阅读说明：本技术 一种富勒烯衍生物、其用途及包含其的oled器件 (Fullerene derivative, application thereof and OLED (organic light emitting diode) device comprising fullerene derivative ) 是由 丁欢达 魏定纬 谢坤山 陈志宽 于 2019-11-27 设计创作，主要内容包括：本发明提供了一种富勒烯衍生物、其用途及包含其的OLED器件。所述富勒烯衍生物具有式I所示结构,由吸电子基团与富勒烯经加成反应得到。本发明提供的富勒烯衍生物可用作OLED器件的空穴传输层掺杂材料,其具有较低的最低未占有轨道能级,有利于接收空穴传输材料最高占有轨道能级上的电子,使其形成空穴,提高空穴浓度,提高空穴与电子的结合率,降低OLED器件的工作电压并提升发光效率；且本发明提供的富勒烯衍生物具有较高的结构稳定性,有助于提升OLED器件的寿命。(The invention provides a fullerene derivative, application thereof and an OLED device comprising the fullerene derivative. The fullerene derivative has a structure shown in a formula I and is obtained by an electron-withdrawing group and fullerene through an addition reaction. The fullerene derivative provided by the invention can be used as a hole transport layer doping material of an OLED device, has a lower lowest unoccupied orbital level, is beneficial to receiving electrons on the highest occupied orbital level of the hole transport material, so that holes are formed, the hole concentration is improved, the combination rate of the holes and the electrons is improved, the working voltage of the OLED device is reduced, and the luminous efficiency is improved; the fullerene derivative provided by the invention has higher structural stability, and is beneficial to prolonging the service life of an OLED device.)

1. A fullerene derivative having the structure shown in formula I:

in the formula I, R₁、R₂Each independently selected from cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C4-C60 cycloalkenyl, substituted or unsubstituted C5-C60 cycloalkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C2-C60 alkenyloxy, substituted or unsubstituted C2-C60 alkynyloxy, R₃-S-、R₄-S-、R₅-any one of S-;

Y₁、Y₂、Y₃、Y₄each independently selected from cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkenylamino, substituted or unsubstituted C2-C60 alkynylamino, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C2-C60 alkenyloxy, substituted or unsubstituted C2-C60 alkynyloxy, R₃-S-、R₄-S-、R₅-S-, substituted or unsubstituted C1-C60 boryl, substituted or unsubstituted C2-C60 borenyl, substituted or unsubstituted C2-C60 borynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 aryloxy, R₆-any of S-, substituted or unsubstituted C6-C60 boraaryl;

R₃is substituted or unsubstituted C1-C60 alkyl, R₄Is substituted or unsubstituted C2-C60 alkenyl, R₅Is substituted or unsubstituted C2-C60 alkynyl, R₆Is a substituted or unsubstituted C6-C60 aryl group;

and R is₁、R₂、Y₁、Y₂、Y₃And Y₄At least one of which is an electron withdrawing group;

when the group contains a substituent, the substituent is a halogen atom or a cyano group;

n is an integer of 1 to 30.

2. A fullerene derivative according to claim 1 wherein in formula I, R is₁、R₂Each independently selected from any one of cyano, substituted or substituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl and substituted or unsubstituted C1-C10 alkoxy;

preferably, R₁、R₂Each independently selected from any one of cyano, unsubstituted or fluorine substituted C1-C5 alkyl, and unsubstituted or fluorine substituted C1-C5 alkoxy.

3. A fullerene derivative according to claim 1 or 2 wherein in formula I, Y is₁、Y₂、Y₃、Y₄Each independently selected from any one of cyano, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C6-C12 arylamine and substituted or unsubstituted C6-C12 aryloxy;

preferably, Y₁、Y₂、Y₃、Y₄Each independently is a cyano group,

4. A fullerene derivative according to any one of claims 1-3 wherein in formula I, n is an integer from 1 to 4.

5. A fullerene derivative according to any one of claims 1-4 wherein in formula I R₁、R₂Each independently selected from any one of unsubstituted or fluorine-substituted C1-C5 alkyl and unsubstituted or fluorine-substituted C1-C5 alkoxy;

Y₁、Y₂、Y₃、Y₄each independently is a cyano group,Wherein the dotted line represents the attachment position of the group;

n is an integer of 1 to 4.

6. A fullerene derivative according to any one of claims 1-5, wherein the fullerene derivative is selected from any one of the following compounds 1-n to 19-n:

wherein n is 1, 2,3 or 4.

7. Use of a fullerene derivative according to any one of claims 1-6 as a hole transport layer doping material for an OLED.

8. An OLED device comprising a hole transport layer, and wherein the hole transport layer comprises a hole transport material and a doping material;

the doping material is selected from one or a combination of at least two of the fullerene derivatives of any one of claims 1 to 6.

9. The OLED device of claim 8, comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode, which are sequentially stacked.

10. The OLED device of claim 8 or 9, wherein the mass percentage of the doping material in the hole transport layer is 3-5%.

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a fullerene derivative, application thereof and an OLED device containing the fullerene derivative.

Background

In 1987, Tang et al of Kodak company in America successfully developed low-voltage and high-brightness organic light emitting diodes by using organic small molecular materials, so that Organic Light Emitting Diodes (OLEDs) are widely concerned due to the advantages of high-efficiency light emitting, simple manufacturing process, large-area flexibility and the like, and have great application prospects in the fields of display and illumination.

It is generally believed that the OLED emission mechanism is: under the drive of an applied voltage, carriers (electrons and holes) are respectively injected from the two electrodes and meet in the organic layer to form excitons, the excitons are released and energy is transferred to the organic light-emitting material, so that the organic light-emitting material is transited from a ground state to an excited state, the excited state is radiated and inactivated, the energy is released, and electroluminescence is generated.

Effective carrier injection, migration and recombination are important factors influencing the luminous efficiency of the OLED. For this reason, the organic material needs to have good electron donating ability or electron withdrawing ability, and the highest occupied orbital (HOMO) level and the lowest unoccupied orbital (LUMO) level of the material can be changed to facilitate the acceptance and migration of holes or electrons. However, since the mobility of electrons in the device is greater than that of holes, which easily causes hole quenching and reduces the light emitting efficiency of the device, it is very important for the development of OLED to develop materials with high hole and electron receiving and transmitting capabilities.

The hole transport layer is doped with the material with the low LUMO energy level, so that electrons on the HOMO energy level of the hole transport material can be received, holes can be formed, the hole concentration is improved, the combination rate of the holes and the electrons is improved, and the efficiency of the device is improved.

However, the research on the OLED device is less accumulated, the available hole transport layer doping materials are less, and the development of novel hole transport layer doping materials is still needed.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a fullerene derivative, a use thereof and an OLED device comprising the fullerene derivative. The fullerene derivative has a lower LUMO energy level and higher stability, can be used as a hole transport layer doping material of an OLED device, and is beneficial to reducing the working voltage of the OLED device, improving the luminous efficiency and prolonging the service life of the device.

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

in a first aspect, the present invention provides a fullerene derivative having a structure represented by formula I below:

in the formula I, R₁、R₂Each independently selected from cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C4-C60 cycloalkenyl, substituted or unsubstituted C5-C60 cycloalkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C2-C60 alkenyloxy, substituted or unsubstituted C2-C60 alkynyloxy, R₃-S-、R₄-S-、R₅-any one of S-;

Y₁、Y₂、Y₃、Y₄each independently selected from cyano, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkylamino, substituted or unsubstituted C2-C60 alkenylamino, substituted or unsubstituted C2-C60 alkynylamino, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C2-C60 alkenyloxy, substituted or unsubstituted C2-C60 alkynyloxy, R₃-S-、R₄-S-、R₅-S-, substituted or unsubstituted C1-C60 boryl, substituted or unsubstituted C2-C60 borenyl, substituted or unsubstituted C2-C60 borynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C6-C60 aryloxy, R₆-any of S-, substituted or unsubstituted C6-C60 boraaryl;

R₃is substituted or unsubstituted C1-C60 alkyl, R₄Is substituted or unsubstituted C2-C60 alkenyl, R₅Is substituted or unsubstituted C2-C60 alkynyl, R₆Is a substituted or unsubstituted C6-C60 aryl group;

and R is₁、R₂、Y₁、Y₂、Y₃And Y₄At least one of which is an electron withdrawing group;

when the group contains a substituent, the substituent is a halogen atom or a cyano group;

n is an integer of 1 to 30.

In the above formula I

Represents a fullerene, which may be C60, C70, or other species of fullerene known in the art.

The fullerene derivative has a stable structure, a high melting point and a certain electron-withdrawing ability, and is synthesized by carrying out addition reaction on the fullerene derivative and a group with the electron-withdrawing ability. The fullerene derivative has a lower LUMO energy level and a better electron receiving capacity, can be used as a hole transport layer doping material of an OLED, receives electrons on the HOMO energy level of the hole transport material, promotes the formation of holes, improves the combination rate of the holes and the electrons, and thus reduces the working voltage of an OLED device and improves the luminous efficiency; and because the fullerene derivative contains a fullerene structure, the fullerene derivative has higher structural stability and thermal stability, and is beneficial to prolonging the service life of the OLED device.

In the present invention, the C1-C60 alkyl group may be an alkyl group such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, or C60.

The C2-C60 alkenyl group may be an alkenyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C2-C60 alkynyl group may be an alkynyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C3-C60 cycloalkyl group may be a cycloalkyl group of C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, or C60, and the like.

The C4-C60 cycloalkenyl group can be C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60 or the like cycloalkenyl group.

The C5-C60 cycloalkynyl group may be a cycloalkynyl group of C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C1-C60 alkoxy group may be an alkoxy group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C2-C60 alkenyloxy group may be an alkenyloxy group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60 or the like.

The C2-C60 alkynyloxy can be C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60.

The C1-C60 alkylamino group may be an alkylamino group such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60.

The C2-C60 enamine group may be an enamine group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60.

The C2-C60 alkynylamine group can be an alkynylamine group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60.

The C1-C60 boryl group may be a boryl group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C2-C60 borenyl group may be a borenyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C2-C60 boronyl group may be a boronyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C6-C60 aryl group may be an aryl group of C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60, and the like.

The heteroaryl group of C5-C60 may be a heteroaryl group of C5, C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55, C60, or the like.

The C6-C60 arylamine group may be an arylamine group of C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.

The C6-C60 aryloxy group may be an aryloxy group of C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60, and the like.

The C6-C60 boron aryl group can be C6, C7, C8, C9, C10, C12, C15, C18, C20, C25, C30, C35, C40, C45, C50, C55 or C60 boron aryl group and the like.

As a preferred embodiment of the present invention, in formula I, R₁、R₂Each independently selected from any one of cyano, substituted or substituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl and substituted or unsubstituted C1-C10 alkoxy.

Preferably, R₁、R₂Each independently selected from any one of cyano, unsubstituted or fluorine substituted C1-C5 alkyl, and unsubstituted or fluorine substituted C1-C5 alkoxy.

As a preferred embodiment of the present invention, in formula I, Y₁、Y₂、Y₃、Y₄Each independently selected from any one of cyano, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C6-C12 arylamine and substituted or unsubstituted C6-C12 aryloxy.

Preferably, the first and second electrodes are formed of a metal,Y₁、Y₂、Y₃、Y₄each independently is a cyano group,

Wherein the dotted line represents the attachment position of the group.

In the formula I, n is an integer of 1 to 4.

As a preferred embodiment of the present invention, in formula I, R₁、R₂Each independently selected from any one of unsubstituted or fluorine-substituted C1-C5 alkyl and unsubstituted or fluorine-substituted C1-C5 alkoxy;

Y₁、Y₂、Y₃、Y₄each independently is a cyano group,

Wherein the dotted line represents the attachment position of the group;

n is an integer of 1 to 4.

In a preferred embodiment of the present invention, the fullerene derivative is selected from any one of the following compounds 1-n to 19-n:

wherein n is 1, 2,3 or 4.

N in the number of the compound is the same as n in the structural formula, and for example, when n is 2 in the structural formula of the compound 1-n, the compound is numbered 1-2; a compound numbered 2-3 wherein n-3.

In a second aspect, the present invention provides a use of the fullerene derivative according to the first aspect as a hole transport layer doping material for an OLED.

In a third aspect, the present invention provides an OLED device comprising a hole transport layer, and the hole transport layer comprises a hole transport material and a doping material;

the doping material is selected from one or a combination of at least two of the fullerene derivatives provided by the first aspect of the present invention.

As a preferred technical scheme of the invention, the OLED device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked.

As a preferred technical scheme of the invention, the mass percent of the doping material in the hole transport layer is 3-5%; for example, it may be 3%, 3.2%, 3.3%, 3.5%, 3.6%, 3.8%, 4%, 4.2%, 4.3%, 4.5%, 4.6%, 4.8%, 5%, etc.

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

the fullerene derivative provided by the invention has the LUMO energy level of-4.5-5.8 eV, has good electron receiving capacity, can be used as a hole transport layer doping material of an OLED, receives electrons on the HOMO energy level of the hole transport material, promotes the formation of holes, and improves the combination rate of the holes and the electrons, thereby reducing the working voltage of the OLED device and improving the luminous efficiency; the fullerene derivative provided by the invention contains a fullerene structure, has a thermal decomposition temperature of 310-380 ℃, has high structural stability and thermal stability, is not easy to decompose and damage in the OLED preparation and use processes, and is beneficial to prolonging the service life of an OLED device.

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 specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Preparation example 1

The compound 1-1 is prepared by the following synthetic route:

the specific synthesis steps are as follows:

(1) anhydrous tetrahydrofuran (500mL) was added to a 1000mL three-necked flask, sodium hydride (28.8g, 1.2mol) was added under ice bath conditions, malononitrile (66.1g, 1.0mol) was slowly added dropwise under nitrogen protection,

after the dropwise addition, stirring for 1 hour in an ice bath, dropwise adding acetyl chloride (78.5g, 1.0mol), stirring for 4 hours at room temperature after the dropwise addition is finished, slowly dropwise adding methanol (10mL), stirring for 10 minutes, adding water (500mL), extracting with ethyl acetate (300mL × 2), merging organic phases, washing once with water (200mL), washing once with saturated common salt water (100mL), drying with sodium sulfate, filtering, and spin-drying to obtain a crude product as a yellow solid (98.5g), and performing rapid column purification (eluent: petroleum ether/ethyl acetate ═ 10:1-4:1, and performing stepwise elution at different ratios) to obtain an off-white compound A (91.3g) with a yield of 84.5%;

(2) a1000 mL three-necked flask was charged with Compound A (54.0g, 0.50mol), p-toluenesulfonylhydrazide (116.4g, 0.625mol), and methanol (600mL), purged with nitrogen, and heated to 75 ℃ under reflux for 7 hours; after the reaction is finished, the reaction bottle is placed in a refrigerator to be cooled overnight, a yellow solid product is obtained by filtering, a filter cake is washed three times (100mL multiplied by 3) by cold methanol, and a compound B (99.3g) is obtained by drying, wherein the yield is 71.9%;

(3) adding the compound B (13.8g, 0.050mol) into a 1000mL three-neck flask, injecting redistilled pyridine (150mL) under the protection of nitrogen, stirring to dissolve, adding sodium methoxide (4.05g, 0.075mol), and then heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding a solution of fullerene C60(25.2g, 0.035mol) in o-dichlorobenzene (500mL), and continuing to react at 80 ℃ for 24 hours after the dropwise addition is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and after filter cakes are re-dispersed, column separation is carried out (toluene/petroleum ether is 1:1), so as to obtain 12.5g of crude product; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions and the solvent was removed, and dried under vacuum to give compound 1-1(7.8g, 24.7% yield).

Elemental analysis: c₇₀H₆N₄The theoretical value is as follows: c, 93.12; h,0.67; n, 6.21; measured value: c, 93.33; h, 0.69; and N, 5.98.

HRMS(ESI)m/z(M⁺): theoretical value: 902.0593, respectively; measured value: 902.0537.

preparation example 2

Compound 1-2

The preparation method comprises the following specific synthetic steps:

(1) adding the compound B (13.8g, 0.050mol) into a 1000mL three-neck flask, injecting redistilled pyridine (150mL) under the protection of nitrogen, stirring to dissolve, adding sodium methoxide (4.05g, 0.075mol), and then heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding a solution of fullerene C60(12.5g, 0.017mol) in o-dichlorobenzene (500mL), and continuing to react at 80 ℃ for 24 hours after the dropwise adding is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and a filter cake is subjected to column separation after being redispersed (toluene/petroleum ether is 1:1), so that 6.7g of a crude product is obtained; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions and the solvent was removed, and dried under vacuum to give compound 1-2(4.1g, 22.2% yield).

Elemental analysis: c₈₀H₁₂N₈The theoretical value is as follows: c, 88.56; h, 1.11; n, 10.33; measured value: c, 88.65; h, 1.13; n, 10.22.

HRMS(ESI)m/z(M⁺): theoretical value: 1084.1185, respectively; measured value: 1084.1235.

preparation example 3

The preparation of compound 16-1, the synthetic route is as follows:

the specific synthesis steps are as follows:

(1) anhydrous tetrahydrofuran (500mL) was added to a 1000mL three-necked flask, sodium hydride (14.4g, 0.60mol) was added under ice bath conditions, 4-cyanomethyl-2, 3,5, 6-tetrafluorobenzonitrile (compound C, 107.1g, 0.50mol) was slowly added dropwise under nitrogen, after completion of the dropwise addition, the mixture was stirred in ice bath for 1 hour, acetyl chloride (39.25g, 0.5mol) was added dropwise, the mixture was stirred at room temperature for 4 hours, methanol (10mL) was slowly added dropwise, after 10 minutes of stirring, water (500mL) was added, extraction was performed with ethyl acetate (300 mL. times.2), after the organic phases were combined, washing was performed once with water (200mL), saturated brine was washed once with water (100mL), sodium sulfate was dried, filtration was performed, and spin-dried to obtain a crude product as a yellow solid (123.7g), flash column purification was performed (eluent: petroleum ether/ethyl acetate 10:1-4:1, stepwise elution with different ratios), off-white compound D (112.3g) was obtained in 87.7% yield;

(2) a1000 mL three-necked flask was charged with Compound D (51.2g, 0.20mol), p-toluenesulfonylhydrazide (46.6g, 0.25mol), and methanol (600mL), purged with nitrogen, and heated to 75 ℃ under reflux for 7 hours; after the reaction is finished, the reaction bottle is placed in a refrigerator to be cooled overnight, a yellow solid product is obtained by filtering, a filter cake is washed three times (100mL multiplied by 3) by cold methanol, and a compound E (61.3g) is obtained by drying, wherein the yield is 72.3%;

(3) adding the compound B (11.0g and 0.040mol) and the compound E (17.0g and 0.040mol) into a 1000mL three-necked bottle under the protection of nitrogen, injecting redistilled pyridine (150mL), stirring to dissolve, adding sodium methoxide (5.4g and 0.10mol), and then heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding a solution of fullerene C60(20.2g, 0.028mol) in o-dichlorobenzene (400mL), and continuing to react at 80 ℃ for 24 hours after the dropwise addition is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and after filter cakes are re-dispersed, column separation is carried out (toluene/petroleum ether is 1:1), so as to obtain 11.3g of crude product; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions and the solvent was removed, and dried under vacuum to give compound 16-1(7.3g, 25.4% yield).

Elemental analysis: c₇₄H₆F₄N₄The theoretical value is as follows: c, 86.55; h, 0.59; n, 5.46; measured value: c, 86.59; h, 0.57; n, 5.46.

HRMS(ESI)m/z(M⁺): theoretical value: 1026.05286, respectively; measured value: 1026.0416.

preparation example 4

Compound 16-3

The preparation method comprises the following specific synthetic steps:

(1) adding compound B (24.9g, 0.090mol) and compound E (38.2g, 0.090mol) into a 1000mL three-necked flask under nitrogen protection, injecting redistilled pyridine (350mL), stirring to dissolve, adding sodium methoxide (11.7g, 0.216mol), and heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding an o-dichlorobenzene (300mL) solution of fullerene C60(21.6g, 0.030mol), and continuing to react at 80 ℃ for 24 hours after the dropwise adding is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and after filter cakes are re-dispersed, column separation is carried out (toluene/petroleum ether is 1:1), so as to obtain 13.2g of crude product; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions to remove the solvent, and dried under vacuum to give compound 16-3(9.7g, 18.9% yield).

Elemental analysis: c₁₀₈H₁₈F₁₂N₁₂The theoretical value is as follows: c, 75.80; h, 1.06; n, 9.82; measured value: c, 75.81; h, 1.04; and N, 9.81.

HRMS(ESI)m/z(M⁺): theoretical value: 1711.1619, respectively; measured value: 1711.2152.

preparation example 5

Compound 18-1

The preparation method comprises the following specific synthetic steps:

(1) adding the compound E (25.4g, 0.060mol) into a 1000mL three-necked bottle under the protection of nitrogen, injecting redistilled pyridine (250mL), stirring to dissolve, adding sodium methoxide (3.9g, 0.072mol), and then heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding an o-dichlorobenzene (300mL) solution of fullerene C60(21.6g, 0.03mol), and continuing to react at 80 ℃ for 24 hours after the dropwise adding is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and after filter cakes are re-dispersed, column separation is carried out (toluene/petroleum ether is 1:1), so as to obtain 15.1g of crude product; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions and the solvent was removed, and dried under vacuum to give compound 16-1(10.9g, 30.3% yield).

Elemental analysis: c₈₂H₈F₈N₄The theoretical value is as follows: c, 82.01; h, 0.67; n, 4.67; measured value: c, 82.03; h, 0.66; and N, 4.59.

HRMS(ESI)m/z(M⁺): theoretical value: 1200.0621, respectively; measured value: 1200.0561.

preparation example 6

Compound 18-4The preparation method comprises the following specific synthetic steps:

(1) adding compound E (33.9g, 0.080mol) into a 1000mL three-neck flask under the protection of nitrogen, injecting redistilled pyridine (350mL), stirring to dissolve, adding sodium methoxide (5.2g, 0.096mol), and then heating to 80 ℃; stirring the reaction system at 80 ℃ for 10 minutes, then dropwise adding an o-dichlorobenzene (100mL) solution of fullerene C60(7.2g, 0.01mol), and continuing to react at 80 ℃ for 24 hours after the dropwise adding is finished; after the reaction, the reaction solution is naturally cooled to room temperature, then the reaction solution is poured into methanol for standing for 4 hours, then the reaction solution is filtered, and a filter cake is subjected to column separation after being redispersed (toluene/petroleum ether is 1:1), so that 6.9g of a crude product is obtained; the crude product was dissolved in chloroform, filtered through a 0.20 μm Polytetrafluoroethylene (PTFE) filter membrane, passed through a gel exclusion volume chromatography column (Bio-Rad Bio-Beads S-X1, chloroform as eluent) in small portions and the solvent was removed, and dried under vacuum to give compound 16-1(4.8g, 18.3% yield).

Elemental analysis: c₁₄₉H₃₀F₃₁N₁₅The theoretical value is as follows: c, 68.33; h, 1.15; f, 22.49; n, 8.02; measured value: c, 68.22; h, 1.21; and N, 8.12.

HRMS(ESI)m/z(M⁺): theoretical value: 2619.23806, respectively; measured value: 2619.30543.

thermal decomposition temperature test:

the compound synthesized in the above preparation example was subjected to thermal decomposition temperature measurement using a thermogravimetric analyzer (TGA) in the range of 25 to 600 ℃, at a temperature rise rate of 10 ℃/min, and the temperature at which weight loss is 0.5% in a nitrogen atmosphere was defined as the decomposition temperature (T)_d)。

LUMO energy level test:

the LUMO energy level and the energy band width of the compound synthesized in the above preparation example were measured using Cyclic Voltammetry (CV) using an electrochemical workstation. Taking a platinum wire (Pt) as a counter electrode, taking silver/silver chloride (Ag/AgCl) as a reference electrode, testing in dichloromethane electrolyte containing 0.1mol/L tetrabutylammonium hexafluorophosphate under the nitrogen atmosphere at a scanning rate of 100mV/s, carrying out potential calibration with ferrocene, setting the absolute energy level of the potential of the ferrocene under the vacuum state to be-4.8 eV, and calculating the LUMO energy level according to the following formula:

wherein the content of the first and second substances,

to reduce the voltage, E_Fc/Fc+Is the ferrocene reduction voltage. And calculating to obtain the HOMO value according to the LUMO energy level and the energy band width.

The results of the above tests are shown in table 1 below:

TABLE 1

The results in table 1 show that the fullerene derivative provided by the invention has a high thermal decomposition temperature, is not easy to decompose and damage in the preparation process of an OLED device, and ensures that the device has good thermal stability; the LUMO energy level of the compounds is low (-4.5-5.8 eV), and the compounds can be matched with common hole transport materials, thereby being beneficial to promoting the generation of holes, improving the hole concentration of a hole transport layer, improving the combination rate of electrons and holes, reducing the working voltage of an OLED device and improving the luminous efficiency of the OLED device.