝HOMO-LUMO，E_gThe absolute value of (a) is taken.

TABLE 1

TABLE 2

Compound (I)	HOMO(eV)	LUMO(eV)	S₁(eV)	T₁(eV)	E_g(eV)
						M001	5.52	1.23	3.78	3.17	4.29
M002	5.41	1.23	3.71	3.18	4.19
						M003	5.62	1.40	3.45	3.13	4.23
M013	5.43	1.59	3.36	2.89	3.84
						M015	5.55	1.57	3.39	3.02	3.99
M113	5.75	1.19	3.90	3.12	4.56
						M114	5.76	1.33	3.88	3.20	4.43
M115	5.92	1.39	3.98	3.22	4.53
						M134	5.02	1.53	3.11	3.02	3.50
M173	5.38	1.41	3.50	3.18	3.96
						M191	5.39	1.43	3.49	3.21	3.97

As can be seen from table 2, the compound of the present application has a spiro structure containing a phosphino P ═ O group as a core of the compound, and the core unit is an electron accepting unit, which itself has a good electron transport ability; further, by substituting an electron-donating substituent on the core unit, a compound with good electron and hole bipolar transport capacity can be obtained, and the compound with appropriate HOMO and LUMO energy levels is beneficial to energy level matching of the compound and compounds of adjacent layers, so that the hole and electron injection barrier can be reduced, and the driving voltage of the device can be reduced.

The compound of the application has high triplet energy level, can prevent triplet energy backflow from a guest material to a host material, so that triplet excitons are limited in a light emitting layer to the maximum extent, the exciton utilization rate can be improved, the light emitting efficiency of an OLED device is improved, and the compound is suitable for being used as a blue light phosphorescence material.

The compound of the application has poor planarity in spatial configuration and weak intermolecular acting force, so the film forming property is good, and the compound is favorable for forming a stable and uniform amorphous film in the thermal vacuum evaporation process, thereby prolonging the service life of an organic light-emitting device. In addition, when the compound is applied to a light-emitting layer of an OLED device, the phenomenon of aggregation luminescence quenching in the light-emitting layer can be effectively inhibited, so that the luminous efficiency can be improved, and the service life of the OLED device can be prolonged.

In summary, the present application provides a donor-acceptor type bipolar host material in which an electron donating group and an electron accepting group are connected by a chemical bond. On one hand, the conjugated length is effectively interrupted by adopting a spiral ring structure, so that a high triplet state energy level can be realized, and meanwhile, good bipolar carrier transmission characteristics of holes and electrons are maintained. On the other hand, the spiro structure containing phosphine oxide P ═ O group is adopted as the core of the compound, the aromatic group connected with the phosphorus atom P is connected through supersaturated C-P bond, the electronic effects such as conjugation in the molecule and the like are effectively inhibited, thereby expanding and functionalizing the molecular system and simultaneously preventing the negative effects such as the reduction of the energy level of the excited state and the like to the maximum extent. The P ═ O group has a moderate electron-withdrawing induction effect and can effectively polarize molecules, so that the electron transmission capability of the material is enhanced; and the P ═ O group has a typical triangular pyramid type stereo configuration, and the steric hindrance effect is remarkable. The molecular configuration can be changed in a targeted way by selecting different modification positions, so that the space effect among groups and the stacking form among molecules are changed.

The following application examples provide illustrative examples for illustrating the practical application of the compounds of the present application in organic light emitting display panels.

Application example 1

The application example provides an OLED device, the structure of which is shown in fig. 1, and the OLED device includes a substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, and a cathode 9, which are sequentially stacked, and arrows in fig. 1 represent the light emitting direction of the device.

The preparation method of the OLED device comprises the following steps:

1) the glass substrate 1 was cut into a size of 50mm × 50mm × 0.7mm, ultrasonically cleaned in acetone, isopropyl alcohol, and deionized water, respectively, for 30 minutes, and then cleaned under UV ozone for 30 minutes. Mounting the resulting glass substrate with Indium Tin Oxide (ITO) anode on a vacuum deposition apparatus;

2) evaporating a hole injection layer material (compound a) as a hole injection layer 3 on the ITO anode 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material is 10 nm;

3) a hole transport layer material (compound b) was vacuum-evaporated on the hole injection layer 3 as a first hole transport layer 4 with a thickness of 100 nm;

4) a hole transport type material (compound c) was vacuum-evaporated as a second hole transport layer 5 on the first hole transport layer 4 to a thickness of 10 nm;

5) and a light-emitting layer 6 is vacuum-evaporated on the second hole transport layer 5, wherein a compound M001 is used as a host material of the light-emitting layer, a compound d is used as a guest material of the light-emitting layer, and the ratio of the compound M001: chemical d 92:8, thickness 30 nm;

6) an electron transport material (compound e) as a first electron transport layer 7 was vacuum-deposited on the light-emitting layer 6 to a thickness of 10 nm;

7) vacuum evaporating an electron transport material (compound f and compound g in a mass ratio of 1:1) on the first electron transport layer 7 to form a second electron transport layer 8 with a thickness of 30 nm;

8) a silver electrode as a cathode 9 was vacuum-evaporated on the second electron transport layer 8 to a thickness of 15 nm.

The preparation of the OLED devices of application examples 2 to 11 and comparative example 1 was similar to application example 1, except that compound M001 was replaced in step 5) with compounds M002, M003, M013, M015, M113, M114, M115, M134, M173, M191 and comparative compound 1, respectively, as detailed in table 3.

Performance evaluation of OLED devices:

the current of the OLED device under different voltages is tested by a Keithley 2365A digital nano-volt meter, and then the current is divided by the light-emitting area to obtain the current density of the OLED device under different voltages. The luminance and radiant energy flux density of the OLED devices at different voltages were tested using a Konicaminolta CS-2000 spectroradiometer. According to the OLED device inThe current density and the brightness under different voltages are obtained at the same current density (10 mA/cm)²) Operating voltage Von and current efficiency CE_(10mA/cm2)(in cd/A). The lifetime T95 (at 50 mA/cm) was obtained by measuring the time when the luminance of the organic light emitting device reached 95% of the initial luminance²Under test conditions).

The organic light-emitting device thus produced was applied with a dc voltage, and the results of measuring the light-emitting properties of the device are summarized in table 3.

TABLE 3

From the data in table 3, it can be seen that the blue OLED device prepared by using the compound provided herein as the host material of the light emitting layer has lower operating voltage, higher current efficiency and longer operating life compared to the comparative compound 1. The compound provided by the application is reasonably matched with the substituent group through the core unit, realizes a high triplet state energy level, has proper HOMO energy level and LUMO energy level, can be matched with an object material of a luminous layer, and realizes an efficient energy transfer process in the luminous layer. In addition, the compound has good hole and electron bipolar transmission capacity, can effectively adjust a light-emitting composite region in an OLED device, improves the light-emitting efficiency and the long service life of the OLED device, and reduces the working voltage. The compound of the application has poor planarity in spatial configuration and weak intermolecular acting force, so that the compound can be ensured to have excellent film stability, thereby being beneficial to improving the stability of long-time work of devices.

In accordance with the embodiments of the present application as described above, these embodiments are not exhaustive and do not limit the application to the specific embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and its practical application, to thereby enable others skilled in the art to best utilize the application and its various modifications as are suited to the particular use contemplated. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A compound having the structure shown in formula I:

m and n are each independently selected from 0, 1 or 2.

2. The compound of claim 1, wherein Ar is Ar₁And Ar₂Is a substituted or unsubstituted aryl group with C6-C30, and is respectively and independently selected from phenyl, naphthyl, phenanthryl, anthryl, biphenyl, triphenylene, pyrenyl, spirobifluorenyl,

At least one of perylene, indenyl and azulenyl.

3. The compound of claim 2, wherein Ar is Ar₁Is phenyl; and/or Ar₂Is phenyl.

4. The compound of claim 1, wherein Ar is Ar₁And Ar₂Is a substituted or unsubstituted heteroaryl group of C2-C20, and is independently selected from at least one of pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, isoquinolyl, acridinyl, purinyl, pteridinyl, benzofuryl, benzothienyl, benzimidazolyl, benzothiazolyl, cinnoline, quinoxalinyl, dibenzofuryl, dibenzothienyl and phenanthrolinyl.

5. The compound of claim 4, wherein Ar is Ar₁And Ar₂Each independently selected from at least one of furyl, thienyl, benzofuryl, benzothienyl, dibenzofuryl and dibenzothienyl.

6. The compound of claim 1, wherein Ar is Ar₁、Ar₂、D₁And D₂In (b) is a substituted or unsubstituted C12-C40 carbazolyl group, and each is independently selected from at least one of the following groups:

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

7. The compound of claim 6, wherein Ar is Ar₁、Ar₂、D₁And D₂Each independently selected from at least one of the following groups:

8. The compound of claim 1, wherein Ar is Ar₁、Ar₂、D₁And D₂Is a substituted or unsubstituted C12-C40 arylamine group, and is respectively and independently selected from at least one of the following groups:

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

9. The compound of claim 8, wherein Ar is Ar₁、Ar₂、D₁And D₂Each independently selected from at least one of the following groups:

10. the compound of claim 1, wherein Ar is Ar₁、Ar₂、D₁And D₂Is a substituted or unsubstituted acridine group of C18-C40, and is selected from at least one of the following groups:

x and Y independently represent O, S, N (Z), C (Z)₂、Si(Z)₂Wherein Z independently represents hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, or substitutedOr unsubstituted C6-C40 aryl;

α, β and γ each independently represent 0, 1 or 2;

# denotes the ligation site.

11. The compound of claim 10, wherein Ar is Ar₁、Ar₂、D₁And D₂Each independently selected from at least one of the following groups:

12. the compound of claim 1, wherein L is₁And L₂Is a substituted or unsubstituted aryl group with C6-C30, and is respectively and independently selected from phenyl, naphthyl, phenanthryl, anthryl, biphenyl, triphenylene, pyrenyl, spirobifluorenyl,

Perylene, indenyl or azulenyl.

13. The compound of claim 12, wherein L is₁Is phenyl; and/or L₂Is phenyl.

14. The compound of claim 1, wherein L is₁And L₂Is a substituted or unsubstituted heteroaryl group of C2-C20, and is independently selected from pyrrolyl, furyl, oxazolyl, isoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazole, pyridazinyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, quinolyl, pyridyl, and the like,An isoquinolyl group, an acridinyl group, a purinyl group, a pteridinyl group, a benzofuranyl group, a benzothiophenyl group, a benzimidazolyl group, a benzothiazolyl group, a cinnoline, a quinoxalinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, or a phenanthrolinyl group.

15. The compound of claim 14, wherein L is₁And L₂Each independently selected from furyl, thienyl, benzofuryl, benzothienyl, dibenzofuryl or dibenzothienyl.

16. The compound of claim 1, wherein the compound is selected from any one of:

17. a display panel comprising an organic light emitting device comprising an anode, a cathode, a light emitting layer between the anode and the cathode, wherein the light emitting layer comprises a host material and a guest material, characterized in that the host material or the guest material of the light emitting layer comprises one or more of the compounds of any one of claims 1 to 16.

18. The display panel according to claim 17, wherein the host material of the light-emitting layer further comprises a dopant material, and wherein the dopant material comprises at least one of a material having an electron-transporting function and a material having a hole-blocking function.

19. The display panel according to claim 17 or 18, wherein the organic light-emitting device further comprises one or more layers selected from a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

20. A display device comprising the display panel of any one of claims 17 to 19.