阅读说明：本技术 基于卤代芳胺类的新型空穴传输材料及其制备方法与应用 (Novel hole transport material based on halogenated arylamine and preparation method and application thereof ) 是由 李战峰 郭珊珊 刘宝友 张晓晔 焦正旭 田跃 田碧凝 于 2021-10-29 设计创作，主要内容包括：本发明属于有机光电功能材料技术领域；目前使用最多的空穴传输材料需要使用掺杂剂来提高导电性和空穴迁移率,导致使用掺杂剂使器件不稳定并且增加了成本,甲氧基会导致更高的最高占据分子轨道水平和较低的玻璃转变温度,降低开路电压和器件稳定性,本发明提供一种基于卤代芳胺类的新型空穴传输材料及其制备方法与应用,新型空穴传输材料含有卤取代芳胺基的分子结构,通过Buchwald偶联反应或Suzuki偶联反应得到新型空穴传输材料,在钙钛矿太阳能电池、有机场效应晶体管、有机电致发光器件、光催化制氢和有机光伏太阳能电池领域的应用,原材料成本低,合成方法简单方便,空穴传输材料性能较好。(The invention belongs to the technical field of organic photoelectric functional materials; the invention provides a novel hole transport material based on halogenated arylamine and a preparation method and application thereof, wherein the novel hole transport material contains a molecular structure with halogen substituted arylamine groups, and the novel hole transport material is obtained through Buchwald coupling reaction or Suzuki coupling reaction and is applied to the fields of perovskite solar cells, organic field effect transistors, organic electroluminescent devices, photocatalytic hydrogen production and organic photovoltaic solar cells, the cost of raw materials is low, the synthesis method is simple and convenient, and the performance of the hole transport material is better.)

1. A novel hole transport material based on halogenated aromatic amines, characterized in that: the novel hole transport material contains a molecular structure of halogen substituted arylamine, and has the following molecular structural formula:

in the molecular formula, X, Y1, Y1', Y2, Y2', Z1, Z1', Z2 and Z2' are hydrogen, fluorine, chlorine, bromine or trifluoromethyl; pi is an aryl, aryl derivative, oligothienyl, or oligothienyl derivative; r is spirobifluorene, spiro [ fluorene-9, 9 '-xanthene ], pyrene, bispirocyclic, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenylene, bithiophenepyrrole, dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorenediamine, tetraphenylbutadiene, bisphenylene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatripolyindene, thiophene or anthracene, or spirobifluorene, spiro [ fluorene-9, 9' -xanthene ], pyrene, bisphenocyclo, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenoethylene, bithiophene pyrrole, pyrene, bis (thiophene), Derivatives of dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorene diamine, tetraphenylbutadiene, bisspiroalkene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatriindene, thiophene, anthracene.

2. A novel hole transport material based on halogenated aromatic amines according to claim 1 characterized in that: the hydrogen, fluorine, chlorine, bromine or trifluoromethyl are substituted in the ortho, meta and para positions of the phenyl ring, the number of substituents being 1,2, 3, 4 or 5.

3. A process for the preparation of novel hole transport materials based on halogenated aromatic amines, as claimed in claim 1, characterized in that: the novel hole transport material is obtained through Buchwald coupling reaction or Suzuki coupling reaction.

4. A process for the preparation of novel hole transport materials based on halogenated aromatic amines according to claim 3, characterized in that: the Buchwald coupling reaction steps are as follows: under the nitrogen atmosphere, in the presence of a catalyst tris (Biya Bian acetone) dipalladium and tri-tert-butylphosphine, 2 mol/L of K₂CO₃In the solution, the bromo-central nucleus reacts with the halogenated aryl amino group to synthesize the halogenated aryl amine hole transport main body material.

5. A process for the preparation of novel hole transport materials based on halogenated aromatic amines according to claim 3, characterized in that: under the nitrogen atmosphere of Suzuki coupling reaction, under the existence of catalyst tris (Bian acetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, the intermediate bromination product and halogenated arylamine undergo Suzuki coupling reaction to synthesize the halogenated arylamine hole transport main body material.

6. The use of a novel hole transport material based on a halogenated aromatic amine according to claim 1, which is prepared by the method according to claims 2 to 5, wherein the method comprises the following steps: the novel hole transport material is applied to the fields of perovskite solar cells, organic field effect transistors, organic electroluminescent devices, photocatalytic hydrogen production and organic photovoltaic solar cells.

Technical Field

The invention relates to an organic photoelectric functional material technology, in particular to a novel hole transport material based on halogenated arylamine and a preparation method and application thereof.

Background

Perovskite Solar Cells (PSCs) are widely studied for their low cost, ease of fabrication and high Photoelectric Conversion Efficiency (PCE), currently being comparable to traditional silicon-based solar cells (Nature 2021, 592, 381).

The perovskite solar cell is composed of five parts, namely a transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode. The hole transport layer is used as an all-solid-state electrolyte, can be perfectly combined with a perovskite energy band structure, and plays a key role in improving the stability and the efficiency of the perovskite battery (Sci. Rep. 2012, 2, 591). An ideal hole transport layer should have high hole transport efficiency, high thermodynamic stability, good solubility and film-forming properties, while having a certain hydrophobicity to protect the perovskite absorption layer.

Compared with inorganic and polymer hole transport materials, the organic micromolecule hole transport material has the advantages of low cost, simple synthesis, determined molecular structure and the like, and is widely applied to PSCs (Small Methods 2018, 2, 1700280; Nano Energy 2018, 45 and 28). The most used hole transport material is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (spiro-OMeTAD) at present, but since spiro-OMeTAD requires the use of a dopant to improve conductivity and hole mobility, the use of a dopant makes the device unstable and increases cost. In addition, methoxy groups generally lead to higher levels of highest occupied molecular orbitals and lower glass transition temperatures, which may lead to a reduction in open circuit voltage and device stability (j. mater. chem. a 2021, 9, 8598). In order to overcome the bottleneck of methoxyl group, it is necessary to develop a new hole transport material as a substitute for methoxyl arylamine hole transport materials. Therefore, the development of undoped small molecule hole transport materials which are easy to synthesize, energy level matched, and good in hole mobility and conductivity is the key to realizing high-efficiency stable and low-cost PSCs.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a novel hole transport material based on halogenated arylamine and a preparation method and application thereof.

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

a novel hole transport material based on halogenated arylamine, which contains a molecular structure of halogen substituted arylamine group, has the following molecular structural formula:

in the molecular formula, X, Y1, Y1', Y2, Y2', Z1, Z1', Z2 and Z2' are hydrogen, fluorine, chlorine, bromine or trifluoromethyl; pi is an aryl, aryl derivative, oligothienyl, or oligothienyl derivative; r is spirobifluorene, spiro [ fluorene-9, 9 '-xanthene ], pyrene, bispirocyclic, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenylene, bithiophenepyrrole, dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorenediamine, tetraphenylbutadiene, bisphenylene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatripolyindene, thiophene or anthracene, or spirobifluorene, spiro [ fluorene-9, 9' -xanthene ], pyrene, bisphenocyclo, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenoethylene, bithiophene pyrrole, pyrene, bis (thiophene), Derivatives of dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorene diamine, tetraphenylbutadiene, bisspiroalkene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatriindene, thiophene, anthracene.

Further, hydrogen, fluorine, chlorine, bromine or trifluoromethyl are substituted at the ortho-, meta-and para-positions of the benzene ring, and the number of the substituents is 1,2, 3, 4 or 5.

The preparation method of the novel hole transport material based on the halogenated arylamine obtains the novel hole transport material through Buchwald coupling reaction or Suzuki coupling reaction.

Further, the Buchwald coupling reaction steps are as follows: under the nitrogen atmosphere, in the presence of a catalyst tris (Biya Bian acetone) dipalladium and tri-tert-butylphosphine, 2 mol/L of K₂CO₃In the solution, the bromo-central nucleus reacts with the halogenated aryl amino group to synthesize the halogenated aryl amine hole transport main body material.

Further, under the nitrogen atmosphere of Suzuki coupling reaction, under the existence of catalyst tris (Bian acetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, the intermediate bromination product and halogenated arylamine undergo Suzuki coupling reaction to synthesize the halogenated arylamine hole transport main body material.

The novel hole transport material is prepared by the method, and is applied to the fields of perovskite solar cells, organic field effect transistors, organic electroluminescent devices, photocatalytic hydrogen production and organic photovoltaic solar cells.

In conclusion, the invention has the following beneficial effects:

the novel hole transport material has the advantages of low cost, simple synthetic route, high yield, easy purification and great contribution to industrial production; the preparation method disclosed by the invention has the advantages that the cost of raw materials is low, the synthesis method is simple and convenient, and the synthesized hole transport material is proved to have better performance through photophysical property tests and electrochemical performance tests, so that the synthesized hole transport material can be applied to perovskite solar cells, organic field effect transistors, organic electroluminescent devices, photocatalytic hydrogen production and organic photovoltaic solar cells.

Drawings

FIG. 1 is a molecular structural diagram of a novel hole transport material of the present invention;

FIGS. 2, 4 and 6 are absorption curves of the halogenated aromatic amine hole transport main body material 1, the hole transport main body material 2 and the hole transport main body material 3 in a dichloromethane solution and a film according to the invention;

fig. 3, fig. 5 and fig. 7 are cyclic voltammograms of the halogenated arylamine hole transport host material 1, the hole transport host material 2 and the hole transport host material 3 in a dichloromethane solution.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.

As shown in fig. 1 to 7, the invention discloses a novel hole transport material based on halogenated arylamine, the novel hole transport material contains a molecular structure of halogen substituted arylamine group, and the novel hole transport material has the following molecular structural formula:

in the above formula, X, Y1, Y1', Y2, Y2', Z1, Z1', Z2 and Z2' are hydrogen, fluorine, chlorine, bromine or trifluoromethyl, and the hydrogen, fluorine, chlorine, bromine or trifluoromethyl are substituted at ortho, meta and para positions of a benzene ring, and the number of the substituents is 1,2, 3, 4 or 5; pi is an aryl, aryl derivative, oligothienyl, or oligothienyl derivative; r is spirobifluorene, spiro [ fluorene-9, 9 '-xanthene ], pyrene, bispirocyclic, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenylene, bithiophenepyrrole, dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorenediamine, tetraphenylbutadiene, bisphenylene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatripolyindene, thiophene or anthracene, or spirobifluorene, spiro [ fluorene-9, 9' -xanthene ], pyrene, bisphenocyclo, spirocyclopentadithiophene, benzothiadiazole, arylamine, carbazole, benzodithiazole, pyridine, ethylenedioxythiophene, fluorene, trithiophene, indenothiophene, tetrathiophenoethylene, bithiophene pyrrole, pyrene, bis (thiophene), Derivatives of dibenzothiophene, tetraphenylethylene, spirocyclopentadithiophene fluorene, dioxolane ketal fluorene diamine, tetraphenylbutadiene, bisspiroalkene dibenzopropene, thiadiazolopyridine, phenothiazine, indolocarbazole, fluoranthene, enamine, triazatriindene, thiophene, anthracene.

The invention also discloses a preparation method of the novel hole transport material based on the halogenated arylamine, and the novel hole transport material is obtained through Buchwald coupling reaction or Suzuki coupling reaction.

The Buchwald coupling reaction procedure was as follows: under the nitrogen atmosphere, in the presence of a catalyst tris (Biya Bian acetone) dipalladium and tri-tert-butylphosphine, 2 mol/L of K₂CO₃In the solution, the bromo-central nucleus reacts with the halogenated aryl amino group to synthesize the halogenated aryl amine hole transport main body material.

Under the nitrogen atmosphere of Suzuki coupling reaction, under the existence of catalyst tris (Biya Bian acetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, the intermediate bromination product and halogenated arylamine undergo Suzuki coupling reaction to synthesize the halogenated arylamine hole transport main body material.

The novel hole transport material based on the halogenated arylamine is prepared based on the method, and the novel hole transport material is applied to the fields of perovskite solar cells, organic field effect transistors, organic electroluminescent devices, photocatalytic hydrogen production and organic photovoltaic solar cells.

Example 1:

synthesis of halogenated arylamine hole transport host material 1:

the molecular structure of the halogenated aromatic amine hole transport main body material 1 is as follows:

the synthesis steps are as follows:

a100 mL two-necked flask was charged with 4-fluorodiphenylamine (0.4 g, 2.137 mmol), 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene (0.31 g, 0.49 mmol), sodium tert-butoxide (0.28 g, 2.91 mmol), tris (dibenzylideneacetone) dipalladium (0.017 g, 0.02 mmol) and tri-tert-butylphosphine (0.06 g, 0.03 mmol) and mixed. Next, 15 mL of anhydrous toluene was added to the flask under a nitrogen atmosphere. The reaction mixture was heated to reflux under nitrogen at 110 ℃ for 36 hours. After cooling to room temperature, the reaction mixture was washed with ethyl acetate and brine, and anhydrous MgSO₄And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (ethyl acetate/petroleum ether = 1/15) to give 1 (0.32 g) as a pale yellow solid in 62% yield.¹H NMR (400 MHz, CDCl₃) δ 7.399 (s, 1H), 7.378 (s, 1H), 7.187 (s, 2H), 7.08 – 7.14 (q, 4H), 6.8 – 6.91 (m, 19H), 1.978 (s, 1H), 1.16 – 1.22 (q, 2H)。

Example 2:

synthesis of halogenated arylamine hole transport host material 2:

the molecular structure of the halogenated aromatic amine hole transport main body material 2 is as follows:

the synthesis steps are as follows:

a100 mL two-necked flask was charged with 4-chlorodiphenylamine (0.4 g, 1.964 mmol), 2,2',7,7' -tetrabromo-9, 9' -spirobifluorene (0.28 g, 0.45 mmol), sodium tert-butoxide (0.26 g, 2.68 mmol), tris (dibenzylideneacetone) dipalladium (0.016 g, 0.02 mmol) and tri-tert-butylphosphine (0.05 g, 0.03 mmol) and mixed. Next, 15 mL of anhydrous toluene was added to the flask under a nitrogen atmosphere. The reaction mixture was heated to reflux under nitrogen at 110 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was washed with ethyl acetate and brine, and anhydrous MgSO₄And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (ethyl acetate/petroleum ether = 1/15) to give 2 (0.27 g) as a pale yellow solid in 54% yield.¹H NMR (400 MHz, CDCl₃) δ 7.739 (s, 1H), 7.58 – 7.3 (m, 14H), 7.231–7.082 (t, 1H), 6.98 – 6.73 (d, 41H), 6.555 (s, 3H), 6.474 – 6.4 (d, 1H), 6.337 (s, 3H), 4.09 – 4.01 (d, 2H), 1.97 (s, 3H), 1.477 (s, 3H), 1.188 (s, 6H), 0.798 (s, 2H)。

Example 3:

synthesis of halogenated arylamine hole transport host material 3:

the molecular structure of the halogenated aromatic amine hole transport main material 3 is as follows:

the synthesis steps are as follows:

a100 mL two-necked flask was charged with 3-chlorodiphenylamine (0.4 g, 1.964 mmol), 4, 7-bis (4-bromophenyl) benzo [1,2,5 ]]Thiadiazole (0.2 g, 0.45 mmol), sodium tert-butoxide (0.26 g, 2.68 mmol), tris (dibenzylideneacetone) dipalladium (0.016 g, 0.02 mmol) and tri-tert-butylphosphine (0.05 g, 0.03 mmol) were combined. Next, 15 mL of anhydrous toluene was added to the flask under a nitrogen atmosphere. The reaction mixture was heated to reflux at 110 ℃ for 48 hours under nitrogen atmosphere. After cooling to room temperature, the reaction mixture was washed with ethyl acetate and brine, and anhydrous MgSO₄And (5) drying.After evaporation of the solvent, the residue was purified by column chromatography (dichloromethane/petroleum ether = 1/10) to give 3 (0.22 g) as a light yellow solid in 70% yield.¹H NMR (400 MHz, CDCl₃) δ 7.915 – 7.875 (m, 1H), 7.75 – 7.7 (s, 1H), 7.52 – 7.46 (m, 1H)。

The synthesis of the intermediate comprises two steps:

a100 mL two-necked flask was charged with 4, 7-dibromo-2, 1, 3-benzothiadiazole (2 g, 6.8 mmol), phenylboronic acid (1.83 g, 14.9 mmol), and 2 mol/L K₂CO₃Solution (2.76 g, 20 mmol), tetrakis (triphenylphosphine) palladium (0.786 g, 0.68 mmol). Next, 15 mL of anhydrous toluene was added to the flask under a nitrogen atmosphere. The reaction mixture was heated to reflux under nitrogen at 110 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was washed with ethyl acetate and brine, and anhydrous MgSO₄And (5) drying. After evaporation of the solvent, the residue was recrystallized from dichloromethane to give 2,1, 3-benzothiadiazole-4, 7-diphenyl as an intermediate (1.7 g) in 86.7% yield.

The intermediate 2,1, 3-benzothiadiazole-4, 7-diphenyl (1.7 g, 5.9 mmol) was added to a three-necked flask equipped with magnetons under a nitrogen atmosphere,N,N3 mL of-dimethyl formamide, after diazosulfide-4, 7-diphenyl is completely dissolved, preparing a solution A with the concentration of 1.96 mol/L, and reducing the reaction system to 3 ℃ by using an ice water bath;N-bromosuccinimide (2.31 g, 12.97 mmol) dissolved in 20 mLN, NPreparation of a 0.65 mol/L solution B in dimethylformamideN, NThe amount of dimethylformamide used in relation to solution AN,N-dimethylformamide in a ratio of 20: 3. The reaction temperature was controlled to 3 ℃ and solution B was slowly added dropwise to solution A using a constant pressure funnel. After the completion of the dropwise addition, the reaction was carried out at room temperature for 10 hours. 200 mL of distilled water was poured in, a white precipitate appeared immediately, the white precipitate was filtered, washed with water three times, and dried at 100 ℃ to obtain a crude product. Recrystallizing with dichloromethane to purify the crude product to obtain high-purity 4, 7-bis (4-bromophenyl) benzo [1,2,5 ]]Thiadiazole 2.3 g, yield 87%.

And testing the photophysical and electrochemical properties of the synthesized halogenated arylamine hole transport material. As shown in FIGS. 2 to 7, the results show that: host materials 1,2, and 3 have HOMO energy levels similar to the spiro-omtad, matching the perovskite energy levels.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.