Synthesis and application of novel self-assembled monomolecular hole transport material with conjugated extended tail end

Abstract

The invention belongs to the technical field of perovskite solar cells, and provides synthesis and application of a novel self-assembled monomolecular hole transport material with conjugated extended tail ends. According to the self-assembled monomolecular hole transport material, a carbazole group is used as a terminal core, an aromatic ring is introduced to the terminal of carbazole to extend a conjugated structure, an alkyl chain is used as a connecting unit, phosphoric acid or acetic acid is used as an anchoring group, and the self-assembled monomolecular hole transport material with conjugated extended terminal is formed. And the stability, the hole transport property, the hole extraction capability and the interface passivation capability of the material are improved. Experiments show that the self-assembled monomolecular hole transport material has an HOMO energy level matched with a perovskite layer, and hole transport is facilitated. When the self-assembled monomolecular hole transport material disclosed by the invention is applied to a trans-perovskite solar cell with a band gap of 1.53 eV, the photoelectric conversion efficiency as high as 26.11% is obtained, and excellent device stability is shown.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite solar cells, and particularly to a self-assembled single-molecule hole transport material, a preparation method and application thereof, and a reverse perovskite solar cell. Background Art

[0002] In recent years, perovskite solar cells have developed rapidly as the third-generation photovoltaic power generation technology, and their certified efficiency has exceeded 26%, approaching that of the most advanced crystalline silicon solar cells. As an important component of perovskite solar cells, the performance of the hole transport material directly determines the photovoltaic performance of the device. Generally, perovskite solar cells are divided into two types in structure: normal and reverse. The commonly used hole transport material (spiro-OMeTAD) in the normal structure inevitably needs to be doped, which seriously affects the stability of the device. In contrast, the reverse structure has the advantages of simple preparation, small hysteresis effect, and low-temperature preparation, etc., and realizes the same photoelectric conversion efficiency as the normal structure, having good commercial application prospects. Due to the advantages of easy energy level adjustment, low cost, and low parasitic absorption of self-assembled monolayer materials, they have gradually replaced traditional polymer hole transport materials such as PTAA and PEDOT:PSS, etc., and are used in reverse perovskite solar cells and have attracted wide attention.

[0003] Carbazole derivatives have excellent optoelectronic properties, low price, good thermodynamic stability, and multiple substitution sites for modifying and adjusting energy levels, etc., making them the most widely used self-assembled single-molecule hole transport materials at present. However, these common self-assembled hole transport materials, such as MeO-2PACz, 2PACz, Me-4PACz, etc., are limited in their applications due to the mismatch of the hole extraction interface energy levels. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a self-assembled single-molecule hole transport material, a preparation method and application thereof, and a reverse perovskite solar cell. The self-assembled single-molecule hole transport material provided by the present invention has a low HOMO energy level, making it well-matched with perovskite, reducing the interfacial energy loss, and improving the stability of the reverse perovskite solar cell in which it participates in the assembly; and the self-assembled single-molecule hole transport material has an extended conjugation, which is expected to distort the molecular structure, inhibit molecular aggregation, and improve the uniformity of the self-assembled single-molecule hole transport material on the substrate, thereby further improving the stability of the reverse perovskite solar cell.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a self-assembled single-molecule hole transport material having the structure shown in Formula I:

[0007]

[0008] In formula I, the terminal group is selected from one of G1 to G4;

[0009]

[0010] Among G1 to G4, represents the connection site with the linking unit;

[0011] R in G1 to G4 is an extended conjugated group, independently selected from A1 to A54:

[0012]

[0013] The linking unit is selected from one of B1 to B3:

[0014]

[0015] The anchoring group is selected from one of C1 to C2:

[0016]

[0017] Preferably, when the terminal group is selected from G1, R is selected from A1, A2, A3, A5, A6, A7, A8, A9, A10, A12, A15, A17, A18, A23, A25, A26, A27, A28, A43, A44, A45, A46 or A47; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0018] Preferably, when the terminal group is selected from G2, R is selected from A1, A2, A3, A6, A18, A23, A25, A26, A30, A33, A34, A35, A36, A38 or A51; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0019] Preferably, when the terminal group is selected from G3, R is selected from A1, A2, A3 or A38; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0020] Preferably, when the terminal group is selected from G4, R is selected from A1, A2, A3, A6, A8, A10 or A35; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0021] Preferably, the self-assembled single-molecule hole transport material specifically has the following structure:

[0022]

[0023] The present invention also provides a preparation method of the self-assembled single-molecule hole transport material according to the above technical solution, comprising the following steps:

[0024] Mix the carbazole derivative, the first raw material, the palladium-based catalyst, the basic substance and the first solvent, and carry out the Suzuki coupling reaction under the protection of nitrogen to obtain the first intermediate;

[0025] The carbazole derivative has the following structure:

[0026]

[0027] The first raw material has the following structure:

[0028] The palladium-based catalyst is selected from [1,1-bis(diphenylphosphino)ferrocene] dichloropalladium and / or tetrakis(triphenylphosphine)palladium;

[0029] The basic substance is selected from potassium carbonate and / or sodium carbonate;

[0030] The first solvent is selected from one or more of tetrahydrofuran, N,N-dimethylformamide and toluene;

[0031] The first intermediate has the following structure:

[0032]

[0033] Mix the first intermediate, the linking unit compound, tetrabutylammonium bromide and the aqueous alkali solution, and carry out the first substitution reaction to obtain the second intermediate;

[0034] The linking unit compound includes 1,2-dibromoethane, 1,3-dibromopropane or 1,4-dibromobutane;

[0035] The second intermediate has the following structure:

[0036]

[0037] I. When the anchoring group is selected from C1, mix the second intermediate and triethyl phosphite, and reflux to carry out the second substitution reaction to obtain the third intermediate, and the third intermediate has the following structure;

[0038]

[0039] Mix the third intermediate, the hydrolyzing agent and the good solvent, and carry out the hydrolysis reaction to obtain the self-assembled single-molecule hole transport material; the self-assembled single-molecule hole transport material has the following structure:

[0040]

[0041] The hydrolyzing agent is selected from trimethylsilyl bromide;

[0042] II. When the anchoring group is selected from C2, the second intermediate, bromoalkyl carboxylate, and sodium hydroxide are mixed to carry out the third substitution reaction, and then reflux hydrolysis is carried out under the conditions of sodium hydroxide and tetrahydrofuran to obtain the self-assembled single-molecule hole transport material. The self-assembled single-molecule hole transport material has the following structure:

[0043]

[0044] The present invention also provides an application of the self-assembled single-molecule hole transport material described in the above technical solution in a perovskite solar cell.

[0045] The present invention also provides a perovskite solar cell, which successively includes, from bottom to top: a transparent conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a hole blocking layer, and a silver electrode;

[0046] The material of the hole transport layer is the self-assembled single-molecule hole transport material described in the above technical solution.

[0047] Preferably, the transparent conductive substrate is ITO or FTO; the material of the electron transport layer is PC 61 BM; the material of the hole blocking layer is BCP.

[0048] The present invention provides a self-assembled single-molecule hole transport material.

[0049] The self-assembled single-molecule hole transport material of the present invention selects a carbazole group as the terminal core, extends the conjugated structure by introducing an aromatic ring at the carbazole terminal, uses an alkyl chain as the linking unit, and designs and prepares a self-assembled single-molecule hole transport material with extended terminal conjugation using phosphoric acid or carboxylic acid as the anchoring group, improving the stability, solubility, hole transportability, hole extraction ability, and interface passivation ability of the material. Measuring the cyclic voltammetry curve shows that the self-assembled single-molecule hole transport material of the present invention has a HOMO energy level matching the perovskite layer, which is beneficial to hole transport. Applying the self-assembled single-molecule hole transport material of the present invention to a perovskite solar cell with a bandgap of 1.53 eV obtains a photoelectric conversion efficiency as high as 26.11% and exhibits excellent device stability.

[0050] The present invention also provides a preparation method of the self-assembled single-molecule hole transport material described in the above technical solution. The synthesis steps of the preparation method of the present invention are simple, the preparation cost is low, and large-scale commercial production can be achieved. Description of the Drawings

[0051] Figure 1 It is a schematic structural diagram of the perovskite solar cell provided by the present invention;

[0052] Figure 2 The UV-Vis absorption spectra of Me-4PACz, A1G1, A5G1, and A6G1 in Test Example 1;

[0053] Figure 3 The energy level diagrams of Me-4PACz, A1G1, A5G1, A6G1, and the perovskite light-absorbing layer in Test Example 1;

[0054] Figure 4 The photoelectric conversion efficiency diagrams of the inverted perovskite solar cells assembled with Me-4PACz, Ph-4PACz, A1G1, A5G1, A6G1, A38G3, A38G2, A1G2, and A1G3 in Test Example 2;

[0055] Figure 5 The aging performance test result diagrams of the inverted perovskite solar cells assembled with Me-4PACz, Ph-4PACz, A1G1, A5G1, and A6G1 in Test Example 2. Detailed implementation manners

[0056] The present invention provides a self-assembled single-molecule hole transport material having the structure shown in Formula I:

[0057]

[0058] In the present invention, in Formula I, the terminal group is selected from one of G1 to G4;

[0059]

[0060] Among G1 to G4, represents the connection site with the linking unit.

[0061] In the present invention, R in G1 to G4 is an extended conjugated group, independently selected from A1 to A54:

[0062]

[0063] In the present invention, in Formula I, the linking unit is selected from one of B1 to B3:

[0064]

[0065] In the present invention, in Formula I, the anchoring group is selected from one of C1 to C2:

[0066]

[0067] In a specific embodiment of the present invention, when the terminal group is selected from G1, R is selected from A1, A2, A3, A5, A6, A7, A8, A9, A10, A12, A15, A17, A18, A23, A25, A26, A27, A28, A43, A44, A45, A46 or A47; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0068] In a specific embodiment of the present invention, when the terminal group is selected from G2, R is selected from A1, A2, A3, A6, A18, A23, A25, A26, A30, A33, A34, A35, A36, A38 or A51; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0069] In a specific embodiment of the present invention, when the terminal group is selected from G3, R is selected from A1, A2, A3 or A38; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0070] In a specific embodiment of the present invention, when the terminal group is selected from G4, R is selected from A1, A2, A3, A6, A8, A10 or A35; the linking unit is selected from B1, and the anchoring group is selected from C1.

[0071] In a specific embodiment of the present invention, the self-assembled single-molecule hole transport material specifically has the following structure:

[0072]

[0073] The present invention also provides a preparation method of the self-assembled single-molecule hole transport material described in the above technical solution, including the following steps:

[0074] Mix a carbazole derivative, a first raw material, a palladium-based catalyst, a basic substance and a first solvent, and carry out a Suzuki coupling reaction under the protection of nitrogen to obtain a first intermediate;

[0075] The carbazole derivative has the following structure:

[0076]

[0077] The first raw material has the following structure:

[0078] The palladium-based catalyst is selected from [1,1-bis(diphenylphosphino)ferrocene] dichloropalladium and / or tetrakis(triphenylphosphine)palladium;

[0079] The basic substance is selected from potassium carbonate and / or sodium carbonate;

[0080] The first solvent is selected from one or more of tetrahydrofuran, N,N-dimethylformamide and toluene;

[0081] The first intermediate has the following structure:

[0082]

[0083] Mix the first intermediate, the linking unit compound, tetrabutylammonium bromide, and an aqueous alkali solution, and carry out a first substitution reaction to obtain a second intermediate;

[0084] The linking unit compound includes 1,2-dibromoethane, 1,3-dibromopropane, or 1,4-dibromobutane;

[0085] The second intermediate has the following structure:

[0086]

[0087] I. When the anchoring group is selected from C1, mix the second intermediate and triethyl phosphite, and reflux to carry out a second substitution reaction to obtain a third intermediate;

[0088] The third intermediate has the following structure;

[0089]

[0090] Mix the third intermediate, a hydrolyzing agent, and a good solvent, and carry out a hydrolysis reaction to obtain the self-assembled single-molecule hole transport material; the self-assembled single-molecule hole transport material has the following structure:

[0091]

[0092] The hydrolyzing agent is selected from trimethylsilyl bromide;

[0093] II. When the anchoring group is selected from C2, mix the second intermediate, bromoalkyl carboxylate, and sodium hydroxide, carry out a third substitution reaction, and then carry out reflux hydrolysis under the conditions of sodium hydroxide and tetrahydrofuran to obtain the self-assembled single-molecule hole transport material, and the self-assembled single-molecule hole transport material has the following structure:

[0094]

[0095] In the present invention, a carbazole derivative, a first raw material, a palladium-based catalyst, a basic substance, and a first solvent are mixed, and a Suzuki coupling reaction is carried out under the protection of nitrogen to obtain a first intermediate.

[0096] In the present invention, the molar ratio of the carbazole derivative to the first raw material is preferably 1:2 to 8, specifically preferably 1:2, 1:2.2, 1:3, 1:4, 1:5, 1:6, 1:7, or 1:8.

[0097] In the present invention, the molar ratio of the carbazole derivative to the palladium-based catalyst is preferably 20 to 40:1, and specifically preferably 30:1.

[0098] In the present invention, the molar ratio of the carbazole derivative to the basic substance is preferably 1 to 5:10 to 60, and specifically preferably 1:10.67.

[0099] In the present invention, the temperature of the Suzuki coupling reaction is preferably 70 to 90 °C, specifically preferably 70 °C, 75 °C, 80 °C, 85 °C or 90 °C; the heat preservation time is preferably 6 h to 24 h, specifically preferably 6 h, 12 h, 18 h or 24 h.

[0100] After the Suzuki coupling reaction, the present invention preferably further includes: allowing the obtained reaction solution to stand and cool to room temperature, pouring the cooled reaction material into a cold sodium sulfate solution, and the crude product precipitates in the form of a yellow solid, and after filtration, the crude product is obtained; drying the crude product to obtain a crude product; purifying the crude product by column chromatography (denoted as the first column chromatography purification) to obtain the first intermediate. In the present invention, the eluent for the first column chromatography purification is preferably a mixed solvent of dichloromethane and petroleum ether with a volume ratio of 1:1.

[0101] In the present invention, the reaction formula of the Suzuki coupling reaction is as follows:

[0102]

[0103] After obtaining the first intermediate, the present invention mixes the first intermediate, the linking unit compound, tetrabutylammonium bromide and an aqueous alkali solution, and performs a first substitution reaction to obtain a second intermediate.

[0104] In the present invention, the mass concentration of the aqueous alkali solution is preferably 2 to 70%; the alkali in the aqueous alkali solution is preferably an inorganic alkali, and the inorganic alkali preferably includes one or more of potassium hydroxide, sodium hydroxide and sodium carbonate.

[0105] In the present invention, the molar ratio of the first intermediate to the linking unit compound is preferably 1:5 to 15, specifically preferably 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15.

[0106] In the present invention, the molar ratio of the first intermediate to tetrabutylammonium bromide is preferably 1 to 5:0.5 to 6.

[0107] In the present invention, the molar ratio of the first intermediate to the alkali in the aqueous alkali solution is preferably 1 to 5:10 to 50.

[0108] In the present invention, the first substitution reaction is preferably carried out in an inert atmosphere. In the present invention, the temperature of the first substitution reaction is preferably 60-90 °C, specifically preferably 60 °C, 70 °C, 75 °C, 80 °C, 85 °C or 90 °C; the heat preservation time is preferably 6 h-24 h, specifically preferably 6 h, 12 h, 18 h or 24 h.

[0109] After the first substitution reaction is completed, the present invention preferably further includes allowing the obtained reaction liquid to stand and cool to room temperature, extracting the cooled reaction liquid, and collecting the organic layer; after the organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure to obtain a crude product; the crude product is purified by column chromatography (denoted as the second column chromatography purification) to obtain the second intermediate. In the present invention, the extraction reagent is preferably dichloromethane. In the present invention, the eluent for the column chromatography purification is preferably a mixed solvent of dichloromethane and petroleum ether with a volume ratio of 2:3.

[0110] In the present invention, the reaction formula of the first substitution reaction is as follows:

[0111]

[0112] After obtaining the second intermediate, if the anchoring group is selected from C1, the present invention mixes the second intermediate and triethyl phosphite and refluxes to carry out the second substitution reaction to obtain the third intermediate.

[0113] In the present invention, the molar ratio of the second intermediate to triethyl phosphite is preferably 1:10-30, specifically preferably 1:20.

[0114] The second substitution reaction is preferably carried out in an inert atmosphere. In the present invention, the temperature of the second substitution reaction is preferably 100-160 °C, specifically preferably 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C or 160 °C; the heat preservation time is preferably 8-24 h, specifically preferably 8 h, 12 h, 16 h, 18 h or 24 h.

[0115] After the second substitution reaction, the present invention preferably further includes: allowing the obtained reaction liquid to stand and cool to room temperature, then distilling off the solvent under reduced pressure to obtain a crude product; purifying the crude product by column chromatography (denoted as the third column chromatography purification) to obtain the third intermediate. In the present invention, the eluent for the third column chromatography purification is dichloromethane and ethyl acetate in sequence.

[0116] In the present invention, the reaction formula of the second substitution reaction is as follows:

[0117]

[0118] After obtaining the third intermediate, the present invention mixes the third intermediate, a hydrolysis agent, and a good solvent, and conducts a hydrolysis reaction to obtain the self-assembled single-molecule hole transport material.

[0119] In the present invention, the hydrolysis agent is selected from trimethylsilyl bromide.

[0120] In the present invention, the good solvent preferably includes one or more of dichloromethane, 1,4-dioxane, and chloroform.

[0121] In the present invention, the molar ratio of the third intermediate to the hydrolysis agent is preferably 1-5:4-40.

[0122] In the present invention, the mass ratio of the third intermediate to the good solvent is preferably 1-5:5-40.

[0123] In the present invention, the mixing of the third intermediate, the hydrolysis agent, and the good solvent preferably includes the following steps: under nitrogen, dissolving the third intermediate in the good solvent to obtain a third intermediate solution; dropping the hydrolysis agent into the third intermediate solution drop by drop.

[0124] In the present invention, the hydrolysis reaction is preferably carried out under an inert atmosphere and stirring. In the present invention, the temperature of the hydrolysis reaction is preferably 15-40 °C, specifically preferably 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, or 40 °C; the heat preservation time is preferably 6-24 h, specifically preferably 6 h, 12 h, 18 h, or 24 h.

[0125] After the hydrolysis reaction ends, the present invention preferably distills off the solvent in the obtained reaction stock solution under reduced pressure to obtain a solid residue; dissolving the solid residue in methanol, adding water, precipitating a solid, and after filtration, collecting the obtained solid and drying it to obtain the self-assembled single-molecule hole transport material.

[0126] In the present invention, the reaction formula of the hydrolysis reaction is as follows:

[0127]

[0128] In the present invention, when the anchoring group is selected from C2, the second intermediate, a bromoalkyl carboxylate, and sodium hydroxide are mixed to conduct a third substitution reaction, and then reflux hydrolysis is carried out under the conditions of sodium hydroxide and tetrahydrofuran to obtain the self-assembled single-molecule hole transport material.

[0129] In the present invention, the bromoalkyl carboxylate preferably has the following structure:

[0130]

[0131] In the present invention, the molar ratio of the second intermediate to the bromoalkyl carboxylic acid is preferably 1-2:5-15.

[0132] In the present invention, the molar ratio of the second intermediate to sodium hydroxide is preferably 1:5-10.

[0133] In the present invention, the temperature of the third substitution reaction is preferably room temperature, and the time is preferably 12-24 h.

[0134] In the present invention, the reaction formula of the third substitution reaction is as follows:

[0135]

[0136] In the present invention, during the reflux hydrolysis process, the dosage ratio of sodium hydroxide to tetrahydrofuran is preferably 4-10 mol:15 mL.

[0137] In the present invention, the time of the reflux hydrolysis is preferably 12-24 h.

[0138] After the reflux hydrolysis is completed, the present invention preferably further includes post-treatment, and the post-treatment preferably includes the following steps: after cooling to room temperature, the crude product is obtained by liquid separation, and then purified by column chromatography.

[0139] In the present invention, the reaction formula of the reflux hydrolysis is as follows:

[0140]

[0141] The present invention also provides an application of the self-assembled single-molecule hole transport material described in the above technical solution in a perovskite solar cell.

[0142] The present invention also provides a perovskite solar cell, which from bottom to top is successively: a transparent conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a hole blocking layer, and a silver electrode;

[0143] The material of the hole transport layer is the self-assembled single-molecule hole transport material described in the above technical solution.

[0144] Figure 1 It is a schematic structural diagram of the perovskite solar cell provided by the present invention. Next, in conjunction with Figure 1 The structure of the perovskite solar cell of the present invention will be described in detail.

[0145] The perovskite solar cell provided by the present invention includes a transparent conductive substrate, and the transparent conductive substrate is preferably ITO or FTO.

[0146] The inverted perovskite solar cell provided by the present invention includes a hole transport layer (SAM) disposed on the transparent conductive substrate, and the material of the hole transport layer is the self-assembled monolayer hole transport material described in the above technical solution. In the present invention, the thickness of the hole transport layer is preferably the thickness of a single molecular layer, and more preferably 1 to 4 nm.

[0147] The inverted perovskite solar cell provided by the present invention includes a perovskite light-absorbing layer (Perovskite) disposed on the hole transport layer, and the material of the perovskite light-absorbing layer preferably includes Cs 0.05 MA 0.1 FA 0.85 PbI3, one or more of FAPbI3 and MAPbI3. In the present invention, the thickness of the perovskite light-absorbing layer is preferably 500 to 900 nm.

[0148] The inverted perovskite solar cell provided by the present invention includes an electron transport layer disposed on the perovskite light-absorbing layer, and the material of the electron transport layer is preferably PC 61 BM. In the present invention, the thickness of the electron transport layer is preferably 10 to 50 nm.

[0149] The inverted perovskite solar cell provided by the present invention includes a hole blocking layer disposed on the electron transport layer, and the material of the hole blocking layer is preferably BCP. In the present invention, the thickness of the hole blocking layer is preferably 10 to 50 m.

[0150] The inverted perovskite solar cell provided by the present invention includes a silver electrode disposed on the hole blocking layer; the thickness of the silver electrode is preferably 50 to 100 nm.

[0151] The following describes in detail the self-assembled monolayer hole transport material provided by the present invention, its preparation method and application, and the inverted perovskite solar cell in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0152] Synthesis of Example 1 A1G1

[0153]

[0154] Synthesis of the first intermediate: 3,6-Dibromocarbazole (0.49 g, 1.5 mmol), 4,4,5,5-tetramethyl-2-(p-tolyl)-1,3,2-dioxaborolane (0.72 g, 3.3 mmol), tetrakis(triphenylphosphine)palladium (0.05 mmol, 60 mg), N,N-dimethylformamide (20 mL), and a solution of 2 mol / L potassium carbonate (16 mmol, 2.2 g) were added to a 100 mL two-necked round-bottom flask, protected with nitrogen, and reacted at 90 °C for 24 h. After cooling to room temperature, the reaction mixture was poured into 300 mL of cold sodium sulfate solution (prepared by dissolving 1 g of sodium sulfate in 300 mL of water). The crude product precipitated as a yellow solid, was filtered, dried, and then purified by column chromatography using dichloromethane / petroleum ether (1:1, v:v) as the eluent to obtain a white flocculent solid (0.37 g, 69%).

[0155] Synthesis of the second intermediate: The first intermediate (0.7 mmol, 0.27 g), 1,4-dibromobutane (7 mmol, 1.5 g), tetrabutylammonium bromide (0.12 mmol, 0.04 g), and 50% aqueous potassium hydroxide solution (5 eq, 3.5 mmol) were added to a flask. The reaction mixture was heated to 60 °C and stirred continuously under nitrogen overnight. After cooling to room temperature, the reaction mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure to obtain the crude product. The crude product was simply purified by column chromatography using dichloromethane / petroleum ether (2:3, v / v) to obtain a white solid (0.31 g, ~85%).

[0156] Synthesis of the third intermediate: The second intermediate (~0.6 mmol, 0.31 g) was dissolved in triethyl phosphite (20 eq, 12 mmol, 2 g). The reaction mixture was heated to 140 °C and stirred under nitrogen overnight. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography (successively using dichloromethane and ethyl acetate) to obtain a colorless oil (0.32 g, 92%).

[0157] Synthesis of A1G1: The third intermediate (0.56 mmol, 0.32 g) was dissolved in anhydrous dichloromethane (10 mL) under nitrogen, and then trimethylsilyl bromide (10 eq, 5.6 mmol) was added dropwise. The reaction mixture was stirred at room temperature overnight, and then the solvent was removed by distillation under reduced pressure. The solid residue was redissolved. Then, methanol (3 mL) was added and stirred for 3 h. Finally, distilled water (20 mL) was added dropwise until the solution became opaque. The product was filtered out and dried to obtain a white solid (0.25 g, 85%). The total yield of A1G1 was approximately 66%.

[0158] 1HNMR (600 MHz, DMSO) δ 8.57 (s, 2H), 7.83 - 7.58 (m, 8H), 7.27 (d, J = 6.7 Hz, 4H), 4.40 (d, J = 4.3 Hz, 2H), 2.34 (s, 6H), 1.87 (m, 2H), 1.54 (m, 4H). 13 CNMR (151 MHz, DMSO) δ 140.34, 138.63, 136.04, 131.55, 129.95, 126.91, 125.07, 123.41, 118.84, 110.26, 42.73, 36.26, 30.10, 28.34, 27.43, 21.12, 20.96. 31 PNMR (162 MHz, DMSO) δ 25.93.

[0159] Synthesis of Example 2 A2G1

[0160] The synthesis steps of A2G1 are as follows, and finally a white solid is obtained, and the yield of the first intermediate is 64%.

[0161]

[0162] 1 H NMR (600 MHz, DMSO) δ 8.55 (d, J = 1.5 Hz, 2H), 7.72 (dd, J = 8.5, 1.7 Hz, 2H), 7.63 (d, J = 8.5 Hz, 2H), 7.58 (s, 2H), 7.53 (d, J = 7.8 Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.09 (d, J = 7.5 Hz, 2H), 4.39 (t, J = 7.1 Hz, 2H), 2.36 (s, 6H), 1.91 - 1.76 (m, 2H), 1.50 (d, J = 8.5 Hz, 4H). 13 C NMR (151 MHz, DMSO) δ 139.63, 138.62, 136.50, 129.90, 127.33, 125.93, 125.70, 123.43, 122.40, 121.57, 117.30, 108.38, 40.89, 28.34, 28.24, 26.45, 25.54, 19.84, 19.10. 31 P NMR (324 MHz, DMSO) δ 26.50.

[0163] Synthesis of Example 3 A3G1

[0164] The synthesis steps of A3G1 are as follows, and finally a white solid is obtained, and the yield of the first intermediate is about 67%.

[0165]

[0166] 1 1H NMR (600 MHz, DMSO) δ 8.11 (s, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.36 (dd, J = 8.4, 1.6 Hz, 2H), 7.23 (m, 8H), 4.40 (t, J = 7.1 Hz, 2H), 2.24 (s, 6H), 1.92…1.82 (m, 2H), 1.61 - 1.50 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 140.76, 137.97, 133.62, 130.64, 128.82, 128.69, 125.60, 125.35, 124.41, 120.72, 119.44, 107.59, 40.92, 28.37, 28.27, 26.45, 25.54, 19.17, 19.07. 31 31P NMR (324 MHz, DMSO) δ 26.33.

[0167] Synthesis of Example 4 A5G1

[0168] The synthesis steps of A5G1 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 71%.

[0169]

[0170] 1 1H NMR (400 MHz, DMSO-d6) δ 8.50 (d, 2H), 7.79 - 7.47 (m, 8H), 6.99 (d, J = 8.7 Hz, 4H), 4.33 (s, 2H), 3.76 (s, 6H), 1.83 (s, 2H), 1.55 (s, 4H). 13 13C NMR (101 MHz, DMSO) δ 158.67, 140.05, 134.00, 131.33, 128.08, 124.90, 123.40, 118.53, 114.74, 110.13, 55.58, 42.80, 30.20, 29.01, 27.63, 21.25. 31 31P NMR (162 MHz, DMSO) δ 24.40.

[0171] Synthesis of Example 5 A6G1

[0172] The synthesis steps of A6G1 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 66%.

[0173]

[0174] 1 H NMR (400 MHz, DMSO) δ 8.57 (s, 2H), 7.68 (t, J = 9.2 Hz, 6H), 7.57 (d, J = 8.5 Hz, 2H), 7.32 (d, J = 8.3 Hz, 4H), 4.34 (s, 2H), 2.48 (s, 6H), 1.83 (s, 2H), 1.55 (s, 4H). 13 C NMR (101 MHz, DMSO) δ 140.41, 138.12, 136.56, 130.94, 127.48, 127.05, 125.00, 123.42, 118.82, 110.31, 42.82, 30.30, 30.16, 28.94, 27.63, 27.58, 26.81, 21.16, 15.37. 31 P NMR (162 MHz, DMSO) δ 24.61.

[0175] Synthesis of Example 6 A12G1

[0176] The synthesis steps of A12G1 are shown as follows, and finally a white solid is obtained. The yield of the first intermediate is about 67%.

[0177]

[0178] 1 H NMR (400 MHz, DMSO) δ 8.63 (d, 2H), 7.79 (d, 2H), 7.68 (d, J = 8.6 Hz, 2H), 7.55 (m, 4H), 7.20 (dd, 2H), 4.44 (t, J = 6.8 Hz, 2H), 1.99 - 1.83 (m, 2H), 1.60 (d, J = 8.3 Hz, 4H). 13 C NMR (101 MHz, DMSO) δ 145.23, 140.47, 128.85, 125.74, 124.76, 124.63, 123.05, 122.88, 118.14, 110.57, 42.79, 36.25, 30.21, 30.06, 28.66, 27.30, 20.98. 31 P NMR (162 MHz, DMSO) δ 25.95.

[0179] Synthesis of Example 7 A17G1

[0180] The synthesis steps of A17G1 are shown as follows, and finally a white solid is obtained. The yield of the first intermediate is about 66%.

[0181]

[0182] 1 1H NMR (600 MHz, DMSO) δ 8.33 (s, 2H), 8.00 (d, J = 8.1 Hz, 2H), 7.93 (m 4H), 7.81 (d, J = 8.4 Hz, 2H), 7.53 (m, 10H), 4.54 (t, J = 6.9 Hz, 2H), 2.09 - 1.96 (m, 2H), 1.74 - 1.58 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 140.90, 140.28, 133.99, 131.95, 131.27, 128.73, 128.38, 127.77, 127.54, 126.62, 126.22, 126.01, 122.80, 122.21, 109.76, 42.93, 30.30, 30.20, 28.46, 27.55, 21.11.

[0183] 31 31P NMR (324 MHz, DMSO) δ 26.20.

[0184] Synthesis of Example 8A18G1

[0185] The synthesis steps of A18G1 are as follows, and finally a white solid is obtained with a yield of about 71% for the first intermediate.

[0186]

[0187] 1 1H NMR (600 MHz, DMSO) δ 8.83 (d, J = 1.4 Hz, 2H), 8.35 (s, 2H), 8.08 - 7.99 (m, 6H), 7.95 (m, 4H), 7.76 (d, J = 8.6 Hz, 2H), 7.52 (m, 4H), 4.49 (t, J = 6.9 Hz, 2H), 1.92 (m, 2H), 1.57 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 138.78, 137.00, 132.18, 130.44, 129.55, 126.92, 126.57, 126.10, 124.91, 124.22, 124.11, 123.74, 123.18, 121.73, 117.72, 108.62, 40.93, 28.37, 28.27, 26.51, 25.60, 19.09. 31 31P NMR (324 MHz, DMSO) δ 26.26.

[0188] Synthesis of Example 9 A23G1

[0189] The synthesis steps of A23G1 are as follows, and finally a light green solid is obtained. The yield of the first intermediate is about 73%.

[0190]

[0191] 1 H NMR (600 MHz, DMSO) δ 8.78 (s, 2H), 8.28 (s, 2H), 8.05 - 7.85 (m, 8H), 7.75 (d, J = 8.5 Hz, 2H), 7.37 (s, 2H), 7.21 (m, 2H), 4.49 (s, 2H), 3.91 (s, 6H), 2.04 - 1.90 (m, 2H), 1.59 (m, 4H). 13 C NMR (151 MHz, DMSO) δ 156.54, 139.40, 135.58, 132.50, 130.54, 128.94, 128.45, 126.68, 125.32, 124.33, 123.92, 122.53, 118.29, 118.18, 109.36, 105.18, 54.60, 41.73, 29.19, 29.09, 27.26, 26.36, 19.92.

[0192] Synthesis of Example 10 A25G1

[0193] The synthesis steps of A25G1 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 69%.

[0194]

[0195] 1 H NMR (600 MHz, DMSO) δ 8.64 (s, 2H), 8.22 (d, J = 1.3 Hz, 2H), 8.12 (d, J = 8.5 Hz, 4H), 7.95 (dd, J = 8.4, 2.8 Hz, 2H), 7.61 (dd, J = 8.8, 1.7 Hz, 4H), 7.48 (t, J = 7.6 Hz, 6H), 7.37 (dd, J = 8.3, 7.1 Hz, 4H), 4.65 (m, 2H), 2.10 (m, 2H), 1.82 - 1.68 (m, 4H).

[0196] Synthesis of Example 11 A26G1

[0197] The synthesis steps of A26G1 are as follows, and finally a green solid is obtained. The yield of the first intermediate is about 65%.

[0198]

[0199] 1 H NMR(600 MHz, DMSO) δ 8.91 (s, 2H), 8.73–8.42 (m, 6H), 8.22 (d, J = 8.8 Hz, 2H), 8.06 (m, 8H), 7.80 (d, J = 8.3 Hz, 2H), 7.51 (s, 4H), 4.51 (s, 2H), 1.95 (s, 2H), 1.60 (s, 4H). 31 P NMR(324 MHz, DMSO) δ 25.54.

[0200] Synthesis of Example 12 A43G1

[0201] The synthesis steps of A43G1 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 54%.

[0202]

[0203] 1 H NMR(600 MHz, DMSO) δ 8.53 (s, 2H), 7.81…7.74 (m, 4H), 7.70 (m, 1.6 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.26 (t, J = 8.8 Hz, 4H), 4.39 (t, J = 7.0 Hz, 2H), 1.90…1.79 (m, 2H), 1.49 (m, 4H). 13 C NMR(151 MHz, DMSO) δ 161.58, 159.97, 139.39, 136.97, 129.62, 127.89, 124.23, 122.30, 118.16, 115.06, 114.92, 109.33, 41.69, 29.13, 29.02, 27.30, 26.39, 19.86.

[0204] Synthesis of Example 13 A47G1

[0205] The synthesis steps of A47G1 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 61%.

[0206]

[0207] 11H NMR (600 MHz, DMSO) δ 8.72 (s, 2H), 7.92 (d, J = 8.0 Hz, 4H), 7.84 (d, J = 8.3 Hz, 2H), 7.80…7.69 (m, 10H), 7.49 (t, J = 7.6 Hz, 4H), 7.38 (t, J = 7.3 Hz, 2H), 4.45 (s, 2H), 1.99…1.89 (m, 2H), 1.64 - 1.53 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 139.53, 139.43, 139.16, 137.51, 129.95, 128.37, 126.76, 126.50, 126.45, 125.88, 124.13, 122.43, 118.07, 109.36, 41.76, 29.18, 29.08, 27.46, 26.56, 19.99.

[0208] Synthesis of Example 14 A1G2

[0209] The synthesis steps of A1G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 65%.

[0210]

[0211] 1 1H NMR (600 MHz, DMSO) δ 8.35 (s, 1H), 8.14 (d, J = 7.5 Hz, 1H), 7.66 - 7.42 (m, 5H), 7.34 (s, 1H), 7.24…7.05 (m, 3H), 4.27 (s, 2H), 2.27 (s, 3H), 1.76 (s, 2H), 1.60 - 1.36 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 140.88, 139.83, 138.70, 135.97, 131.47, 129.92, 126.94, 126.30, 124.96, 123.12, 122.70, 120.97, 119.18, 118.48, 110.06, 109.85, 42.73, 30.32, 30.22, 28.97, 28.01, 21.12.

[0212] Synthesis of Example 15 A6G2

[0213] The synthesis steps of A6G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 65%.

[0214]

[0215] 1 1H NMR (600 MHz, DMSO) δ 8.38 (s, 1H), 8.16 (d, J = 7.5 Hz, 1H), 7.63 (d, J = 7.2 Hz, 3H), 7.51 (d, J = 6.9 Hz, 2H), 7.36 (s, 1H), 7.28 (d, J = 7.8 Hz, 2H), 7.12 (t, J = 6.9 Hz, 1H), 4.30 (s, 2H), 2.45 (s, 3H), 1.77 (s, 2H), 1.54 - 1.37 (m, 4H). 31 31P NMR (324 MHz, DMSO) δ 23.00.

[0216] Synthesis of Example 16 A18G2

[0217] The synthesis steps of A18G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 67%.

[0218]

[0219] 1 1H NMR (600 MHz, DMSO) δ 8.58 (d, 1H), 8.30 - 8.21 (m, 2H), 7.95 (q, J = 8.4 Hz, 3H), 7.87 (d, 2H), 7.66 (d, J = 8.5 Hz, 1H), 7.57 (d, J = 8.2 Hz, 1H), 7.50 - 7.38 (m, 3H), 7.17 (t, J = 7.4 Hz, 1H), 4.37 (t, J = 6.8 Hz, 2H), 1.88 - 1.77 (m, 2H), 1.49 (m, 4H). 13 13C NMR (201 MHz, DMSO) δ 139.91, 139.07, 137.92, 132.98, 131.22, 130.23, 127.72, 127.40, 126.89, 125.69, 125.34, 125.01, 124.98, 124.40, 124.05, 122.22, 121.72, 119.99, 118.28, 118.13, 109.21, 108.90, 41.63, 39.24, 39.14, 39.04, 38.93, 38.83, 38.72, 38.62, 29.14, 29.07, 27.37, 26.69, 20.02. 31 31P NMR (324 MHz, DMSO) δ 25.40.

[0220] Synthesis of Example 17 A23G2

[0221] The synthesis steps of A23G2 are as follows, and finally a light green solid is obtained. The yield of the first intermediate is about 68%.

[0222]

[0223] 1 H NMR(600MHz,DMSO)δ8.58(s,1H),8.31 - 8.16(m,2H),7.87(m,4H),7.63(m,2H),7.44(s,1H),7.34(s,1H),7.20(m,2H),4.39(s,2H),3.90(s,3H),1.86(s,2H),1.62 - 1.44(m,4H). 13 C NMR(151MHz,DMSO)δ156.48,139.83,138.81,135.60,132.42,130.37,128.92,128.39,126.64,125.30,124.18,123.90,122.16,121.68,119.92,118.22,117.76,109.06,108.78,105.11,54.56,41.70,29.32,29.23,27.97,27.96,27.02,20.38.

[0224] Synthesis of Example 18 A25G2

[0225] The synthesis steps of A25G2 are as follows, and finally a yellow solid is obtained. The yield of the first intermediate is about 58%.

[0226]

[0227] 1 H NMR(600MHz,DMSO)δ8.63(s,1H),8.15(d,1H),8.11(d,J=8.2Hz,3H),7.80(d,J=8.2Hz,1H),7.65(d,J=8.3Hz,1H),7.57(d,J=8.8Hz,2H),7.50 - 7.40(m,4H),7.37 - 7.31(m,2H),7.13(t,J=7.4Hz,1H),4.46(t,J=6.9Hz,2H),1.97 - 1.87(m,2H),1.70 - 1.53(m,4H). 13C NMR (201 MHz, DMSO) δ 140.98, 139.85, 137.94, 131.47, 130.74, 128.94, 128.81, 128.54, 127.06, 126.59, 126.47, 126.04, 125.68, 123.09, 122.78, 122.42, 121.07, 119.28, 109.92, 109.79, 42.81, 30.22, 30.15, 28.20, 27.52, 21.09. 31 P NMR (324 MHz, DMSO) δ 26.43.

[0228] Synthesis of Example 19 A26G2

[0229] The synthesis steps of A26G2 are as follows, and finally a yellow solid is obtained. The yield of the first intermediate is about 59%.

[0230]

[0231] 1 H NMR (600 MHz, DMSO) δ 8.69 (s, 1H), 8.61 (d, 2H), 8.45 (s, 1H), 8.30 (d, J = 7.6 Hz, 1H), 8.19 (d, J = 8.7 Hz, 1H), 8.09 (d, J = 2.8 Hz, 2H), 8.03 (d, J = 8.7 Hz, 1H), 7.96 (d, J = 7.9 Hz, 1H), 7.74 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.1 Hz, 1H), 7.54 - 7.45 (m, 3H), 7.24 (t, J = 7.3 Hz, 1H), 4.44 (s, 2H), 1.89 (d, J = 6.1 Hz, 2H), 1.61 - 1.50 (m, 4H). 13 C NMR (201 MHz, DMSO) δ 140.98, 140.17, 138.31, 132.24, 132.08, 131.59, 131.17, 130.66, 129.12, 128.58, 128.44, 126.51, 126.44, 126.24, 126.08, 125.82, 125.42, 124.67, 123.31, 122.79, 121.07, 119.38, 119.22, 110.31, 109.97, 42.74, 40.31, 40.21, 40.10, 40.00, 39.89, 39.79, 39.69, 30.27, 30.20, 21.20.

[0232] Synthesis of Example 20 A30G2

[0233] The synthesis steps of A30G2 are as follows, and finally a green solid is obtained. The yield of the first intermediate is about 53%.

[0234]

[0235] 1 H NMR(600MHz,DMSO)δ8.43(s,1H),8.24(d,J=7.7Hz,1H),7.77 - 7.71(m,3H),7.66(d,J=8.5Hz,1H),7.62(d,J=8.2Hz,1H),7.45(t,J=7.7Hz,1H),7.24 - 7.15(m,3H),4.82(q,J=8.9Hz,2H),4.41(t,J=7.0Hz,2H),1.93 - 1.82(m,2H),1.54(m,4H).

[0236] Synthesis of Example 21 A33G2

[0237] The synthesis steps of A33G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 67%.

[0238]

[0239] 1 H NMR(600MHz,DMSO)δ8.41(s,1H),8.20(d,J=7.7Hz,1H),7.68(d,J=8.3Hz,1H),7.64 - 7.52(m,4H),7.42(t,J=7.6Hz,1H),7.14(m,11H),7.06 - 7.01(m,6H),7.00 - 6.96(m,2H),4.37(t,J=7.0Hz,2H),1.94 - 1.76(m,2H),1.51(m,4H). 13 C NMR(201MHz,DMSO)δ142.71,140.61,139.85,139.74,139.70,138.93,138.36,131.28,130.66,130.17,130.09,129.68,127.33,127.23,126.01,125.21,123.84,122.07,121.66,119.94,118.20,117.57,113.01,109.02,108.82,41.59,29.07,28.99,27.31,26.63,19.99.

[0240] Synthesis of Example 22 A34G2

[0241] The synthesis steps of A34G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 55%. 。

[0242]

[0243] 1 H NMR (600 MHz, DMSO) δ 8.43 (s, 1H), 8.23 (d, J = 7.7 Hz, 1H), 7.78 - 7.69 (m, 1H), 7.62 (dd, J = 17.9, 8.4 Hz, 2H), 7.45 (t, J = 7.6 Hz, 1H), 7.34 (d, J = 1.9 Hz, 1H), 7.27 (dd, J = 8.3, 1.7 Hz, 1H), 7.20 (t, J = 7.4 Hz, 1H), 7.04 (t, J = 7.0 Hz, 1H), 4.40 (t, J = 6.9 Hz, 2H), 4.26 - 4.18 (m, 2H), 4.14 - 4.06 (m, 2H), 3.86 - 3.78 (m, 4H), 3.65 (d, J = 2.8 Hz, 8H), 1.97 - 1.78 (m, 2H), 1.53 (d, J = 9.5 Hz, 4H). 13 C NMR (151 MHz, DMSO) δ 149.40, 148.05, 140.91, 139.71, 134.95, 131.59, 126.29, 125.07, 123.09, 122.75, 121.01, 119.61, 119.15, 118.51, 114.80, 113.09, 110.00, 109.89, 70.90, 70.29, 69.41, 69.10, 42.63, 30.19, 30.09, 28.46, 27.55, 21.04. 31 P NMR (324 MHz, DMSO) δ 25.78.

[0244] Synthesis of Example 23 A35G2

[0245] The synthesis steps of A35G2 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 54%.

[0246]

[0247] 11H NMR (600 MHz, DMSO) δ 8.36 (s, 1H), 8.17 (d, J = 7.6 Hz, 1H), 7.78 - 7.49 (m, 3H), 7.37 (t, J = 7.2 Hz, 1H), 7.27 (s, 1H), 7.24 - 7.09 (m, 2H), 6.97 (d, J = 8.3 Hz, 1H), 4.33 (s, 2H), 4.18 (s, 2H), 4.07 (s, 2H), 3.81 - 3.71 (m, 4H), 3.60 - 3.55 (m, 4H), 3.54 - 3.47 (m, 8H), 1.79 (s, 2H), 1.45 (m, 4H). 13 13C NMR (151 MHz, DMSO) δ 146.49, 145.14, 138.41, 137.21, 132.23, 129.12, 123.79, 122.59, 120.60, 120.26, 118.52, 116.89, 116.63, 116.02, 111.60, 109.91, 107.49, 107.38, 67.86, 67.80, 66.83, 66.80, 66.20, 40.17, 27.74, 27.64, 26.14, 25.24, 18.64. 31 31P NMR (324 MHz, DMSO) δ 25.10.

[0248] Synthesis of Example 24 A38G2

[0249] The synthesis steps of A38G2 are shown below, and finally a white solid is obtained. The yield of the first intermediate is about 63%.

[0250]

[0251] 1 1H NMR (600 MHz, DMSO) δ 8.46 (d, J = 1.4 Hz, 1H), 8.23 (d, J = 7.7 Hz, 1H), 7.73 (dd, J = 22.8, 7.8 Hz, 3H), 7.62 (dd, J = 27.3, 8.3 Hz, 2H), 7.45 (dt, J = 20.8, 7.7 Hz, 3H), 7.32 (t, J = 7.3 Hz, 1H), 7.19 (t, J = 7.4 Hz, 1H), 4.38 (t, J = 6.9 Hz, 2H), 1.93 - 1.80 (m, 2H), 1.60 - 1.46 (m, 4H). 1313C NMR (151 MHz, DMSO) δ 141.61, 140.92, 140.00, 131.56, 129.33, 127.15, 126.87, 126.38, 125.18, 123.18, 122.73, 121.01, 119.27, 118.84, 110.12, 109.89, 42.72, 30.28, 30.18, 28.75, 27.83, 21.25. 31 31P NMR (324 MHz, DMSO) δ 24.41.

[0252] Synthesis of Example 25 A51G2

[0253] The synthesis steps of A51G2 are as follows, and finally a green solid is obtained. The yield of the first intermediate is about 69%.

[0254]

[0255] 1 1H NMR (600 MHz, DMSO) δ 8.59 (s, 3H), 8.33 (s, 5H), 7.92 (s, 1H), 7.76 (s, 1H), 7.65 (s, 3H), 7.44 (s, 3H), 7.23 (s, 1H), 4.46 (s, 2H), 1.93 (s, 3H), 1.58 (s, 4H).

[0256] Synthesis of Example 26 A1G3

[0257] The synthesis steps of A1G3 are as follows, and finally a white solid is obtained. The yield of the first intermediate is about 67%.

[0258]

[0259] 1 1H NMR (500 MHz, DMSO) δ 8.88 (d, J = 8.4 Hz, 1H), 8.75 (s, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.95 (q, J = 8.9 Hz, 2H), 7.85 - 7.63 (m, 5H), 7.48 (t, J = 7.4 Hz, 1H), 7.31 (d, J = 7.9 Hz, 2H), 4.56 (t, J = 6.9 Hz, 2H), 2.38 (s, 3H), 1.89 (dd, J = 13.7, 6.8 Hz, 2H), 1.69 - 1.40 (m, 4H). 1313C NMR (126 MHz, DMSO) δ 138.99, 138.75, 138.67, 136.10, 132.69, 129.96, 129.77, 129.58, 128.96, 127.72, 127.67, 127.39, 123.73, 123.60, 123.50, 123.30, 119.73, 114.31, 112.19, 110.89, 42.77, 36.24, 30.74, 30.62, 28.69, 27.59, 21.15. 31 31P NMR (202 MHz, DMSO) δ 24.98.

[0260] Synthesis of Example 27 A38G3:

[0261] The synthesis steps of A38G3 are shown below, and finally a white solid is obtained. The yield of the first intermediate is about 62%.

[0262]

[0263] 1 1H NMR (500 MHz, DMSO) δ 8.90 (d, J = 8.3 Hz, 1H), 8.79 (s, 1H), 8.08 (d, J = 7.9 Hz, 1H), 7.99 (q, J = 9.0 Hz, 2H), 7.88 (dd, J = 7.9, 2.7 Hz, 3H), 7.83 - 7.71 (m, 2H), 7.58 - 7.46 (m, 3H), 7.38 (t, J = 7.4 Hz, 1H), 4.61 (t, J = 7.1 Hz, 2H), 2.03 - 1.79 (m, 2H), 1.68 - 1.45 (m, 4H). 13 13C NMR (126 MHz, DMSO) δ 140.07, 137.07, 136.88, 130.93, 127.91, 127.74, 127.51, 127.14, 125.93, 125.84, 125.78, 125.14, 122.06, 121.77, 121.69, 121.50, 118.24, 112.49, 110.37, 109.14, 40.88, 28.81, 28.69, 26.55, 25.46, 19.07. 31 31P NMR (202 MHz, DMSO) δ 26.22.

[0264] Comparative Example

[0265] The difference between the comparative example and the examples lies only in the different compounds used in the hole transport layer. The compounds used in Comparative Example 1 are [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) and [4-(3,6-diphenyl-9H-carbazol-9-yl)butyl]phosphonic acid (Ph-4PACz), and their structural formulas are as follows:

[0266]

[0267] Test Example 1

[0268] The molecules to be tested were selected as: Me-4PACz, A1G1, A5G1, and A6G1

[0269] (1) Cyclic voltammogram of self-assembled single-molecule hole transport materials

[0270] The cyclic voltammogram of the material was measured using a CHI660D electrochemical analyzer (CH Instruments, Inc., China). A normal three-electrode system consisting of a platinum wire counter electrode, a platinum working electrode, and a calomel reference electrode was used. The redox potential of the material was tested in a solution of tetrabutylammonium hexafluorophosphate in N,N-dimethylformamide (0.1 mol / L), and the scanning rate was 100 mV s -1 . Ferrocene was used as an internal standard for calibration, and its oxidation potential was set to -5.1 eV relative to the zero vacuum level. According to the formula HOMO (eV) = -(E(ox) onset -E (ferrocene) onset +5.1), the HOMO energy levels of the obtained materials were calculated. The results were that the HOMO energy levels of Me-4PACz, A1G1, A2G1, A5G1, A6G1, A12G1, A18G1, A23G1, A25G1, A1G2, A18G2, A34G2, A51G2, A1G3, A38G3 were -5.25, -5.35, -5.34, -5.29, -5.29, -5.31, -5.32, -5.31, -5.33, -5.31, -5.32, -5.30, -5.35, -5.31, -5.30 eV respectively.

[0271] (2) Energy levels of self-assembled single-molecule hole transport materials

[0272] The material was dissolved in DMF (1×10 -4 M) to measure the ultraviolet-visible absorption spectrum of the solution. The ultraviolet-visible absorption spectrum was measured on a UV-vis spectrophotometer (UV-3600plus, Shimadzu Co., Ltd, Japan). The results are as Figure 2 shown, Figure 2UV-Vis absorption spectra of Me-4PACz, A1G1, A5G1, and A6G1. The wavelength (λ Figure 2 ) of the maximum absorption edge of the curve is obtained from max . According to the formula band gap E g = 1240 / λ max , the E g values of Me-4PACz, A1G1, A5G1, and A6G1 are 3.33 eV, 3.34 eV, 3.24 eV, and 3.46 eV, respectively.

[0273] Then, according to LUMO = HOMO + E g , the LUMO energy levels of the materials are obtained. The results are as shown in Figure 3 . Figure 3 is the energy level diagram of Me-4PACz, A1G1, A5G1, A6G1, and the perovskite light-absorbing layer. It can be seen from Figure 3 that extending the terminal conjugation can effectively reduce the HOMO of the material, making it better match the energy levels of the perovskite layer, which will help improve the open-circuit voltage of the perovskite solar cell and enhance the device performance.

[0274] Test Example 2

[0275] The molecules to be measured are selected as Me-4PACz, Ph-4PCAz, A1G1, A5G1, A6G1, A38G2, A1G2, A38G3, and A1G3.

[0276] According to Figure 1 , a reverse perovskite solar cell is assembled. Specifically, the reverse perovskite solar cell from bottom to top is as follows: 1. Transparent conductive substrate ITO or FTO; 2. Self-assembled single-molecule hole transport material; 3. Perovskite light-absorbing layer; 4. Electron transport layer (PC61BM); 5. Hole blocking layer (BCP); 6. Silver electrode.

[0277] (1) Performance of the reverse perovskite solar cell

[0278] The photoelectric conversion efficiency of the obtained reverse perovskite solar cell is as shown in Figure 4 and Table 1. Figure 4 is the photoelectric conversion efficiency diagram of the reverse perovskite solar cell assembled with Me-4PACz, Ph-4PACz, A1G1, A5G1, A6G1, A38G3, A38G2, A1G2, and A1G3.

[0279] Table 1 Parameters of the reverse perovskite solar cell

[0280]

[0281]

[0282] From Figure 4 Table 1, it can be seen that the photoelectric conversion efficiency of the self-assembled monolayer hole transport material with an extended terminal conjugate system prepared by the present invention is higher than that of Me-4PACz. Among them, due to the lower HOMO of A1G1, the voltage is significantly increased, and a photoelectric conversion efficiency as high as 26.11% is obtained.

[0283] (2) Stability test of inverted perovskite solar cells

[0284] Figure 5 Figure showing the aging performance test results of inverted perovskite solar cells assembled with Me-4PACz, Ph-4PACz, A1G1, A5G1, and A6G1. From Figure 5 it can be seen that: when tracking the photoelectric conversion efficiency of the device for 70 days at a relative humidity of about 10%, the results show that the stability of the device can also be effectively improved by extending the terminal conjugate of Me-4PACz.

[0285] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A self-assembled single molecule hole transport material, characterized in that: It has the structure shown in formula I: In formula I, the terminal group is selected from one of G1 to G4; In G1 to G4, represents the site of attachment to the attachment unit; R in G1-G4 is a group extending the conjugation, independently selected from A1-A54: The connection unit is selected from one of B1 to B3: The anchoring group is selected from one of C1 to C2:

2. The self-assembled monomolecular hole transport material according to claim 1, characterized in that: When the terminal group is selected from G1, R is selected from A1, A2, A3, A5, A6, A7, A8, A9, A10, A12, A15, A17, A18, A23, A25, A26, A27, A28, A43, A44, A45, A46 or A47; the connecting unit is selected from B1, and the anchoring group is selected from C1.

3. The self-assembled monomolecular hole transport material according to claim 1, characterized in that: When the terminal group is selected from G2, R is selected from A1, A2, A3, A6, A18, A23, A25, A26, A30, A33, A34, A35, A36, A38 or A51; the connecting unit is selected from B1, and the anchoring group is selected from C1.

4. The self-assembled monomolecular hole transport material according to claim 1, characterized in that: When the terminal group is selected from G3, R is selected from A1, A2, A3 or A38; the connecting unit is selected from B1, and the anchoring group is selected from C1.

5. The self-assembled monomolecular hole transport material according to claim 1, characterized in that: When the terminal group is selected from G4, R is selected from A1, A2, A3, A6, A8, A10 or A35; the connecting unit is selected from B1, and the anchoring group is selected from C1.

6. The self-assembled monomolecular hole transport material according to any one of claims 1 to 5, characterized in that: The self-assembled monomolecular hole transport material specifically has the following structure:

7. The method for preparing the self-assembled monomolecular hole transport material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The carbazole derivative, the first raw material, the palladium catalyst, the alkaline substance and the first solvent are mixed, and under the protection of nitrogen, a Suzuki coupling reaction is carried out to obtain a first intermediate; The carbazole derivative has the following structure: The first raw material has the following structure: R-Br, The palladium catalyst is selected from [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride and / or tetrakis(triphenylphosphine)palladium; The alkaline substance is selected from potassium carbonate and / or sodium carbonate; The first solvent is selected from one or more of tetrahydrofuran, N,N-dimethylformamide and toluene; The first intermediate has the following structure: The first intermediate, the linking unit compound, tetrabutylammonium bromide and an aqueous alkali solution are mixed to perform a first substitution reaction to obtain a second intermediate; The linking unit compound includes 1,2-dibromoethane, 1,3-dibromopropane or 1,4-dibromobutane; The second intermediate has the following structure: I. When the anchoring group is selected from C1, the second intermediate and triethyl phosphite are mixed and refluxed for a second substitution reaction to obtain a third intermediate, wherein the third intermediate has the following structure: The third intermediate, a hydrolyzing agent and a good solvent are mixed and subjected to a hydrolysis reaction to obtain the self-assembled monomolecular hole transport material; the self-assembled monomolecular hole transport material has the following structure: The hydrolyzing agent is selected from trimethylsilyl bromide; II. When the anchoring group is selected from C2, the second intermediate, the bromoalkyl carboxyl ester and sodium hydroxide are mixed to carry out a third substitution reaction, and then reflux hydrolyzed under the conditions of sodium hydroxide and tetrahydrofuran to obtain the self-assembled monomolecular hole transport material, and the self-assembled monomolecular hole transport material has the following structure:

8. Use of the self-assembled monomolecular hole transport material according to any one of claims 1 to 6 in an inverse perovskite solar cell.

9. An inverted perovskite solar cell, characterized in that: From bottom to top: transparent conductive substrate, hole transport layer, perovskite light absorption layer, electron transport layer, hole blocking layer and silver electrode; The material of the hole transport layer is the self-assembled monomolecular hole transport material according to any one of claims 1 to 6.

10. The inverted perovskite solar cell according to claim 9, characterized in that: The transparent conductive substrate is ITO or FTO; the material of the electron transport layer is PC 61 BM; the material of the hole blocking layer is BCP.

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