A planar triarylamine molecule and a method for synthesizing the same

Abstract

The application relates to a planar triarylamine molecule and a synthesis method thereof. A bridged triarylamine is selected as a molecular core, a terthiophene with high carrier mobility and passivation is selected as a peripheral group, a synthesized molecule is named as FTPA-T3, and a structural formula is as follows: the synthesis steps are few, the reaction condition is simple, the product yield is high, and the structure is stable. The synthesized FTPA-T3 dye has high molecular solubility and carrier mobility; the molecule has a good conjugated plane, and the hole transport efficiency is increased. Meanwhile, the compound has high thermal stability, and the thermal decomposition temperature is higher than 400 DEG C. The compound has potential application prospect as a hole transport material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hole transport material preparation; in particular to a planar triarylamine molecule and a synthesis method thereof. BACKGROUND

[0002] In recent years, perovskite solar cells (PSCs) are widely considered as a renewable technology that can replace traditional solar cells to address the challenges of global energy production and climate change. As an important component of PSCs, hole transport materials (HTMs) usually have the functions of smoothing the energy level between perovskite and electrode and preventing electron transport between perovskite and electrode [1] With the improvement of perovskite cell efficiency, people's research focus gradually shifts to the commercialization of perovskite, and the poor stability of perovskite cells is the most important factor restricting the commercialization of perovskite cells [2] .

[0003] The most successful hole transport material currently used in the laboratory is spiro-OMeTAD, and the high efficiency of perovskite cells of more than 23% is almost obtained by using this hole transport material [3] . But it is expensive, about ten times the price of gold, and more importantly, its intrinsic hole mobility is low (about 1x10 -5 cm -4 cm 2 v- 1 s -1 ), and the hole extraction and transport capacity must be improved by doping [4] . The most commonly used dopant is Li-TFSI and t-BP, but Li-TFSI itself has strong hygroscopicity and can accelerate the decomposition of perovskite; t-BP itself can destroy the perovskite structure, making the interface degrade, and these effects cannot be solved by encapsulation [5] .

[0004] Developing undoped hole transport materials has become an important solution to this problem, and the commonly used undoped hole transport materials are mainly divided into: inorganic hole transport materials [6] , organic polymer hole transport materials [7] and organic small molecule hole transport materials [8] . Because the types of inorganic materials are few, the solvents used are harmful to the perovskite layer; the production of polymer hole transport materials has poor repeatability and is expensive, and relatively less research is conducted. Organic small molecule hole transport materials can be well processed by solution, and their electronic properties can be finely customized through molecular design, showing great potential to replace traditional doped hole transport materials [9,10] . However, undoped hole transport materials generally require good thermal stability and are not easily degraded; the carrier mobility is generally greater than 1x10-5 cm -4 cm 2 v- 1 s -1 ; match the energy level of the functional layer; low price. However, the research on such high-performance materials is still relatively few. Therefore, it is necessary to develop high carrier mobility, high stability, and undoped small molecular hole transport materials.

[0005] Triarylamine has strong electron-donating property, low ionization potential, and can form stable ammonium ion radicals under the action of electric field, and has excellent hole transport performance; compared with triarylamine, bridged triarylamine has a more planar structure, better thermal stability, and high molecular conjugation, which is conducive to charge transport. Bridged triarylamine compounds have outstanding photoelectric properties. They have great development potential. The sulfur atom in thiophene has a lone pair of electrons that is often used to passivate perovskite surface defects. Terthiophene has high carrier mobility. Combining bridged triarylamine structure with terthiophene group provides a new way to develop hole transport materials with high hole mobility and high thermal stability.

[0006] REFERENCES

[0007] [1]Zhang L,Zhou X,Liu C,et al.AReview on Solution-processable Dopant-free Small Molecules as Hole-transporting Materials for Efficient Perovskite Solar Cells[J].Small Methods,2020,4(9):2000254.

[0008] [2]Yin X,Song Z,Li Z,et al.Toward Ideal Hole Transport Materials:aReview on Recent Progress in Dopant-free Hole Transport Materials forFabricating Efficient and Stable Perovskite Solar Cells[J].Energy&Environmental Science,2020,13(11):4057-4086.

[0009] [3] Chen J, Xu X, Tang X, et al. Highly Efficient and ThicknessInsensitive Inverted Triple-cation Perovskite Solar Cells Fabricated By Gas Pumping Method [J]. The Journal of Physical Chemistry Letters, 2021, 12(23): 5580-5586.

[0010] [4] Magomedov A, E, Rakstys K, et al. Pyridination of Hole Transporting Material in Perovskite Solar Cells Questions the Long-term Stability [J]. Journal of Materials Chemistry C, 2018, 6(33): 8874-8878.

[0011] [5] Huang C, Fu W, Li C, et al. Dopant-free Hole-transporting Material with a C 3H Symmetrical Truxene Core for Highly Efficient Perovskite Solar Cells [J]. Journal of the American Chemical Society, 2016, 138(8): 2528-2531.

[0012] [6] Calio L, Salado M, Kazim S, et al. A Generic Route of Hydrophobic Doping in Hole Transporting Material to Increase Longevity of Perovskite Solar Cells [J]. Joule, 2018, 2(9): 1800-1815.

[0013] [7] Zhang L, Liu C, Zhang J, et al. Intensive Exposure of Functional Rings of a Polymeric Hole-transporting Material Enables Efficient Perovskite Solar Cells [J]. Advanced Materials, 2018, 30(39): 1804028.

[0014] [8] Urieta-mora J, Garcia-benito I, Molina-ontoria A, et al. Hole Transporting Materials for Perovskite Solar Cells: a Chemical Approach [J]. Chemical Society Reviews, 2018, 47(23): 8541-8571.

[0015] [9] Zhang M, Wang G, Zhao D, et al. 3D hole-transporting materials based on coplanar quinolizino acridine for highly efficient perovskite solar cells [J]. Chemical Science, 2017, 8(11): 7807-7814.

[0016]

[10] Luponosov Y N, Solodukhin A N, Mannanov A L, et al. Effect of fused triphenylamine core in star-shaped donor-π-acceptor molecules on their physicochemical properties and performance in bulk heterojunction organic solar cells [J]. Dyes and Pigments, 2020, 177: 108260. SUMMARY

[0017] The application aims to improve the stability and intrinsic hole mobility of the hole transport material, and thus selects bridged triarylamine as a molecular core, and triphenylene as peripheral groups with high carrier mobility and passivation effect, and the synthesized molecule is named as FTPA-T3.

[0018] The application provides a non-doped hole transport material and a preparation method thereof, and more particularly to a preparation method of a hole transport material. The application introduces triphenylene groups on the structure of bridged triarylamine to obtain a hole transport material with double functions of passivating the surface defects of perovskite and high carrier mobility. The application has the characteristics of fewer synthesis steps, simple reaction conditions, higher product yield and stable structure. The synthesized FTPA-T3 dye has high molecular solubility and carrier mobility, and the molecule has good conjugated plane and can increase the carrier mobility and hole transport efficiency. Meanwhile, the compound has high thermal stability with a thermal decomposition temperature of 420 DEG C. The application has potential application prospect as a hole transport material.

[0019] The technical scheme of the application is as follows:

[0020] A planar triarylamine derivative hole transport material has the following structural formula:

[0021]

[0022] The preparation method of the planar triarylamine derivative hole transport material comprises the following steps:

[0023] In the first step, 2-aminobenzoic acid methyl ester and 2-iodobenzoic acid methyl ester are used as raw materials to obtain compound 1 through Ullmann reaction, and trimethyl 2,2',2"-nitroso tribenzoate has the following structural formula:

[0024]

[0025] In the second step, compound 1, p-bromomethylbenzene and n-butyllithium are subjected to electrophilic addition to obtain compound 2, namely nitrotris(phen-2,1-diyl))tris(di-p-tolylmethanol), which has the following structural formula:

[0026]

[0027] In the third step, compound 2 is refluxed in acetic acid and concentrated hydrochloric acid solution to obtain compound FTPA, which has the following structural formula:

[0028]

[0029] The fourth step, the compound FTPA-Br3: 2,6,10-tribromo-4,4,8,8,12,12-hexa-p-tolyl-8,12-dihydro-4H-benzo[9,1]quinolino[3,4,5,6,7-defg]acridine is obtained by bromination reaction of FTPA and NBS, and the structural formula is as follows:

[0030]

[0031] The fifth step, the compound 3 is obtained by electrophilic addition reaction of terthiophene and tributyltin chloride, and the structural formula is as follows:

[0032]

[0033] The sixth step, the target product FTPA-T3 is obtained by stille reaction of the compound 3 and FTPA-Br3.

[0034] The synthesis method of the compound 1 is that methyl 2-aminobenzoate and methyl o-iodobenzoate are dissolved in diphenyl ether solution, then anhydrous K2CO3, Cu and CuI are added together under nitrogen atmosphere, and the heating stirrer is adjusted to reflux heating for 48-56 h; wherein after the reaction is completed, the solution is cooled by standing, and the solid raw material is removed by filtration under reduced pressure to obtain a clear filtrate, then n-hexane is added to the filtrate, and after oscillation, the white crude product is generated by standing, and the solid is obtained by filtration under reduced pressure, then the crude product is separated by column chromatography on silica gel to obtain white solid as the compound 1.

[0035] The synthesis method of the compound 2 is that p-bromotoluene is dissolved in dry tetrahydrofuran under nitrogen atmosphere, n-butyllithium is dropped into the reaction system at-78℃, and stirring is carried out for 1-2 h; then the compound 1 is dissolved in dry tetrahydrofuran, and is dropped into the reaction system, and stirring reaction is carried out at room temperature for 10-12 h; after the reaction is completed, the reaction is quenched by dropping water, and the solvent is removed by rotary evaporator to obtain the compound 2.

[0036] The synthesis method of the compound FTPA is that the obtained compound 2 is dissolved in a mixed solution of boiling acetic acid and concentrated hydrochloric acid, and is refluxed for 3-4 h under heating; after the reaction is stopped, the reaction mixture is cooled, and is poured into an ice water bath, and the solid is collected by filtration under reduced pressure, and is washed twice with ethanol, and then is separated by column chromatography on silica gel, and is recrystallized with ethanol, and the white solid FTPA is obtained by filtration.

[0037] The synthesis method of the compound FTPA-Br3 is: dissolving FTPA in chloroform solution, adding N-bromosuccinimide at 0-4 DEG C, stirring the mixture at room temperature for 10-12 hours under nitrogen atmosphere, after the reaction is completed, filtering the reaction solution under reduced pressure, washing the filtrate with water for three times, extracting, drying, filtering under reduced pressure, taking the filtrate, and recrystallizing in ethanol to obtain white solid FTPA-Br3.

[0038] The synthesis method of the compound FTPA-T3 is: dissolving terthiophene in dry tetrahydrofuran under nitrogen atmosphere, reducing the temperature to-78 DEG C, slowly dropping n-butyllithium solution into the above reaction solution, stirring for 1-2 hours at-78 DEG C, then increasing the temperature to room temperature and stirring for 30-60 minutes, then reducing the temperature of the system to-78 DEG C again, slowly dropping tributyltin chloride into the solution and stirring for 1-2 hours, then increasing the temperature to room temperature and continuing to stir for 10-12 hours, after the reaction is completed, adding a small amount of water to quench the reaction, drying with anhydrous sodium sulfate, filtering the reaction solution under reduced pressure, concentrating the filtrate through a rotary evaporator to obtain oily liquid compound 3; adding compound FTPA-Br3, toluene and finally catalyst tetrakis(triphenylphosphine)palladium into the reaction bottle, sealing the device and replacing the air in the bottle with nitrogen, under nitrogen atmosphere, adding compound 3 into the reaction bottle, adjusting the reaction temperature to 100-110 DEG C, and reacting for 10-12 hours; after the reaction is completed, removing the solvent through a rotary evaporator, and then separating and purifying through a silica gel chromatographic column to obtain orange yellow solid FTPA-T3.

[0039] In the present application, the molar ratio of 2-aminobenzoic acid methyl ester, methyl o-iodobenzoate, anhydrous K2CO3, Cu and CuI is 1:2-3:1.8-2.2:4-5:1.8-2.2.

[0040] In the present application, the reaction molar ratio of compound 1, p-bromotoluene and n-butyllithium is 1:10-15:10-15; the volume ratio of acetic acid and concentrated hydrochloric acid is 10-12:1; and the reaction molar amount of FTPA and N-bromosuccinimide is 1:3-4.

[0041] In the present application, the reaction molar ratio of FTPA-Br3, tetrakis(triphenylphosphine)palladium, compound 3, n-butyllithium and tributyltin chloride is 1:0.04-0.1:3-3.3:3.6-4.2:3.6-4.2.

[0042] The hole transport material of the present application has the following structural formula:

[0043]

[0044] The Chinese name of FTPA-T3 is 2,6,10-tri([2,2':5',2"-terthiophen]-5-yl)-4,4,8,8,12,12-hexa-p-tolyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine. The English name is 2,6,10-tri([2,2':5',2"-terthiophen]-5-yl)-4,4,8,8,12,12-hexa-p-tolyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine.

[0045] The reaction equation is as follows:

[0046]

[0047] (1) copper powder, cuprous iodide, potassium carbonate, diphenyl ether, refluxing for 48-72h;

[0048] (2) p-bromotoluene, n-butyllithium, tetrahydrofuran, room temperature, 10-12h;

[0049] (3) acetic acid, concentrated hydrochloric acid, refluxing for 3-4h;

[0050] (4) N-bromosuccinimide, chloroform, room temperature, 10-12h;

[0051] (5) n-butyllithium, tetrahydrofuran, tributyltin chloride, room temperature, 10-12h;

[0052] (6) tetrakis(triphenylphosphine)palladium, toluene, refluxing for 10-12h.

[0053] The specific description is as follows:

[0054] (1) In the first step, 2-aminobenzoic acid methyl ester and 2-iodobenzoic acid methyl ester are used as raw materials, and compound 1 is obtained by Ullmann reaction; in the second step, compound 1, p-bromotoluene and n-butyllithium are used to carry out electrophilic addition to obtain compound 2; in the third step, compound 2 is refluxed in an acetic acid and concentrated hydrochloric acid solution to obtain compound FTPA; in the fourth step, FTPA and NBS are subjected to bromination to obtain compound FTPA-Br3; in the fifth step, terthiophene and tributyltin chloride are subjected to electrophilic addition to obtain compound 3; in the sixth step, compound 3 and FTPA-Br3 are subjected to stille reaction to obtain the target product FTPA-T3.

[0055] (2) The preparation method of the compound 1 is: methyl 2-aminobenzoate, methyl o-iodobenzoate are dissolved in a diphenyl ether solution, then anhydrous K2CO3, Cu, CuI are added together under a nitrogen atmosphere, and the heating stirrer is adjusted to reflux for 48-56 h. The molar ratio of methyl 2-aminobenzoate, methyl o-iodobenzoate, anhydrous K2CO3, Cu, CuI is 1:2-3:1.8-2.2:4-5:1.8-2.2. After the reaction is completed, the solution is allowed to stand and cool, and the solid raw materials are removed by vacuum filtration to obtain a clear filtrate. Then n-hexane is added to the filtrate, which is shaken and then allowed to stand, producing white crude products. The solid is obtained by vacuum filtration, and the crude products are separated by column chromatography on a silica gel column to obtain white solids as compound 1.

[0056]

[0057] (3) The preparation method of the compound 2 is: p-bromotoluene is dissolved in dry THF under a nitrogen atmosphere, the system is cooled to -78°C and stirred, and n-butyllithium is added dropwise into the reaction system, and stirred for 1-2 h. Then a dry THF solution of compound 1 is slowly added dropwise into the reaction system, and the system is stirred at room temperature for 10-12 h. After the reaction is completed, a small amount of water is added to quench the reaction, and the solvent is removed by a rotary evaporator. The reaction mixture is extracted with dichloromethane, washed with water three times, dried over Na2SO4, concentrated, and separated by chromatography to obtain compound 2. The molar ratio of compound 1, p-bromotoluene, and n-butyllithium is 1:10-15:10-15.

[0058]

[0059] (4) The preparation method of the compound FTPA is: compound 2 is dissolved in a boiling mixture of acetic acid and concentrated hydrochloric acid, and refluxed for 3-4 h under heating. After the reaction stops, the reaction mixture is cooled and poured into an ice water bath, and the solid is collected by vacuum filtration. The solid is washed twice with ethanol, and then separated by column chromatography on a silica gel column to obtain white solids. Preferably, the volume ratio of acetic acid to concentrated hydrochloric acid is 10-12:1.

[0060]

[0061] (5) The preparation method of the compound FTPA-Br3 is: FTPA is dissolved in a chloroform solution, and N-bromosuccinimide (NBS) is added at 0-4°C under a nitrogen atmosphere. The mixture is stirred at room temperature for 10-12 h, and then the reaction is completed. The reaction liquid is vacuum filtered, the filtrate is washed with water three times, extracted, dried, vacuum filtered, and then recrystallized from ethanol to obtain white solids. Preferably, the molar ratio of FTPA to NBS is 1:3-4.

[0062]

[0063] (6) The preparation method of the compound 3 is: under the atmosphere of nitrogen, triphenylene is dissolved in dry THF, the temperature is reduced to-78℃, the n-butyllithium solution is slowly added to the above reaction solution, and the reaction is stirred at-78℃ for 1-2h, and then the temperature is increased to room temperature and stirred for 30-60min, and then the temperature of the system is reduced to-78℃ again, the tributyltin chloride is slowly added to the solution and stirred for 1-2h, and then the temperature is increased to room temperature, and the stirring is continued for 10-12h, after the reaction is completed, a small amount of water is added to quench the reaction, anhydrous sodium sulfate is used for drying, the reaction solution is filtered under reduced pressure, the filtrate is concentrated by a rotary evaporator, and the oil liquid compound 3 is obtained; preferably, the molar ratio of triphenylene, n-butyllithium and tributyltin chloride is 1:1.2-1.4:1.2-1.4.

[0064]

[0065] (7) The preparation method of the hole transport material is: compound FTPA-Br3 is added to toluene, and then a catalyst tetrakis(triphenylphosphine)palladium is added, the device system is sealed, and the bottle is quickly replaced with nitrogen to replace the air in the bottle, under the atmosphere of nitrogen, the oil liquid compound 3 obtained in step 4 is injected into the reaction bottle with a needle, the reaction temperature is adjusted to reflux for 10-12h. After the reaction is completed, the reaction solution is concentrated by removing the solvent through a rotary evaporator, and then column chromatography silica gel chromatography column is used for separation and purification, and orange yellow solid FTPA-T3 is obtained. The molar ratio of FTPA-Br3, tetrakis(triphenylphosphine)palladium and compound 3 is 1:0.04-0.1:3-3.3.

[0066]

[0067] 1) Synthesis of compound FTPA-Br3

[0068]

[0069] The preparation method of the hole transport material of the present application comprises the following steps:

[0070] ①2-Aminobenzoic acid methyl ester and 2-iodobenzoic acid methyl ester are used as raw materials, and compound 1 is obtained through Ullmann reaction; ②Compound 1 is subjected to electrophilic addition through p-bromotoluene and n-butyllithium to obtain compound 2; ③Compound 2 is refluxed in acetic acid and concentrated hydrochloric acid solution to obtain compound FTPA; ④FTPA is subjected to bromination reaction with NBS to obtain compound FTPA-Br3.

[0071] The method of ① is: dissolving methyl 2-aminobenzoate and methyl o-iodobenzoate in diphenyl ether solution, then adding anhydrous K2CO3, Cu and Cul under nitrogen atmosphere, the molar ratio of methyl 2-aminobenzoate, methyl o-iodobenzoate, anhydrous K2CO3, Cu and Cul is 1:2-3:1.8-2.2:4-5:1.8-2.2, adjusting the reflux heating of the heating stirrer for 48-56 hours. After the reaction is completed, the solution is cooled by standing, and the solid raw materials are removed by vacuum filtration to obtain a clear filtrate. Then, n-hexane is added to the filtrate, shaken and then allowed to stand, producing white crude product. The solid is obtained by vacuum filtration, and the crude product is separated by column chromatography on silica gel to obtain white solid as compound 1.

[0072]

[0073] The method of ② is: dissolving compound 1 in dry THF under nitrogen atmosphere, dissolving p-bromotoluene in dry THF, stirring the system to -78℃, and dropping n-butyllithium into the reaction system, stirring for 1-2 hours; then slowly dropping the THF solution of compound 1 into the reaction system, and stirring at room temperature for 10-12 hours after rising to room temperature; after the reaction is completed, a small amount of water is added to quench the reaction, the solvent is removed by rotary evaporation, extracted with dichloromethane, washed with water three times, dried with Na2SO4, concentrated, and separated by chromatography to obtain compound 2; the reaction molar ratio of compound 1, p-bromotoluene and n-butyllithium is 1:10-15:10-15.

[0074]

[0075] The method of ③ is: dissolving compound 2 in a mixed solution of boiling acetic acid and concentrated hydrochloric acid, refluxing under heating for 3-4 hours; after the reaction stops, cooling, vacuum filtering and collecting the solid, washing the solid with ethanol twice, and then separating by column chromatography on silica gel to obtain white solid; preferably, the volume ratio of acetic acid to concentrated hydrochloric acid is 10-12:1.

[0076]

[0077] The method of ④ is: dissolving FTPA in chloroform solution, adding N-bromosuccinimide (NBS) at 0-4℃, stirring the mixture at room temperature for 10-12 hours under nitrogen atmosphere, vacuum filtering the reaction liquid after the reaction is completed, washing the filtrate with water three times, extracting, drying, vacuum filtering the filtrate, and recrystallizing with ethanol to obtain white solid; preferably, the reaction molar ratio of FTPA and NBS is 1:3-4.

[0078]

[0079] 2) Synthesis of compound 3

[0080] The compound 3 is obtained by electrophilic addition of tribenzothiophene and tributyltin chloride.

[0081] The synthesis method is as follows: under the nitrogen atmosphere, tribenzothiophene is dissolved in dry THF, the temperature is reduced to-78 DEG C, the n-butyllithium solution is slowly added to the above reaction solution, and the reaction is stirred at-78 DEG C for 1-2 h, then the temperature is increased to room temperature and stirred for 30-60 min, then the temperature of the system is reduced to-78 DEG C again, tributyltin chloride is slowly added to the solution and stirred for 1-2 h, then the temperature is increased to room temperature, and the stirring is continued for 10-12 h, after the reaction is completed, a small amount of water is added to quench the reaction, anhydrous sodium sulfate is used for drying, the reaction solution is filtered under reduced pressure, the filtrate is concentrated by a rotary evaporator, and the oil liquid compound 3 is obtained; preferably, the molar ratio of tribenzothiophene, n-butyllithium and tributyltin chloride is 1:1.2-1.4:1.2-1.4.

[0082]

[0083] 3) Synthesis of compound FTPA-T3

[0084] The target product FTPA-T3 is obtained by stille reaction of compound FTPA-Br3 and compound 3.

[0085] The synthesis method is as follows: compound FTPA-Br3 is added to toluene, and finally, a catalyst tetrakis(triphenylphosphine)palladium is added, the device system is sealed, and the bottle is quickly replaced with nitrogen, under the nitrogen atmosphere, the oil liquid compound 3 obtained in step 4 is injected into the reaction bottle with a needle, the reaction temperature is adjusted to reflux for 10-12 h. After the reaction is completed, the reaction solution is concentrated by removing the solvent through a rotary evaporator, and then separated and purified by a silica gel chromatographic column to obtain orange yellow solid FTPA-T3. Preferably, the molar ratio of FTPA-Br3, tetrakis(triphenylphosphine)palladium and compound 3 is 1:0.04-0.1:3-3.3.

[0086]

[0087] The present application introduces a tribenzothiophene group with high carrier mobility and double function of passivating perovskite defects on the periphery of the bridged triarylamine parent structure to obtain a hole transport material FTPA-T3. The present application has the following characteristics: a large number of sulfur atoms in the tribenzothiophene can more effectively passivate the surface defects of perovskite; the raw material is low in price, widely sourced, and high in product yield; the series of compounds have high thermal stability, and the thermal decomposition temperature is as high as 400 DEG C. As a hole transport material, the present application has potential application prospect.

[0088] 3. Advantages and beneficial effects of the present application are as follows

[0089] 1) The raw material is cheap, widely available, and the product has high yield and stable structure.

[0090] 2) The bridging part is replaced by 4-methylphenyl, which makes the molecule have better solubility.

[0091] 3) The terthiophene structure as a side group, the large number of sulfur atoms in terthiophene can more effectively passivate the perovskite surface defects, and also have high carrier mobility, the carrier mobility of FTPA-T3 is 5X 10 -4 cm -4 cm 2 v -1 s -1 (As shown in the accompanying Figure 16 ).

[0092] 4) The UV-Vis absorption band of this series of molecules in organic solvent dichloromethane is located in the wavelength range of 300-500 nm, the maximum absorption wavelength is 420 nm (attached Figure 11 ), and the maximum absorption of the thin film state is 440 nm (attached Figure 12 ), which proves that there is π-π stacking, which is beneficial to carrier transport; the maximum fluorescence emission wavelength of FTPA-T3 molecule is 525 nm (attached Figure 13 ).

[0093] 5) The molecule has a low oxidation potential and HOMO energy level, which is beneficial to the transport of carriers (attached Figure 15 ).

[0094] 6) The compound has high thermal stability, and the thermal decomposition temperature is more than 400℃ (attached Figure 14 ). BRIEF DESCRIPTION OF DRAWINGS

[0095] Figure 1 The nuclear magnetic resonance hydrogen spectrum of compound 1 in examples 1-3. 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.52 (dd, J = 7.7, 1.5 Hz, 3H), 7.34-7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9 Hz, 6H), 3.30 (s, 9H).

[0096] Figure 2 The nuclear magnetic resonance carbon spectrum of compound 1 in examples 1-3. 13 C NMR (101 MHz, CDCl3, ppm): δ = 167.72, 146.88, 132.21, 130.98, 127.41, 126.15, 123.49, 51.67.

[0097] Figure 3H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0098] Figure 4 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0099] Figure 5 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). 13 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0100] Figure 6 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0101] Figure 7 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). 13 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14 - 7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0102] Figure 8MS (MALDI-TOF) spectrum of compound 3 in Example 1-3. MS (MALDI-TOF) m / z: C 24 H 34 S3 Sn, calcd [M] + : 538.0845; found [M] + : 538.0851.

[0103] Figure 9 NMR spectrum of molecule FTPA-T3 in Example 1-3. 1 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14-7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H).

[0104] Figure 10 NMR spectrum of molecule FTPA-T3 in Example 1-3. 13 C NMR (101 MHz, CDC13, ppm): δ = 143.40, 142.44, 137.16, 136.32, 135.97, 135.62, 134.38, 130.03, 129.43, 128.37, 127.90, 126.95, 125.10, 124.57, 124.46, 124.34, 124.05, 123.65, 122.96, 114.39, 77.35, 77.03, 76.71, 55.36, 21.03.

[0105] Figure 11 UV-Vis absorption spectrum of molecule FTPA-T3 in Example 1-3 in 1 x 10 -5 mol / L CH2Cl2solution, FTPA-T3 solution has an absorption peak at a wavelength of 420 nm.

[0106] Figure 12 UV-Vis absorption spectrum of molecule FTPA-T3 in Example 1-3 in thin film state, FTPA-T3 in thin film state has an absorption peak at a wavelength of 420 nm.

[0107] Figure 13For the fluorescence spectrum of molecule FTPA-T3 in CH2Cl2solution in Example 1-3, the FTPA-T3solution has a fluorescence peak at a wavelength of 440 nm.

[0108] Figure 14 For the thermal gravimetric curve of molecule FTPA-T3 in Example 1-3. The Aza-dipyrromethene 1 has a decomposition temperature of 480 °C

[0109] Figure 15 For the energy level comparison chart of molecule FTPA-T3 and traditional hole transport material spiro-OMeTAD in Example 1-3. The HOMO energy level of FTPA-T3 is -4.64 eV, and the HOMO energy level of spiro-OMeTAD is -4.63 eV.

[0110] Figure 16 For the space charge limited current test (SCLC) chart of molecule FTPA-T3 in Example 1-3. The carrier mobility of FTPA-T3 is about 5 X 10 -4 cm -4 cm 2 v -1 s -1 . DETAILED DESCRIPTION

[0111] Example 1 (Molecule FTPA-T3)

[0112] 1) Preparation of compound 1

[0113]

[0114] Synthesis of trimethyl 2,2',2"-nitrilotribenzoate (compound 1): anhydrous K2CO3 (7 g), Cu (0.3 g), CuI (0.4 g) were dissolved in diphenyl ether solution (30 ml), then 2-aminobenzoic acid methyl ester (3 ml, 23.0 mmol), o-iodobenzoic acid methyl ester (10 ml, 66.1 mmol) were taken and placed in a 100 ml two-necked round-bottom flask under a nitrogen atmosphere, and the temperature of the heating stirrer was adjusted to 190 °C, and reflux heating was performed for 48 h. After the reaction was completed, the solution was allowed to cool by standing, and the solid raw material was removed by filtration under reduced pressure to obtain a clear filtrate, 200 ml of n-hexane was then added to the filtrate, and after shaking, white crude product was produced by standing, which was obtained as a solid by filtration under reduced pressure, and the crude product was separated by column chromatography on silica gel, using dichloromethane as the eluent, and the solution containing the pure product was concentrated by a rotary evaporator to obtain white solid (5.61 g, 13.4 mmol, 58%). 1H NMR (400 MHz, CDC13, ppm): δ = 7.52 (dd, J = 7.7, 1.5 Hz, 3H), 7.34-7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9 Hz, 6H), 3.30 (s, 9H). 13 CNMR (101 MHz, CDC13, ppm): δ = 167.72, 146.88, 132.21, 130.98, 127.41, 126.15, 123.49, 51.67. The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1 1, and the carbon nuclear magnetic resonance spectrum is shown in Figure 12. Figure 1 Figure 2

[0115] 2) Preparation of compound 2

[0116]

[0117] A 50 ml two-necked round-bottom flask was selected, and p-bromotoluene (2.44 g, 14.3 mmol) was dissolved in 20 ml of dry THF under a nitrogen atmosphere. The flask was placed in a Dewar flask and immersed in anhydrous ethanol, and the temperature in the Dewar flask was lowered to -78°C by liquid nitrogen. n-Butyllithium (2.5 mol / L, 5.71 ml, 14.3 mmol) was added dropwise to the reaction flask, and stirring was performed for 1 h. Compound 1 (0.6 g, 1.43 mmol) was then dissolved in 20 ml of dry THF, and the solution was slowly added dropwise to the reaction system. The reaction was stirred at room temperature for 10 h. After the reaction was completed, a small amount of water was added dropwise to quench the reaction, and the solvent was removed by a rotary evaporator to obtain compound 2 (0.88 g, 1 mmol, yield 70%). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.52 (dd, J = 7.7, 1.5 Hz, 3H), 7.34-7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9 Hz, 6H), 3.30 (s, 9H). Figure 3

[0118] 3) Preparation of FTPA

[0119]

[0120] ​​​Into a 100 ml two-necked round-bottom flask, compound 2 was dissolved in a boiling mixture of acetic acid (48 ml) and concentrated hydrochloric acid (4 ml) and refluxed for 3 h. After the reaction was stopped, the reaction mixture was cooled and poured into a 200 ml ice-water bath, filtered under reduced pressure and the solid was washed twice with ethanol and separated by column chromatography on silica gel using petroleum ether / dichloromethane = 3:1 (v / v) as eluent. After concentration by rotary evaporator, the product was recrystallized from ethanol and filtered to obtain a white solid (482.9 mg, 0.33 mmol, 59.2%). 1 H NMR (400 MHz, CDC13, ppm): δ = 6.97-6.88 (m, 3H), 6.83 (d, J = 7.5 Hz, 18H), 6.63 (d, J = 8.2 Hz, 12H), 2.28 (s, 18H). The H nuclear magnetic resonance spectrum is shown in Figure 1. The C nuclear magnetic resonance spectrum is shown in Figure 2. Figure 4 The H nuclear magnetic resonance spectrum is shown in Figure 1. Figure 5 The C nuclear magnetic resonance spectrum is shown in Figure 2.

[0121] 4) Preparation of FTPA-Br3

[0122]

[0123] Into a 50 ml two-necked round-bottom flask, FTPA (0.5 g, 0.608 mmol) was dissolved in chloroform solution (10 ml) and N-bromosuccinimide (0.324 g, 1.820 mmol) was added at 0°C. The mixture was stirred at room temperature for 10 h under a nitrogen atmosphere. After the reaction was completed, the reaction solution was filtered under reduced pressure and the filtrate was washed with water three times, then separated, the organic phase was collected and dried with anhydrous sodium sulfate. The filtrate was concentrated by rotary evaporator and recrystallized from hexanol to obtain a white solid (332.7 mg, 0.31 mmol, 63%). 1 H NMR (400 MHz, CDC13, ppm): δ = 9.81 (s, 3H), 7.72-7.62 (m, 6H), 7.39-7.29 (m, 12H), 7.22-7.11 (m, 18H), 7.02 (t, J = 5.5 Hz, 6H). The H nuclear magnetic resonance spectrum is shown in Figure 1. The C nuclear magnetic resonance spectrum is shown in Figure 2. Figure 6 The C nuclear magnetic resonance spectrum is shown in Figure 2. Figure 7 The C nuclear magnetic resonance spectrum is shown in Figure 2.

[0124] 5) Preparation of FTPA-T3

[0125]

[0126] Take a 100ml double-necked round-bottom flask and, under a nitrogen atmosphere, dissolve compound T3 (0.83g, 3.342mmol) in 30ml of dry THF. Take a Dewar flask and add an appropriate amount of anhydrous ethanol to it. Place the double-necked round-bottom flask inside the Dewar flask and lower the reaction temperature to -78℃ using liquid nitrogen. Slowly add n-butyllithium solution (2.5mol / L, 1.6ml, 4.01mmol) dropwise to the above reaction solution and stir at -78℃ for 1h. Then raise the temperature to room temperature and stir for 30min. Next, lower the system temperature to -78℃ again and slowly add tributyltin chloride (1.31g, 4.01mmol) dropwise to the solution and stir for 1h. Then raise the temperature to room temperature and continue stirring for 10h. After the reaction is complete, add a small amount of water to quench the reaction, then add anhydrous sodium sulfate for drying. Filter the reaction solution under reduced pressure and concentrate the filtrate using a rotary evaporator to obtain an oily liquid compound 3. Proceed directly to the next step without further processing. MS(MALDI-TOF)m / z:C 24 H 34 S3Sn,calcd[M] + :538.0845; found [M] + The 538.0851.MS (MALDI-TOF) image is attached. Figure 8 As shown.

[0127]

[0128] Take a 50 ml double-necked round-bottom flask and add the compound FTPA-Br3 (300 mg, 0.284 mmol), toluene (20 ml), and finally the catalyst tetra(triphenylphosphine)palladium (12 mg, 0.011 mmol). Seal the apparatus and quickly purge the air in the flask with nitrogen. Under a nitrogen atmosphere, add the oily liquid obtained in the first step to the reaction flask, adjust the reaction temperature to 100 °C, and react for 10 h. After the reaction is complete, remove the solvent and concentrate the reaction solution using a rotary evaporator, and then separate and purify it using a silica gel column chromatography with petroleum ether:dichloromethane = 2:1 (v / v) as the eluent to obtain an orange-yellow solid (98.34 mg, 0.063 mmol, 22.2%). 1H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14-7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). The nuclear magnetic resonance hydrogen spectrum is shown in Figure 1. Figure 9 The nuclear magnetic resonance carbon spectrum is shown in Figure 2. Figure 10 The 1 x 10 -5 The UV-Vis absorption spectrum of the methylene chloride solution of FTPA-T3 is shown in Figure 3. Figure 11 The UV-Vis absorption spectrum of the thin film of FTPA-T3 is shown in Figure 4. Figure 12 The fluorescence emission spectrum of FTPA-T3 is shown in Figure 5. Figure 13 The thermogravimetric plot of FTPA-T3 is shown in Figure 6. Figure 14 The HOMO and LUMO energy level diagram of the density functional theory calculation of FTPA-T3 is shown in Figure 7. Figure 15 The SCLC plot of FTPA-T3 is shown in Figure 8. Figure 16

[0129] Example 2 (molecule FTPA-T3)

[0130] 1) Preparation of compound 1

[0131]

[0132] Anhydrous K2CO3 (8 g), Cu (0.35 g), CuI (0.5 g) were dissolved in diphenyl ether solution (30 ml), then 2-aminobenzoic acid methyl ester (3 ml, 23.0 mmol), methyl o-iodobenzoate (13.5 ml, 89.2 mmol) were taken and placed in a 100 ml two-necked round-bottom flask, under nitrogen atmosphere, the temperature of the heating stirrer was adjusted to 190 °C, and reflux heating was carried out for 56 h. After the reaction was completed, the solution was allowed to cool by standing, and the solid raw material was removed by filtration under reduced pressure to obtain a clear filtrate, then 200 ml of n-hexane was added to the filtrate, shaken and allowed to stand, producing a white crude product, which was obtained by filtration under reduced pressure, and the crude product was separated by column chromatography on silica gel, using dichloromethane as the eluent, and the solution containing the pure product was concentrated by a rotary evaporator to obtain a white solid (6.9 g, 16.5 mmol, 71 %). 1 ​H NMR (400 MHz, CDC13, ppm): δ = 7.52 (dd, J = 7.7, 1.5 Hz, 3H), 7.34-7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9 Hz, 6H), 3.30 (s, 9H). 13 C NMR (101 MHz, CDC13, ppm): δ = 167.72, 146.88, 132.21, 130.98, 127.41, 126.15, 123.49, 51.67. The1H NMR spectrum is shown in Figure 1 1 and the13C NMR spectrum is shown in Figure 12. Figure 1 Figure 2

[0133] 2) Preparation of compound 2

[0134]

[0135] A 50 ml two-necked round-bottom flask was selected, and p-bromotoluene (2.58 g, 15.084 mmol) was dissolved in 20 ml of dry THF under a nitrogen atmosphere. The flask was placed in a Dewar flask and immersed in anhydrous ethanol, and the temperature in the Dewar flask was lowered to -78°C by means of liquid nitrogen. n-Butyllithium (2.5 mol / L, 6.96 ml, 17.408 mmol) was added dropwise to the reaction flask, and stirring was carried out for 1 h. Compound 1 (0.6 g, 1.43 mmol) was then dissolved in 20 ml of dry THF, and the solution was added slowly dropwise to the reaction system. The reaction was stirred at room temperature for 11 h. After the reaction was completed, a small amount of water was added to quench the reaction, and the solvent was then removed by means of a rotary evaporator to obtain compound 2 (0.96 g, 1.03 mmol, yield 72%). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.52 (dd, J = 7.7, 1.5 Hz, 3H), 7.34-7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9 Hz, 6H), 3.30 (s, 9H). Figure 3

[0136] 3) Preparation of FTPA

[0137]

[0138] ​​​Into a 100 ml two-necked round-bottom flask, compound 2 was dissolved in a boiling mixture of acetic acid (44 ml) and concentrated hydrochloric acid (4 ml) and refluxed for 3.5 h. After the reaction was stopped, the reaction mixture was cooled, poured into a 200 ml ice-water bath, filtered under reduced pressure and the solid was collected, washed twice with ethanol and separated by column chromatography on silica gel with petroleum ether / dichloromethane = 3:1 (v / v) as eluent, concentrated by a rotary evaporator and recrystallized from ethanol to obtain a white solid (543.2 mg, 0.37 mmol, 67%). 1 H NMR (400 MHz, CDC13, ppm): δ = 6.97-6.88 (m, 3H), 6.83 (d, J = 7.5 Hz, 18H), 6.63 (d, J = 8.2 Hz, 12H), 2.28 (s, 18H). The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2. Figure 4 The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2. Figure 5 The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2.

[0139] 4) Preparation of FTPA-Br3

[0140]

[0141] Into a 50 ml two-necked round-bottom flask, FTPA (0.5 g, 0.608 mmol) was dissolved in chloroform solution (10 ml), N-bromosuccinimide (0.38 g, 2.13 mmol) was added at 0 °C, the mixture was stirred at room temperature for 11 h under a nitrogen atmosphere, after the reaction was completed, the reaction solution was filtered under reduced pressure, the filtrate was washed with water three times, then separated, the organic phase was collected and dried with anhydrous sodium sulfate, the filtrate was filtered under reduced pressure, the filtrate was concentrated by a rotary evaporator and recrystallized from hexanol to obtain a white solid (395.3 mg, 0.373 mmol, 60.8%). 1 H NMR (400 MHz, CDC13, ppm): δ = 9.81 (s, 3H), 7.72-7.62 (m, 6H), 7.39-7.29 (m, 12H), 7.22-7.11 (m, 18H), 7.02 (t, J = 5.5 Hz, 6H). The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2. Figure 6 The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2. Figure 7 The hydrogen nuclear magnetic resonance spectrum is shown in Figure 1. The carbon nuclear magnetic resonance spectrum is shown in Figure 2.

[0142] 5) Preparation of FTPA-T3

[0143]

[0144] Take a 100ml double-necked round-bottom flask and, under a nitrogen atmosphere, dissolve compound T3 (0.83g, 3.342mmol) in 30ml of dry THF. Take a Dewar flask and add an appropriate amount of anhydrous ethanol to it. Place the double-necked round-bottom flask inside the Dewar flask and lower the reaction temperature to -78℃ using liquid nitrogen. Slowly add n-butyllithium solution (2.5mol / L, 1.4ml, 3.5mmol) dropwise to the above reaction solution and stir at -78℃ for 1h. Then raise the temperature to room temperature and stir for 30min. Next, lower the system temperature to -78℃ again and slowly add tributyltin chloride (1.43g, 4.39mmol) dropwise to the solution and stir for 1h. Then raise the temperature to room temperature and continue stirring for 11h. After the reaction is complete, add a small amount of water to quench the reaction, then add anhydrous sodium sulfate for drying. Filter the reaction solution under reduced pressure and concentrate the filtrate using a rotary evaporator to obtain an oily liquid compound 3. Proceed directly to the next step without further processing. MS(MALDI-TOF)m / z:C 24 H 34 S3Sn,calcd[M] + :538.0845; found [M] + The 538.0851.MS (MALDI-TOF) image is attached. Figure 8 As shown.

[0145]

[0146] Take a 50 ml double-necked round-bottom flask, add the compound FTPA-Br3 (300 mg, 0.284 mmol), toluene (20 ml), and finally the catalyst tetra(triphenylphosphine)palladium (20 mg, 0.018 mmol). Seal the apparatus and quickly purge the air in the flask with nitrogen. Under a nitrogen atmosphere, add the oily liquid obtained in the first step to the reaction flask, adjust the reaction temperature to 100 °C, and react for 11 h. After the reaction is complete, remove the solvent and concentrate the reaction solution using a rotary evaporator, then separate and purify it using a silica gel column chromatography with petroleum ether:dichloromethane = 2:1 (v / v) as the eluent to obtain an orange-yellow solid (163.9 mg, 0.105 mmol, 37%). 1 1H NMR (400MHz, CDCl3, ppm): δ=7.21(d, J=5.0Hz, 3H), 7.15(d, J=3.4Hz, 3H), 7.14–7.07(m, 8H), 7.05(d, J=3.7Hz, 3H), 7.01(dd, J=10.4, 4.2Hz, 9H), 6.90(d, J=8.2Hz, 12H), 6.77(d, J=3.7Hz, 3H), 6.71(d, J=8.1Hz, 10H), 2.29(d, J=35.4Hz, 19H). The 1H NMR spectrum is attached.Figure 9 The attached carbon NMR spectrum is shown in the figure. Figure 10 As shown. FTPA-T3 1x10 -5 The UV-Vis absorption spectrum of M dichloromethane solution is as follows: Figure 11 As shown, the UV-Vis absorption spectrum of the FTPA-T3 thin film is as follows: Figure 12 As shown. The fluorescence emission spectrum of FTPA-T3 is as follows. Figure 13 As shown. The thermogram of FTPA-T3 is as follows. Figure 14 As shown. The HOMO and LUMO energy level diagrams calculated by FTPA-T3 density functional theory are shown below. Figure 15 As shown. The SCLC diagram of FTPA-T3 is as follows. Figure 16 As shown.

[0147] Example 3 (Molecular FTPA-T3)

[0148] 1) Preparation of compound 1

[0149]

[0150] Anhydrous K₂CO₃ (7 g), Cu (0.3 g), and CuI (0.4 g) were dissolved in diphenyl ether solution (30 ml). Then, methyl 2-aminobenzoate (3 ml, 23.0 mmol) and methyl o-iodobenzoate (10 ml, 66.1 mmol) were added to a 100 ml double-necked round-bottom flask. The mixture was heated under nitrogen atmosphere with the stirrer at 190 °C for reflux for 72 h. After the reaction was complete, the solution was allowed to cool and stand. The solid raw material was removed by vacuum filtration to obtain a clear filtrate. 200 ml of n-hexane was added to the filtrate, and after shaking and standing, a white crude product was produced. This product was filtered under vacuum to obtain a solid. The crude product was then separated by column chromatography using a silica gel column with dichloromethane as the eluent. The solution containing the pure product was concentrated by rotary evaporation to obtain a white solid (5.61 g, 13.4 mmol, 58%). 1 H NMR (400MHz, CDCl3, ppm): δ = 7.52 (dd, J = 7.7, 1.5Hz, 3H), 7.34–7.26 (m, 3H), 7.01 (dd, J = 15.5, 7.9Hz, 6H), 3.30 (s, 9H). 13 C10 NMR (101MHz, CDCl3, ppm): δ=167.72, 146.88, 132.21, 130.98, 127.41, 126.15, 123.49, 51.67. The proton NMR spectrum is attached. Figure 1 The attached carbon NMR spectrum is shown in the figure. Figure 2 As shown.

[0151] 2) Preparation of compound 2

[0152]

[0153] A 50ml two-necked round-bottom flask was selected, and p-bromotoluene (3.66g, 15.084 21.45mmol) was dissolved in 20ml of dry THF under a nitrogen atmosphere. The flask was placed in a Dewar flask and immersed in anhydrous ethanol. The temperature in the Dewar flask was reduced to -78°C by liquid nitrogen, and n-butyllithium (3.1mol / L, 8.56ml, 21.45mmol) was added dropwise to the reaction flask, and stirred for 1h. Compound 1 (0.6g, 1.43mmol) was dissolved in 20ml of dry THF, and the solution was slowly added dropwise to the reaction system, which was stirred at room temperature for 12h. After the reaction was completed, a small amount of water was added to quench the reaction, and the solvent was removed by a rotary evaporator to obtain compound 2 (0.97g, 1.1mmol, yield 77%). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14-7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). The hydrogen nuclear magnetic resonance spectrum is shown in the accompanying Figure 3

[0154] 3) Preparation of FTPA

[0155]

[0156] A 100ml two-necked round-bottom flask was selected, and compound 2 was dissolved in a mixture of boiling acetic acid (40ml) and concentrated hydrochloric acid (4ml). The mixture was refluxed for 4h under heating. After the reaction stopped, the reaction mixture was cooled and poured into a 200ml ice water bath. The solid was collected by filtration under reduced pressure, washed twice with ethanol, separated by column chromatography on silica gel, eluted with petroleum ether / dichloromethane = 3:1 (v / v), concentrated by a rotary evaporator, and recrystallized with ethanol to obtain a white solid (603.6mg, 0.411mmol, 74%). 1 H NMR (400 MHz, CDC13, ppm): δ = 6.97-6.88 (m, 3H), 6.83 (d, J = 7.5 Hz, 18H), 6.63 (d, J = 8.2 Hz, 12H), 2.28 (s, 18H). The hydrogen nuclear magnetic resonance spectrum is shown in the accompanying Figure 4 The hydrogen nuclear magnetic resonance spectrum is shown in the accompanying​Figure 5 as shown.

[0157] 4) Preparation of FTPA-Br3

[0158]

[0159] Take 50 ml two-port round-bottom flask, dissolve FTPA (0.5 g, 0.608 mmol) in chloroform solution (10 ml), add N-bromosuccinimide (0.4 g, 2.247 mmol) at 0°C, under nitrogen atmosphere, the mixture is stirred at room temperature for 12 h, after the reaction is completed, the reaction liquid is filtered under reduced pressure, the filtrate is washed with water three times, then separated, collect the organic phase, and dry the organic phase with anhydrous sodium sulfate, filter under reduced pressure, take the filtrate, concentrate the filtrate by rotary evaporator, then recrystallize with hexanol to obtain white solid (409.6 mg, 0.386 mmol, 63%). 1 H NMR (400 MHz, CDC13, ppm): δ = 9.81 (s, 3H), 7.72-7.62 (m, 6H), 7.39-7.29 (m, 12H), 7.22-7.11 (m, 18H), 7.02 (t, J = 5.5 Hz, 6H). The nuclear magnetic resonance hydrogen spectrum is shown in the attached Figure 6 carbon spectrum is shown in the attached Figure 7 carbon spectrum is shown in the attached

[0160] 5) Preparation of FTPA-T3

[0161]

[0162] Take 100 ml two-port round-bottom flask, dissolve compound T3 (0.83 g, 3.342 mmol) in 30 ml dry THF under nitrogen atmosphere, take a dewar flask, add appropriate amount of anhydrous ethanol to the dewar flask, place the two-port round-bottom flask in the dewar flask, reduce the reaction temperature to -78°C by liquid nitrogen, slowly drop n-butyllithium solution (2.5 mol / L, 2.32 ml, 4.68 mmol) into the above reaction liquid, and stir for 1 h at -78°C, then raise the temperature to room temperature and stir for 30 min, then reduce the temperature of the system to -78°C again, slowly drop tributyltin chloride (1.53 g, 4.39 4.68 mmol) into the solution, stir for 1 h, then raise the temperature to room temperature, continue to stir for 12 h, after the reaction is completed, quench the reaction by adding a small amount of water, then dry with anhydrous sodium sulfate, filter the reaction liquid under reduced pressure, concentrate the filtrate by rotary evaporator to obtain oily liquid compound 3. No treatment is needed for the next step. MS (MALDI-TOF) m / z: C 24 H 34 S3Sn, calcd [M] +:538.0845; found [M] + :538.0851. MS (MALDI-TOF) spectrum as shown in Figure Figure 8

[0163]

[0164] A 50 ml two-necked round-bottom flask was charged with compound FTPA-Br3 (300 mg, 0.284 mmol), toluene (20 ml), and finally catalyst palladium tetrakis(triphenylphosphine) (30 mg, 0.027 mmol). The apparatus was sealed and the air in the flask was replaced rapidly with nitrogen. The oily liquid obtained in the first step was added to the reaction flask under a nitrogen atmosphere. The reaction temperature was adjusted to 100 °C and the reaction was allowed to proceed for 12 h. After the reaction was completed, the reaction solution was concentrated by removing the solvent using a rotary evaporator and then separated and purified using a silica gel column chromatography column with petroleum ether:dichloromethane = 2:1 (v / v) as the eluent to obtain an orange-yellow solid (327.8 mg, 0.21 mmol, 74%). 1 H NMR (400 MHz, CDC13, ppm): δ = 7.21 (d, J = 5.0 Hz, 3H), 7.15 (d, J = 3.4 Hz, 3H), 7.14-7.07 (m, 8H), 7.05 (d, J = 3.7 Hz, 3H), 7.01 (dd, J = 10.4, 4.2 Hz, 9H), 6.90 (d, J = 8.2 Hz, 12H), 6.77 (d, J = 3.7 Hz, 3H), 6.71 (d, J = 8.1 Hz, 10H), 2.29 (d, J = 35.4 Hz, 19H). The H NMR spectrum is shown in Figure Figure 9 Figure 10 1x10 -5 The UV-Vis absorption spectrum of a dichloromethane solution of FTPA-T3 is shown in Figure Figure 11 The UV-Vis absorption spectrum of a thin film of FTPA-T3 is shown in Figure Figure 12 The fluorescence emission spectrum of FTPA-T3 is shown in Figure Figure 13 The thermogravimetric plot of FTPA-T3 is shown in Figure Figure 14 The HOMO and LUMO energy level diagram of FTPA-T3 calculated by density functional theory is shown in Figure Figure 15 The SCLC plot of FTPA-T3 is shown in Figure Figure 16

[0165] ​​​The technical solutions disclosed and presented in the present application can be implemented by referring to the content of the present application, changing the conditions and routes, etc. Although the method and preparation technology of the present application have been described by means of preferred embodiments, the related technical personnel can obviously make changes or recombine the method and technical route described in the present application without departing from the content, spirit and scope of the present application, to realize the final preparation technology. It is particularly pointed out that all similar substitutions and changes are obvious to the technical personnel in the art, and they are considered to be included in the spirit, scope and content of the present application.

Claims

1. A planar triarylamine derivative hole transport material; characterized in that, The structural formula is as follows:

2. The method for preparing a planar triarylamine derivative hole transport material as described in claim 1, characterized in that, The method comprises the following steps: The first step is to obtain compound 1 with the following structure by Ullmann reaction with 2-aminobenzoic acid methyl ester and 2-iodobenzoic acid methyl ester as raw materials. ； The second step is to obtain compound 2 by electrophilic addition of compound 1, p-bromotoluene and n-butyllithium. ； The third step is to obtain compound FTPA by refluxing compound 2 in a mixed solution of acetic acid and concentrated hydrochloric acid. ； The fourth step is to obtain compound FTPA-Br3 by bromination of FTPA and NBS. ； The fifth step is to obtain compound 3 by electrophilic addition reaction of terthiophene and tributyltin chloride. ； The sixth step is to obtain the target product FTPA-T3 by stille reaction of compound 3 and FTPA-Br3.

3. The production method according to claim 2, wherein The synthesis method of compound 1 is as follows: 2-aminobenzoic acid methyl ester and o-iodobenzoic acid methyl ester are dissolved in a diphenyl ether solution, then anhydrous K2CO3, Cu and CuI are added together under a nitrogen atmosphere, and the heating stirrer is adjusted to reflux heating for 48-56 hours; after the reaction is completed, the solution is cooled by standing, and the solid raw material is removed by filtration under reduced pressure to obtain a clear filtrate; then n-hexane is added to the filtrate, and after oscillation, the white crude product is obtained by standing, which is then separated by column chromatography on silica gel to obtain white solid as compound 1.

4. The production method according to claim 2, wherein The synthesis method of compound 2 is as follows: p-bromotoluene is dissolved in dry tetrahydrofuran under a nitrogen atmosphere, n-butyllithium is added dropwise into the reaction system at-78℃, and stirring is performed for 1-2 hours; then compound 1 is dissolved in dry tetrahydrofuran and added dropwise into the reaction system, and stirring is performed at room temperature for 10-12 hours; after the reaction is completed, the reaction is quenched by adding water dropwise, and the solvent is removed by a rotary evaporator to obtain compound 2.

5. The production method according to claim 2, wherein The synthesis method of compound FTPA is as follows: the obtained compound 2 is dissolved in a boiling mixed solution of acetic acid and concentrated hydrochloric acid, and refluxed under heating for 3-4 hours; after the reaction stops, the reaction mixture is cooled and poured into an ice water bath, and the solid is collected by filtration under reduced pressure, washed with ethanol twice, and then separated by column chromatography on silica gel, recrystallized with ethanol, and filtered to obtain white solid FTPA.

6. The production method according to claim 2, wherein The synthesis method of compound FTPA-Br3 is as follows: FTPA is dissolved in a chloroform solution, N-bromosuccinimide is added at 0-4℃, and the mixture is stirred at room temperature for 10-12 hours under a nitrogen atmosphere; after the reaction is completed, the reaction liquid is filtered under reduced pressure, the filtrate is washed with water three times, extracted, dried, filtered under reduced pressure, and then recrystallized with ethanol to obtain white solid FTPA-Br3.

7. The production method according to claim 2, wherein the production method is characterized by, The synthesis method of FTPA-T3 is: under nitrogen atmosphere, the terthiophene is dissolved in dry tetrahydrofuran, the temperature is reduced to-78℃, the n-butyllithium solution is slowly added to the above reaction liquid, and the reaction is stirred at-78℃ for 1-2h, then the temperature is increased to room temperature and stirred for 30-60min, then the temperature of the system is reduced to-78℃ again, the tributyltin chloride is slowly added to the solution, and the reaction is stirred for 1-2h, then the temperature is increased to room temperature, and the stirring is continued for 10-12h, after the reaction is completed, a small amount of water is added to quench the reaction, anhydrous sodium sulfate is used for drying, the reaction liquid is filtered under reduced pressure, the filtrate is concentrated by a rotary evaporator to obtain an oily liquid compound 3; compound FTPA-Br3, toluene, and finally a catalyst tetrakis(triphenylphosphine)palladium are added to the reaction bottle, the device is sealed, and the bottle is replaced with nitrogen, under nitrogen atmosphere, compound 3 is added to the reaction bottle, the reaction temperature is adjusted to 100-110℃, and the reaction is carried out for 10-12h; after the reaction is completed, the reaction liquid is concentrated by removing the solvent through a rotary evaporator, and then column chromatography silica gel chromatographic column is used for separation and purification, and orange yellow solid FTPA-T3 is obtained.

8. The production method according to claim 3, wherein The molar ratio of 2-amino methyl benzoate, methyl o-iodobenzoate, anhydrous K2CO3, Cu and CuI is 1:2-3:1.8-2.2:4-5:1.8-2.

2.

9. The preparation method according to claim 2, characterized in that the compound 1. The reaction molar ratio of p-bromotoluene and n-butyllithium is 1:10-15:10-15; the volume ratio of acetic acid and concentrated hydrochloric acid is 10-12:1; the reaction molar amount of FTPA and N-bromosuccinimide is 1:3-4.

10. The production method according to claim 7, wherein The reaction molar ratio of FTPA-Br3, tetrakis(triphenylphosphine)palladium, compound 3, n-butyllithium, and tributyltin chloride is 1:0.04-0.1:3-3.3:3.6-4.2:3.6-4.2.

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