CN114478499A

CN114478499A - Spirofluorene anthracene compound and application thereof

Info

Publication number: CN114478499A
Application number: CN202210112366.2A
Authority: CN
Inventors: 王占奇; 李志强; 陆金波; 黄常刚
Original assignee: Fuyang Sineva Material Technology Co Ltd
Current assignee: Fuyang Sineva Material Technology Co Ltd
Priority date: 2022-01-29
Filing date: 2022-01-29
Publication date: 2022-05-13
Anticipated expiration: 2042-01-29
Also published as: CN114478499B

Abstract

The invention provides a spirofluorene heteroanthracene compound and application thereof. The invention provides a compound shown in formula I, wherein spirofluorene xanthene or spirofluorene thioxanthene is taken as a mother nucleus, the substitution position of each substituent group in the mother nucleus is defined, and a specific substituent group is defined simultaneously for improving the material performance, so that an organic electroluminescent device prepared by the compound has longer service life.

Description

Spirofluorene anthracene compound and application thereof

Technical Field

The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a spirofluorene heteroanthracene compound and application thereof.

Background

Currently, organic electroluminescent (OLED) display technology has been applied in the fields of smart phones, tablet computers, and the like, and further will be expanded to large-size application fields such as televisions. In the development process of the last 30 years, various OLED materials with excellent performance are developed, and the commercialization process of the OLED is accelerated by different designs of the device structure and optimization of the device life, efficiency and other properties, so that the OLED is widely applied in the fields of display and illumination. The selection of the hole layer, the light-emitting layer and other organic functional layer materials also has a great influence on the current efficiency, the driving voltage and the lifetime of the device, and functional layer materials with higher performance are still being explored.

CN108864146A discloses a spirofluorene xanthene derivative and its application in OLED devices, which incorporates a hexatomic heterocyclic structure containing nitrogen atoms into a spirofluorene xanthene core skeleton, the spirofluorene xanthene derivative in the present invention has high carrier mobility and high glass transition temperature, and is not easy to crystallize, so that it has good thermal stability and film forming property, and is a functional material applied in organic electroluminescent devices, especially used as a hole transport layer material, a hole injection layer material and a luminescent main body material, and can effectively improve the luminescent efficiency and service life of the devices.

CN110845508A discloses a compound with spirofluorene anthrone as a core, a preparation method and application thereof, belonging to the technical field of semiconductors. The compound is connected with a six-membered ring fused ring derivative structure by spirofluorene anthrone, and the whole molecule is a larger rigid structure and has a high triplet state energy level (T1); the structure has strong stereoscopy, large steric hindrance and difficult rotation, improves the chemical stability of the material, and ensures that the compound has higher glass transition temperature and molecular thermal stability.

CN112794804A discloses a spirofluorene derivative, which is prepared by introducing arylamine and spirofluorene groups with strong electron supply to the outside of binaphthyl derivative molecules, so as to increase the steric hindrance of conjugated molecules, prevent pi-pi conjugation from generating excited state compounds, improve the organic solubility and stability of molecules, reduce the temperature of sublimation purification, and improve the efficiency and lifetime of an organic electroluminescent device containing the spirofluorene derivative as a luminescent layer material.

Therefore, in order to meet the higher requirements of people for OLED devices, the development of more various and higher-performance OLED materials is urgently needed in the art.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a spirofluorene anthracene compound and application thereof. The spirofluorene anthracene compound can be used as an electronic barrier material of an OLED light-emitting device, and the obtained organic electroluminescent device has longer service life.

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

in a first aspect, the present invention provides a spirofluorene heteroanthracene compound having a structure represented by formula I below:

wherein X is selected from O or S. (replacement of the oxygen in spirofluorene xanthene by sulfur, also in the scope of protection.)

R₁₁、R₂₁Each independently selected from hydrogen, deuterium, fluorine, CN, substituted or unsubstituted C1 to C20 linear or branched alkyl groups, substituted or unsubstituted C1 to C20 (for example, C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy groups, substituted or unsubstituted C6 to C40 (for example, C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl groups.

Ar is selected from substituted or unsubstituted C6-C40 aryl.

Ar₁、Ar₂Each independently selected from substituted or unsubstituted C6 to C40 (for example, C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl, substituted or unsubstituted C12 to C40(C12, C14, C16, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) oxaaryl, substituted or unsubstituted C12 to C40(C12, C14, C16, C18, C20, C23, C25, C27, and the like) anthryl, and at least one of anthryl group selected from fluorescein, anthracene group, and 27.

The above oxaaryl group means a structure having an oxygen-containing five-membered heterocyclic ring formed by bridging two aromatic rings connected by a single bond through an O atom. For example, two benzene rings are linked together by a single bond to form biphenyl, and carbon atoms on the two benzene rings constituting biphenyl are simultaneously linked with an O atom to form dibenzofuran.

The above thiaaryl group means a structure having a sulfur-containing five-membered heterocyclic ring formed by bridging two aromatic rings connected by a single bond through an S atom. For example, two benzene rings are linked together by a single bond to form biphenyl, and carbon atoms on the two benzene rings constituting biphenyl are simultaneously linked with an S atom to form dibenzothiophene.

p is an integer of 0 to 1, and may be, for example, 0 or 1.

m and n are each independently an integer of 0 to 4, and may be, for example, 0, 1, 2, 3 or 4.

In the invention, the C6-C40 aryl is selected from any one of phenyl, biphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

In the present invention, the C12-C40 oxaaryl group is selected from any one of dibenzofuranyl, naphthobenzofuranyl or dinaphthofuranyl.

In the invention, the C12-C40 thiaaryl is selected from any one of dibenzothienyl, naphthobenzothienyl or dinaphthothiophenyl.

In the invention, the substituent of the substituted C1-C20 straight-chain or branched alkyl, substituted C1-C20 alkoxy, substituted C6-C40 aryl, substituted C12-C40 oxaaryl and substituted C12-C40 thiaaryl is selected from one of deuterium, fluorine, cyano, C1-C6 straight-chain or branched alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylenyl, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

In the present invention, said R₁₁、R₂₁Each selected from hydrogen, deuterium, fluorine, cyano, C1-C6 straight chain or branched chain alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl,One of anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthracenyl.

Preferably, said R is₁₁、R₂₁Each independently selected from one of hydrogen, phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthracenyl.

In the invention, the spirofluorene anthracene compound has a structure shown as the following formula I-1 or formula I-2:

wherein, X, X₁Each independently selected from O or S. (replacement of the oxygen in spirofluorene xanthenes by sulfur, also in the protective range.) R₁₁、R₂₁Each independently selected from hydrogen, deuterium, fluorine, CN, C1-C20 straight chain or branched chain alkyl, C1-C20 alkoxy and C6-C40 aryl. Ar is selected from C6-C40 aryl. Ar (Ar)₁Any one selected from phenyl, naphthyl, triphenylene or fluoranthenyl. R₃₁Is selected from C1-C20 straight chain or branched chain alkyl, C1-C20 alkoxy and C6-C40 aryl. R₄₁、R₄₂Each independently selected from C1-C20 straight chain or branched chain alkyl, C6-C40 aryl, and R₄₁And R₄₂Independent of each other or linked by a single bond to form a ring.

Preferably, the spirofluorene anthracene compound is selected from any one of the following 1-140S:

wherein, the spirofluorene thianthrene compound 1S-140S is a corresponding compound obtained by replacing oxygen in the spirofluorene xanthene main body structure with sulfur in the spirofluorene xanthene compound 1-140.

I.e., the compounds shown in 1-140 above, all include

Will be provided with

Change to

The structures obtained after the reaction are represented by the symbols 1S to 140S and are also within the scope of the present invention.

Such as compound 2 having the structure

The structure of compound 2S is then:

in a second aspect, the present invention provides a spirofluorene heteroanthracene compound as described in the first aspect for use in an electron blocking layer material.

In a third aspect, the present invention provides an organic electroluminescent device comprising a spirofluorene anthracene compound according to the first aspect.

In the present invention, the organic electroluminescent device comprises an electron blocking layer comprising any one of or a combination of at least two of the spirofluorene heteroanthracene compounds according to the first aspect.

Wherein the electron blocking layer is positioned between the hole layer and the light emitting layer.

In a fourth aspect, the present invention provides a display device, wherein the display device comprises the organic electroluminescent device according to the third aspect.

In a fifth aspect, the present invention provides an intermediate for preparing the spirofluorene heteroanthracene compound of the present invention, the intermediate specifically comprising the following compounds:

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

the invention provides a compound shown in formula (I), which takes spirofluorene xanthene or spirofluorene thioxanthene as a mother nucleus, defines the substitution position of each substituent group in the mother nucleus, and simultaneously defines a specific substituent group for improving the material performance, so that an organic electroluminescent device prepared by the compound has longer service life.

Drawings

FIG. 1 shows a general structural formula of spirofluorene heteroanthracene compounds shown in formula I.

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.

Example 1

This example provides a Compound 1

The synthesis steps are as follows:

500mL of a three-necked flask, purged with nitrogen, 150mL of dry toluene, 4.11g (0.01mol) of a compound represented by M-0, 2.59g (0.01mol) of a compound represented by M-1-2, 0.0575g (0.0001mol) of Pd (dba)₂(bis (dibenzylideneacetone palladium)), 0.4g (0.0002mol) of a toluene solution containing 10% tri-tert-butylphosphine, 1.44g (0.015mol) of sodium tert-butoxide, heated to reflux for 8 hours, cooled, added with water for liquid separation, washed with water for the organic layer to neutrality, dried over magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, petroleum ether: ethyl acetate 10:1 (vol/vol) gave 4.9g of compound 1.

Characterization data for the target product compound 1:

mass spectrum detection, wherein m/z is 589.20;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ8.23(d，1H)，δ8.00(m，1H)，δ7.88(m，2H)，δ7.68(m，2H)，δ7.55(m，1H)，δ7.46(d，1H)，δ7.43～7.14(m，12H)，δ7.11～6.83(m，7H)。

Example 2

This example provides Compound 2

The synthesis steps are as follows:

synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 was changed to the compound represented by M-2-2 to give Compound 2.

Characterization data for the target product compound 2:

mass spectrometric detection of 639.22 m/z.

Example 3

This example provides a compound 11:

the synthesis steps are as follows:

synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 was changed to the compound represented by M-11-2 to give Compound 11.

Characterization data for the target product compound 11:

mass spectrum detection, measuring m/z as 665.24;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ8.09(m，1H)，δ8.03(m，1H)，δ7.91(m，2H)，δ7.68～7.61(m，3H)，δ7.55～7.14(m，17H)，δ7.11～6.96(m，5H)，δ6.95～6.83(m，2H)。

Example 4

This example provides a compound 14

The synthesis steps are as follows:

synthesis method referring to example 1 Synthesis of Compound 1, the difference from example 1 is that only the compound represented by M-1-2 was changed to a compound represented by M-14-2 to give Compound 14.

Characterization data for the target product compound 14:

mass spectrometric detection of 765.27 m/z.

Example 5

This example provides a compound 38

The synthesis steps are as follows:

synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 was changed to the compound represented by M-38-2 to give Compound 38.

Characterization data for target product compound 38:

mass spectrum detection, measuring m/z as 725.27;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ8.99(d，1H)，δ8.35(m，2H)，δ8.29(m，1H)，δ8.09(d，1H)，δ7.91(m，2H)，δ7.83～7.59(m，7H)，δ7.58～7.33(m，15H)，δ7.07～6.96(m，2H)，δ6.95～6.80(m，4H)。

Example 6

This example provides Compound 45

The synthesis steps are as follows:

(1) synthesis of Compound M-45-2

250mL three-necked flask, protected with nitrogen, 100mL dry toluene, 3.23g (0.01mol) 2-bromo-11, 11-dimethyl-11H-benzo [ b ] was added]Fluorene, 2.43g (0.01mol) triphenylen-2-amine, 0.0575g (0.0001mol) Pd (dba)₂(palladium bis-dibenzylideneacetone), 0.4g (0.0002mol) of toluene solution containing 10% of tri-tert-butylphosphine, 1.44g (0.015mol) of sodium tert-butoxide, heating to 60 ℃ for reaction for 4h, heating to reflux for reaction for 2h, cooling, adding water for liquid separation, washing an organic layer to neutrality, drying magnesium sulfate, filtering to remove the magnesium sulfate, concentrating to dryness, separating by silica gel column chromatography, petroleum ether: ethyl acetate 10:0.5 (vol/vol) gave 1.6g of compound M-45-2.

Performing mass spectrum detection on the compound M-45-2, and determining that the molecular M/z is as follows: 485.21.

(2) synthesis of Compound 45

Synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 therein is replaced with a compound represented by M-45-2 to give Compound 45;

characterization data for target product compound 45:

mass spectrum detection, measuring m/z as 815.32;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ9.07(m，1H)，δ8.89(d，1H)，δ8.35(m，1H)，δ8.31(d，1H)，δ8.22(d，1H)，δ8.18～8.13(m，3H)，δ8.09(d，1H)，δ7.96(m，1H)，δ7.89(m，2H)，δ7.78(m，1H)，δ7.72(m，2H)，δ7.66～7.60(m，3H)，δ7.55～7.50(m，3H)，δ7.41(m，1H)，δ7.37～7.22(m，5H)，δ7.21～7.15(m，2H)，δ7.05(m，1H)，δ7.00(m，1H)，δ6.93(m，1H)，δ6.88(m，1H)，δ5.79(m，2H)，δ1.76(s，6H)。

Example 7

This example provides a compound 53

The synthesis steps are as follows:

(1) synthesis of Compound M-53-2

Referring to the synthesis of compound M-45-2 in example 6, except using the corresponding bromide and amine reaction, compound M-53-2 was obtained.

The compound M-53-2 is subjected to mass spectrum detection, and the molecule M/z is determined as follows: 383.13.

(2) synthesis of Compound 53

Synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 is replaced with a compound represented by M-53-2 to give Compound 53;

characterization data for the target product compound 53:

mass spectrum detection, measuring m/z as 713.24;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ8.43(m，2H)，δ8.09(m，2H)，δ7.99(m，1H)，δ7.91(m，2H)，δ7.83～7.73(m，6H)，δ7.66(m，1H)，δ7.58～7.51(m，2H)，δ7.43～7.14(m，11H)，δ7.07～6.83(m，4H)。

Example 8

This example provides a compound 73

The synthesis steps are as follows:

a 250mL three-necked flask was charged with 60mL of toluene, 20mL of ethanol and 10mL of water under nitrogen protection, and then 4.11g (0.01mol) of the compound represented by M-0, 2.89g (0.01mol) of the boronic acid compound represented by M-73-2, 2.12g (0.02mol) of sodium carbonate and 0.115g (0.0001mol) of tetratriphenylphosphine palladium were added, the mixture was slowly heated to reflux reaction for 6 hours, cooled, added with water for liquid separation, the organic layer was washed with water, dried over magnesium sulfate, filtered to remove magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a solid, which was subjected to column chromatography, and eluted with petroleum ether and ethyl acetate in a volume ratio of 10:0.5 to obtain compound 73, having a mass of 4.6 g.

Characterization data for target product compound 73:

mass spectrum detection, measuring m/z as 575.22;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ7.91(m，2H)，δ7.84(m，1H)，δ7.66(m，2H)，δ7.57(m，2H)，δ7.40～7.14(m，15H)，δ7.09(m，4H)，δ7.01(m，3H)。

Example 9

This example provides a compound 86

The synthesis steps are as follows:

the synthesis method refers to the synthesis of compound 73 in example 8, and differs from example 8 only in that the compound represented by M-73-2 is replaced by the compound represented by M-86-2 to obtain compound 86;

characterization data for target product compound 86:

mass spectrometric detection of 751.29 m/z.

Example 10

This example provides a compound 109

The synthesis steps are as follows:

synthesis method referring to the synthesis of Compound 73 of example 8, the difference from example 8 is that only the compound represented by M-73-2 was changed to a compound represented by M-109-2 to give Compound 109;

characterization data for the target product compound 109:

mass spectrometric detection of 691.29 m/z.

Example 11

This example provides a compound 121

The synthesis steps are as follows:

synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 is replaced with a compound represented by M-121-2 to give Compound 121;

characterization data for the target product compound 121:

mass spectrometric detection of 615.26 m/z.

Example 12

This example provides a compound 125

The synthesis steps are as follows:

(1) synthesis of Compound M-125-0

A 250mL three-necked bottle is filled with nitrogen for protection, 2.85g (0.01mol) of a compound shown as M-121-2, 2.83g (0.01mol) of 4-bromoiodobenzene, 1.06g of sodium carbonate, 100mL of DMF, 0.5g of cuprous iodide and 0.2g of 1, 10-o-phenanthroline are added, the temperature is increased to reflux reaction for 24 hours, the temperature is reduced, water is added, the obtained solid is filtered, the solid is heated and dissolved by toluene after being dried, insoluble substances are filtered out, the mother liquor is concentrated to be dry, and the mixed solvent of methanol and toluene is used for recrystallization to obtain 3.0g of the compound shown as M-125-0.

The compound shown as M-125-0 is subjected to mass spectrum detection, the two maximum M/z peaks are 439.09 and 441.09, and the molecular formula of the product is determined as follows: c₂₇H₂₂BrN。

(2) Synthesis of Compound M-125-2

Adding 80mL of tetrahydrofuran and 4.4g (0.01mol) of a compound shown as M-125-1 into a 250mL three-neck flask under the protection of nitrogen, cooling to-78 ℃, slowly dropwise adding 7.5mL (0.012mol) of a 1.6M n-hexane solution of butyllithium, keeping the temperature at-78 ℃ for 30min after the addition is finished, then adding 1.56g (0.015mol) of trimethyl borate, slowly raising the temperature to room temperature for reaction for 2h, adding water and ethyl acetate for liquid separation, washing an organic layer with common salt water, drying magnesium sulfate, filtering to remove the magnesium sulfate, concentrating to dryness to obtain boric acid shown as M-125-2, and directly reacting downwards without further purification.

(3) Synthesis of Compound 125

The synthesis method refers to the synthesis of compound 73 in example 8, and differs from example 8 only in that the compound represented by M-73-2 is replaced by a compound represented by M-125-2 to obtain a compound 125;

characterization data for target product compound 125:

mass spectrum detection is carried out, and m/z is 691.29;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ7.91(m，3H)，δ7.86(m，1H)，δ7.64(m，2H)，δ7.58～7.52(m，4H)，δ7.44～7.14(m，17H)，δ7.09(m，2H)，δ7.01(m，2H)，δ1.69(s，6H)。

Example 13

This example provides a compound 139

The synthesis steps are as follows:

(1) synthesis of Compound M-139-2

The synthesis method refers to the synthesis of the compound M-45-2 in example 6, and is different from the synthesis method in example 6 in that the corresponding bromide and amine are adopted for reaction to obtain the compound M-139-2;

the compound M-139-2 is subjected to mass spectrum detection, and the molecule M/z is determined as follows: 407.17.

(2) synthesis of Compound 139

Synthesis method referring to the synthesis of Compound 1 of example 1, the difference from example 1 is that only the compound represented by M-1-2 therein is replaced with a compound represented by M-139-2 to give Compound 139;

characterization data for target product compound 139:

mass spectrum detection, measuring m/z as 737.27;

the nuclear magnetic detection is carried out on the sample,¹H-NMR (Bruker, Switzerland, Avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl)₃)：δ7.92～7.87(m，5H)，δ7.73(m，2H)，δ7.58～7.55(m，3H)，δ7.49～7.43(m，2H)，δ7.36～7.28(m，5H)，δ7.26～7.15(m，11H)，δ7.06(m，2H)，δ7.04(m，1H)，δ7.02(m，2H)，δ6.91(m，1H)，δ6.88(m，1H)。

Example 14

This example provides a Compound 2S

The synthesis steps are as follows:

the synthesis method refers to the synthesis of compound 2, except that the corresponding bromide is used to obtain compound 2S.

Characterization data for the target product compound 2S:

mass spectrometric detection of 655.20 m/z.

The materials used in the following application examples and comparative application examples are as follows:

application example 1

Application example 1 the compound 1 prepared in example 1 was selected as an electron blocking layer material (EB layer material) in an organic electroluminescent device.

The organic electroluminescent device has the following structure: ITO/HTL HD (5%) (20nm)/HTL (100 nm)/electron barrier material (20nm)/BH: BD (5%) (20nm)/ETL (30nm)/EIL (1nm)/Al (150 nm);

the preparation process comprises the following steps: placing the material in a vacuum chamber, and vacuumizing to 1 × 10^-5～1×10^-6Pa, and sequentially performing vacuum evaporation on the cleaned ITO substrate. Wherein HTL: HD (5%) (20nm) means that in the device, HTL and HD were co-evaporated in a volume ratio of 95:5 to form a hole transport layer having a thickness of 20 nm. Similarly understood, BH: BD (5%) (20nm) means that BH and BD co-evaporate in a volume ratio of 9:5 to form a light-emitting layer having a thickness of 20nm in the device.

Application examples 2 to 14

Application examples 2 to 14 differ from application example 1 only in that compound 1 was replaced with corresponding compounds 2 to 14, respectively, as shown in table 1 below; the other preparation steps are the same.

Comparative application examples 1 to 4

The comparative application examples 1 to 4 are different from the application example 1 only in that the compound 1 is replaced with corresponding HT-1 to HT-4 respectively as shown in the following Table 1; the other preparation steps are the same.

Performance test

Test samples: the organic electroluminescent devices provided in application examples 1 to 14 and the organic electroluminescent devices provided in comparative application examples 1 to 4;

the test method comprises the following steps: testing by using an OLED-1000 multichannel accelerated aging life and light color performance analysis system produced in Hangzhou distance, wherein the test items comprise the brightness, the driving voltage, the current efficiency and LT80 of an organic electroluminescent device; wherein LT80 refers to maintaining the initial brightness of the device at 1000cd/m²The current density of the transistor is not changed, and the efficiency of the device is reduced to 1000cd/m of the initial brightness²The time required for 80% of the corresponding efficiency.

The specific test results are shown in table 1 below:

TABLE 1

As shown in the test data in Table 1, the invention provides a compound shown in formula (I), wherein spirofluorene xanthene or spirofluorene thiaanthracene is used as a mother nucleus, the substitution position of each substituent group on the mother nucleus is limited, and a specific substituent group is also limited, so that the material performance is improved, and one, two or three of the indexes of the driving voltage, the current efficiency and the service life of the organic electroluminescent device prepared by using the compound can be improved. In particular, compounds 45, 53 and 125 have particularly pronounced lifetimes. While the voltage of compound 125 was as low as 3.89V.

The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims

1. A spirofluorene anthracene compound, having a structure represented by formula I:

wherein X is selected from O or S;

R₁₁、R₂₁each independently selected from hydrogen, deuterium, fluorine, CN, substituted or unsubstituted C1-C20 straight chain or branched chain alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C40 aryl;

ar is selected from substituted or unsubstituted C6-C40 aryl;

Ar₁、Ar₂each independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C40 oxaaryl, substituted or unsubstituted C12-C40 thiaaryl, and Ar₁Or Ar₂At least one group is selected from any one of phenyl, naphthyl, triphenylene or fluoranthenyl;

p is an integer of 0 to 1;

m and n are independently selected from integers of 0-4.

2. The spirofluorene heteroanthracene compound according to claim 1, wherein the C6-C40 aryl group is selected from any one of phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylenyl, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthracenyl;

preferably, the C12-C40 oxaaryl is selected from any one of dibenzofuranyl, naphthobenzofuranyl or dinaphthofuranyl;

preferably, the C12-C40 thiaaryl is selected from any one of dibenzothienyl, naphthobenzothienyl or dinaphthothiophenyl.

3. The spirofluorene heteroanthracene compound according to claim 1 or 2, wherein R is₁₁、R₂₁Each selected from one of hydrogen, deuterium, fluorine, cyano, C1-C6 linear or branched alkyl, C1-C6 alkoxy, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylene, fluoranthenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl or hydrogenated benzanthryl.

4. The spirofluorene anthracene compound according to any one of claims 1 to 3, wherein R is₁₁、R₂₁Each independently selected from hydrogen, phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, fluorenyl, benzofluorenyl, diphenylAnd one of a fluorenyl group, a triphenylene group, a fluoranthenyl group, a pyrenyl group, a perylene group, a spirofluorenyl group, an indenofluorenyl group, or a hydrogenated benzanthracenyl group.

5. The spirofluorene anthracene compound according to any one of claims 1 to 4, wherein the spirofluorene anthracene compound has a structure represented by formula I-1 or formula I-2 below:

wherein, X, X₁Each is independently selected from O or S;

R₁₁、R₂₁each independently selected from hydrogen, deuterium, fluorine, CN, C1-C20 straight chain or branched chain alkyl, C1-C20 alkoxy and C6-C40 aryl;

ar is selected from C6-C40 aryl;

Ar₁any one selected from phenyl, naphthyl, triphenylene or fluoranthenyl;

R₃₁selected from C1-C20 straight chain or branched chain alkyl, C1-C20 alkoxy and C6-C40 aryl;

R₄₁、R₄₂each independently selected from C1-C20 straight chain or branched chain alkyl, C6-C40 aryl, and R₄₁And R₄₂Independent of each other or linked by a single bond to form a ring.

6. The spirofluorene anthracene compound according to any one of claims 1 to 5, wherein the spirofluorene anthracene compound is selected from any one of 1 to 140, 1S to 140S:

7. Use of a spirofluorene heteroanthracene compound according to any one of claims 1 to 6 in an electron blocking layer material.

8. An organic electroluminescent device comprising the spirofluorene heteroanthracene compound according to any one of claims 1 to 6;

preferably, the organic electroluminescent device comprises an electron blocking layer which comprises any one or a combination of at least two of the spirofluorene heteroanthracene compounds according to any one of claims 1 to 6.

9. A display device characterized by comprising the organic electroluminescent device according to claim 8.

10. An intermediate for preparing the spirofluorene heteroanthracene compound according to any one of claims 1 to 6, wherein the intermediate specifically comprises the following compounds: