Tertiary amine or quaternary ammonium salt substituted perylene bisimide dimer compound as well as preparation method and application thereof

Abstract

The invention discloses a tertiary amine or quaternary ammonium salt substituted perylene bisimide dimer compound as well as a preparation method and application thereof, and belongs to the technical field of organic photoelectric materials. The structure is shown in the specification. The preparation method comprises the following steps: carrying out condensation reaction on a perylene dimer connected by a single bond or different modules and different amines; a tertiary amine and quaternary ammonium salt substituted perylene bisimide monomer is subjected to coupling reaction with the perylene bisimide monomer or different modules, and the tertiary amine substituted perylene bisimide dimer compound is prepared in one step. The quaternary ammonium salt substituted perylene bisimide dimer compound can be obtained by reacting a tertiary amine substituted perylene bisimide dimer compound with halogenated alkane or oxidizing the tertiary amine substituted perylene bisimide dimer compound with hydrogen peroxide. The compound can be used as an electron transport layer to be applied to the fields of organic solar cells, perovskite solar cells, organic light-emitting diodes and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, specifically relating to a perylene imide dimer compound substituted with a tertiary amine or quaternary ammonium salt, its preparation method, and its application. Background Technology

[0002] Perylene imides are an important class of organic optoelectronic functional molecules. These compounds possess excellent chemical, optical, and thermal stability, broad absorption spectra, and strong electron acceptor properties, exhibiting superior optoelectronic properties. They have found wide applications in organic optoelectronic functional materials, such as solar cell materials, perovskite materials, organic field-effect transistors, and luminescent materials. Due to their outstanding optoelectronic properties and broad application prospects, the design and synthesis of perylene imide materials have attracted widespread attention from researchers.

[0003] Perylene imide monomers, through modification of the imide groups, are widely used as cathode interface materials or electron transport materials in organic solar cells, perovskite cells, organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic electroluminescent devices, and organic thermochromic elements, exhibiting excellent performance. While perylene imide monomers demonstrate superior photoelectric properties as cathode interface materials or electron transport materials, their large planar conjugated framework leads to easy intermolecular aggregation, affecting film quality and contact with materials on both sides of the interface layer, thus impacting overall device performance. Although perylene imide-based polymers possess good film-forming properties and contact surfaces, the disordered assembly structure and batch-to-batch reproducibility of material preparation have consistently limited their further applications. Summary of the Invention

[0004] To address the problems existing in the application of perylene imide materials in organic optoelectronic devices, this invention provides a perylene imide dimer compound substituted with a tertiary amine or quaternary ammonium salt, its preparation method, and its application.

[0005] The first objective of this invention is to provide a perylene diimide dimer compound substituted with a tertiary amine or quaternary ammonium salt.

[0006] A second objective of this invention is to provide two methods for preparing the perylene diimide dimers substituted with the tertiary amine or quaternary ammonium salt.

[0007] A third objective of this invention is to provide the application of the tertiary amine or quaternary ammonium salt-substituted perylene imide dimers in organic solar cells and perovskite solar cells.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides a perylene diimide dimer compound substituted with a tertiary amine or quaternary ammonium salt, having the structure shown in formula (I) or formula (II):

[0010]

[0011] Wherein: R1 is selected from substituted alkyl groups or substituted heteroalkyl groups containing tertiary amines or quaternary ammonium salts.

[0012] Ideally, R1 is one of the following structures:

[0013]

[0014] For example, n = 1-15, etc.

[0015] Where R2 is one of the following structures:

[0016]

[0017] C1 and C1' represent the corresponding C on the benzene ring;

[0018] Among them, the above three R3s are all selected from any one of S, Se, N, and O, and the three R3s may be the same or different;

[0019] The second aspect of the present invention provides two methods for preparing the perylene diimide dimer compounds substituted by the tertiary amine or quaternary ammonium salt. Both methods have short synthesis steps, mild conditions, simple operation, readily available raw materials, and are easy to industrialize.

[0020] The preparation method is as follows:

[0021] Preparation method 1:

[0022]

[0023] 1) The perylene anhydride dimer represented by formula (a1) or (a2) and the amine R1-NH2 represented by formula (a3) ​​related to R1 are charged into the reactor; R1-NH2 has the following structure:

[0024]

[0025] 2) Under inert gas protection, add organic solvent to the reactor in step 1), and stir and heat the solution to 50-180°C for 0.5-72 hours.

[0026] 3) The amine-substituted perylene imide dimer compound is obtained through post-treatment;

[0027] 4) If the corresponding compound is quaternary ammonium salt substituted: The amine-substituted perylene imide dimer obtained in 3) and the haloalkane are loaded into the reactor. Under inert gas protection, organic solvent and THF (tetrahydrofuran) solvent are injected and reacted at room temperature for two days to obtain the corresponding quaternary ammonium salt substituted perylene imide dimer.

[0028] 5) If the corresponding compound is substituted with a nitrogen-oxygen quaternary ammonium salt: Add hydrogen peroxide to the ethanol solution of the amine-substituted perylene imide dimer obtained in 3), under inert gas protection, and react at 80°C for 3 hours to obtain the corresponding nitrogen-oxygen quaternary ammonium salt-substituted perylene imide dimer.

[0029] The equivalent of the compound represented by formula (a1) or formula (a2) is 2 to 50, preferably 5 to 40, of the amine R1-NH2 represented by formula (a3) ​​involved in R1; the equivalent of the haloalkane is 2 to 50, preferably 5 to 40; and the equivalent of the hydrogen peroxide is 2 to 50, preferably 5 to 40.

[0030] The organic solvent mentioned in steps 2) and 4) is one of the following:

[0031] The alkaline solvent is selected from: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), pyridine, ethylenediamine, ammonia, triethylamine, and dimethyl sulfoxide.

[0032] The acidic solvents are selected from: propionic acid, glacial acetic acid, formic acid, sulfuric acid, and phosphoric acid.

[0033] Neutral solvents are selected from: benzene, toluene, chlorobenzene, o-xylene, p-xylene, m-trimethylbenzene, pseudotrimethylbenzene, tetrahydrofuran, and 1,4-dioxane.

[0034] Preparation method two:

[0035]

[0036] 1) The R2 compound of formula (b1) and dibromo-substituted, or the R2 compound of formula (b3) and diboronic acid or ditin-substituted, or the compound of formula (b1) and (b3) is loaded into the reactor;

[0037] The dibromo-substituted R2 compounds are shown in formula (b2), and the diboronic acid or ditin-substituted R2 compounds are shown in formula (b4):

[0038]

[0039] 2) Under inert gas protection, palladium catalyst, base, organic solvent and water are added to the reactor in step 1) via Suzuki or Stille reaction, and the mixture is heated to 50-180°C and reacted for 5-48 hours.

[0040] 3) Cooling to room temperature yields amine-substituted perylene imide dimers;

[0041] 4) If the corresponding compound is quaternary ammonium salt substituted: The amine-substituted perylene imide dimer obtained in 3) and the haloalkane are loaded into the reactor. Under inert gas protection, organic solvent and THF (tetrahydrofuran) solvent are injected and reacted at room temperature for two days to obtain the corresponding quaternary ammonium salt substituted perylene imide dimer.

[0042] 5) If the corresponding compound is substituted with a nitrogen-oxygen quaternary ammonium salt: Add hydrogen peroxide to the ethanol solution of the amine-substituted perylene imide dimer obtained in 3), under inert gas protection, and react at 80°C for 3 hours to obtain the corresponding nitrogen-oxygen quaternary ammonium salt-substituted perylene imide dimer.

[0043] The equivalent of the compound represented by formula (b1) or formula (b3) is 1, and the equivalent ratio of the compounds represented by formulas (b2) and (b4) involved in R2 is 0.2 to 0.5, preferably 0.3 to 0.5; the equivalent ratio of the palladium catalyst is 0.05 to 0.2, preferably 0.05 to 0.1; the equivalent ratio of the base is 2 to 50, preferably 5 to 10; the equivalent ratio of the haloalkane is 2 to 50, preferably 5 to 40; and the equivalent ratio of hydrogen peroxide is 2 to 50, preferably 5 to 40.

[0044] The organic solvents mentioned in 2) and 4) are:

[0045] Alkaline solvents include: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), pyridine, ethylenediamine, ammonia, triethylamine, and dimethyl sulfoxide.

[0046] Acidic solvents include: propionic acid, glacial acetic acid, formic acid, sulfuric acid, and phosphoric acid.

[0047] Neutral solvents include: benzene, toluene, chlorobenzene, o-xylene, p-xylene, m-trimethylbenzene, pseudotrimethylbenzene, tetrahydrofuran, and 1,4-dioxane.

[0048] The palladium reagents mentioned are: tetratetraphenylphosphine palladium and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride.

[0049] When the organic solvent used in step 2) is acidic, alkaline, or neutral, an alkali needs to be added. The alkali reagent is: sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, or disodium hydrogen phosphate.

[0050] The perylene diimide dimer compounds substituted with tertiary amines or quaternary ammonium salts obtained in this invention can be used in organic solar cells and perovskite solar cells, and further applied to electron transport interface materials.

[0051] By adopting the above technical solution, the present invention has the following advantages and beneficial effects:

[0052] This invention provides two methods for preparing perylene imide dimers substituted with tertiary amines or quaternary ammonium salts: one method involves reacting perylene anhydride dimers with tertiary amines to prepare tertiary amine-substituted perylene imide dimers; the other method involves reacting tertiary amine-substituted perylene imide monomers with different R2 modules via Suzuki or Stille coupling reactions to obtain tertiary amine-substituted perylene imide dimers. The tertiary amine-substituted perylene imide dimers prepared by either method can be further reacted with haloalkanes or oxidized with hydrogen peroxide to obtain quaternary ammonium salt-substituted perylene imide dimer compounds. Both methods involve short synthetic steps, mild conditions, simple operation, readily available raw materials, and are easy to industrialize. The perylene diimide dimers substituted with tertiary amines and quaternary ammonium salts described in this invention exhibit strong absorption of visible light, high fluorescence quantum yield, strong electron acceptor properties, excellent charge transport performance, tunable energy level structure, and good solution processability. Illumination and thermal testing show that these materials possess excellent optical and thermal stability and can be used as electron transport layers in organic solar cells, perovskite solar cells, organic light-emitting diodes, and other fields.

[0053] All raw materials used in this invention are commercially available or synthesized using existing technologies. For example, the perylene anhydride dimer compounds shown in formulas (a1) and (a2) were synthesized according to the method reported in the literature (Org. Lett., 2012, 14, 5278-5281.). The tertiary amine-substituted perylene imide monomers shown in formulas (b1) and (b3) were synthesized according to the method reported in the literature (Angew. Chem. Int. Ed. 2019, 58(1), 178-183.). Other reagents and solvents were commercially available. Detailed Implementation

[0054] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0055] Example 1

[0056] This embodiment provides a method for preparing perylene diimide dimers with single-bonded tertiary amines or quaternary ammonium salts, and the synthetic route is shown below:

[0057] Method 1 for preparing a single-bonded tertiary amine-substituted perylene imide dimer (denoted as compound 1):

[0058]

[0059] The specific synthesis steps are as follows:

[0060] (1) Add 65 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of single-bonded perylene anhydride dimer;

[0061] (2) Inject 20 ml of N,N-dimethylformamide into the mixture prepared in step (1) and stir at 130 °C;

[0062] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 68 mg of a purple-red powder of a single-bonded tertiary amine-substituted perylene imide dimer with a yield of 96%.

[0063] Method 2 for preparing single-bonded tertiary amine-substituted perylene imide dimers (denoted as compound 1):

[0064]

[0065] The specific synthesis steps are as follows:

[0066] (1) Add 46 mg (1 eq) of monobromo-substituted perylene imide and 8.4 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of monoboron ester-substituted perylene imide monomer.

[0067] (2) Under nitrogen protection, inject 5 mL of saturated sodium carbonate solution and 15 mL of tetrahydrofuran into the mixture prepared in step (1), and stir at 70 °C.

[0068] (3) After reacting for 12 hours, the mixture was cooled and poured into water. It was then extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 73 mg of a purple-red powder of a single-bonded tertiary amine-substituted perylene imide dimer with a yield of 90%.

[0069] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.82-8.76 (m, 8H), 8.41 (d, 2H), 8.24 (s, 2H), 8 .16(d,2H),4.19-4.15(m,8H),2.43-2.39(m,8H),2.23(d,24H),1.88(m,8H). 13C NMR (CDCl3, 101MHz, 298K): δ = 163.3, 163.2 163.1 162.8, 162.7, 141.6 134.7, 134.6, 134.2, 134.1 133.1 131.9, 131.5 130.7, 129.9 129.1,128.7,128.6 127.7,127.3,124.3 124.1123.4,123.2,122.9,77.3,77.0,76.7,57.1,45.4,39.7,38.9,25.9.MS(MALDI-TOF(P),100%)m / z calcd for C 68 H 62 N8O8: 1118.5, found: 1118.4. TGA testing shows its thermal decomposition temperature is greater than 348℃, indicating good chemical stability.

[0070] Preparation method of single-bonded tertiary amine-substituted selenium-fused perylene imide dimers (denoted as compound 2):

[0071]

[0072] The specific synthesis steps are as follows:

[0073] (1) Add 54 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of single-bonded selenium-fused perylene anhydride dimer;

[0074] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0075] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 61 mg of single-bonded tertiary amine-substituted selenium-fused perylene imide dimer, with a yield of 90%.

[0076] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.82 (s, 2H), 8.73 (s, 2H), 8.33 (d, 2H), 7.89 (s, 2H), 7.6 2(d,2H),4.18-4.14(m,8H),2.44-2.38(m,8H),2.21-2.05(d,24H),1.78-1.58(m,8H); 13CNMR (CDCl3, 101MHz, 298K): δ = 159.0, 146.6, 141.3, 139.7, 136.9, 136.5, 132.0, 131.8, 130.4, 130 .3,127.4,127.2,126.3,124.2,123.8,123.5,122.4,28.4,23.3; MS(MALDI-TOF(P),100%)m / zcalcd for C 68 H 58 N8O8Se2:1274.27,found:1274.41.

[0077] Preparation method of single-bonded tertiary amine-substituted thiofused perylene imide dimers (denoted as compound 3):

[0078]

[0079] The specific synthesis steps are as follows:

[0080] (1) Add 60 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of a single-bonded thiofused perylene anhydride dimer;

[0081] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0082] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 68 mg of thiofused perylene diimide dimer with a single bond tertiary amine substitution, with a yield of 91%.

[0083] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.91 (s, 2H), 8.63 (s, 2H), 8.35 (d, 2H), 7.82 (s, 2H) ),7.73(d,2H),4.25-4.04(m,8H),2.33-2.18(m,8H),2.11(d,24H),1.68(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 160.1, 159.3, 137.8, 137.4, 131.4, 130.9, 129.8, 129.6, 129.2, 128.7, 1 28.1,126.6,124.5,123.4,58.7,56.4,56.1,49.5,47.0,36.2,28.3,26.0; MS(MALDI-TOF(P),100%)m / z calcd for C 68 H 58N8O8S2: 1178.4, found: 1178.7.

[0084] Preparation method of single-bonded quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 4) (reaction with haloalkanes):

[0085]

[0086] The specific synthesis steps are as follows:

[0087] (1) Add 49 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (1 eq) of single-bonded tertiary amine-substituted perylene imide dimer.

[0088] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0089] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 53 mg of purple powder and solid quaternary ammonium salt-substituted perylene imide dimer, with a yield of 76%.

[0090] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 9.20-9.16 (m, 4H), 8.78-8.71 (m, 4H), 8.55-8.53 (m, 2H), 8 .19-8.08(m,4H),4.10-4.05(m,8H),2.94-2.92(t,36H),2.06(m,8H),1.23-1.14(m,16H). 13 C NMR (DMSO-d6, 101MHz, 298K): δ = 163.0, 162.7, 162.5, 162.5, 162.0, 161.1, 143.1, 141. 3,141.1,138.6,138.2,135.3,134.6,134.4,133.7,131.1,130.6,128.4,126.6,126.1, 124.9,124.4,124.2,122.8,60.3,60.1,58.6,54.7,49.3,43.3,43.2,40.1,39.9,39.7, 39.5,39.3,39.1,38.9,37.1,36.7,36.4,25.3,21.1,7.84; MS(MALDI-TOF(P),100%)m / z calcd for C 76 H 82 Br4N8O8:1554.3,found:1554.6.

[0091] Preparation method of single-bonded quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 5) (oxidation with hydrogen peroxide):

[0092]

[0093] The specific synthesis steps are as follows:

[0094] (1) Add 50 mg (1 eq) of a single-bonded tertiary amine-substituted perylene imide dimer to the reaction flask and 25 mL of ethanol.

[0095] (2) Under nitrogen protection, slowly add 30 mg (20 eq) of hydrogen peroxide to the mixture in step (1) and stir at 80 °C;

[0096] (3) After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed by vacuum distillation. The crude product was purified to obtain 45 mg of purple solid quaternary ammonium salt-substituted perylene imide dimer, with a yield of 85%.

[0097] 1 H NMR (D2O, 400MHz, 298K,): δ = 8.64-7.64 (m, 14H), 7.23-6.58 (m, 8H), 3.43-2.87 (m, 40H); MS (MALDI-TOF (P), 100%) m / z calcd for C 68 H6N8O 12 :1182.5,found:1182.1.

[0098] Preparation method of single-bonded quaternary ammonium salt-substituted selenium-fused perylene imide dimers (denoted as compound 6) (reaction with haloalkanes):

[0099]

[0100] The specific synthesis steps are as follows:

[0101] (1) Add 42 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (leq) of single-bonded selenium-fused peryleneimide dimer.

[0102] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0103] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 54 mg of single-bonded quaternary ammonium salt-substituted selenium fused perylene imide dimer, with a yield of 81%.

[0104] 1H NMR (DMSO-d6, 400MHz, 298K): δ = 8.92 (s, 2H), 8.53 (s, 2H), 8.34 (d, 2H), 7.72 (s, 2H), 7.62(d,2H),4.11–4.06(m,8H),2.84-2.72(t,36H),2.01(m,8H),1.22-1.04(m,16H); 13 CNMR (DMSO-d6, 101MHz, 298K): δ = 159.3, 146.6, 138.6, 137.4, 134.7, 129.6, 129.3, 128. 7,126.1,124.2,123.1,61.5,60.3,52.3,41.4,19.7,7.70; MS(MALDI-TOF(P),100%)m / z calcd for C 76 H 78 Br4N8O8Se2:1710.1,found:1710.5.

[0105] Preparation method of single-bonded quaternary ammonium salt-substituted sulfur-fused perylene imide dimer (denoted as compound 7) (reaction with haloalkanes):

[0106]

[0107] The specific synthesis steps are as follows:

[0108] (1) Add 46 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (leq) of single-bonded thiofused perylene imide dimer.

[0109] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0110] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 54 mg of single-bonded quaternary ammonium salt-substituted sulfur-fused perylene imide dimer, with a yield of 79%.

[0111] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 9.12 (s, 2H), 8.93 (s, 2H), 8.24 (d, 2H), 7.71 (s, 2H), 7.63(d,2H),4.10-4.02(m,8H),2.94-2.82(t,36H),2.11(m,8H),1.23-1.04(m,16H); 13CNMR(DMSO-d6,101MHz,298K): δ=159.3,137.8,137.4,130.9,129.8,129.6,129.2,128.7, 128.1,126.1,124.5,123.4,61.5,60.3,52.2,41.4,18.7,6.2; MS(MALDI-TOF(P),100%)m / z calcd for C 76 H 78 Br4N8O8S2:1614.2,found:1614.3.

[0112] Example 2

[0113] This embodiment provides a method for preparing alkyne-linked tertiary amine or quaternary ammonium salt-substituted perylene imide dimers, and the synthetic route is shown below:

[0114] Preparation method 1 for alkyne-linked tertiary amine-substituted perylene imide dimers (denoted as compound 8):

[0115]

[0116] The specific synthesis steps are as follows:

[0117] (1) Add 127 mg (20 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of perylene-linked perylene anhydride dimer;

[0118] (2) Inject 20 ml of N,N-dimethylformamide into the mixture prepared in step (1) and stir at 130 °C;

[0119] (3) After reacting for 20 hours, the mixture was cooled, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified to obtain 68 mg of purplish-red powdery alkyne-linked tertiary amine-substituted perylene imide dimer, with a yield of 96%.

[0120] Method 2 for preparing alkyne-linked tertiary amine-substituted perylene imide dimers (referred to as compound 8):

[0121]

[0122] The specific synthesis steps are as follows:

[0123] (1) Add 11 mg (0.4 eq) of bis(trimethyltin)acetylene and 9 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of tertiary amine-substituted monobromoperyleneimide;

[0124] (2) Under nitrogen protection, inject 5 ml of toluene and 1 ml of N,N-dimethylformamide into the mixture prepared in step (1), and stir at 110°C.

[0125] (3) After reacting for 24 hours, the mixture was cooled, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified to obtain 80 mg of purple-red powdery alkyne-linked tertiary amine-substituted perylene imide dimer, with a yield of 90%.

[0126] 1 H NMR (CDCl3, 400MHz, 298K): δ=9.81-9.73(m,6H),8.39(d,2H),8.17-8.06(t,6H),4.36(s,8H),2.54-2.47(m,8H),2.28(d,24H),2.05-1.96(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ=167.6,167.5,167.2,164.5,164.0,139.6,139.5,133.9,133.7,133.4,133.3,125.4,125.3,1 25.2,125.1,121.4,121.2,121.1,120.5,61.7,61.4,61.3,56.2,56.1,47.2,47.0,38.2,26.5; MS(MALDI-TOF(P),100%)m / z calcd for C 70 H 62 N8O8:1142.4, found:1142.8.

[0127] TGA testing showed that its thermal decomposition temperature is greater than 385℃, indicating that it has good chemical stability.

[0128] Preparation method of alkyne-linked tertiary amine-substituted selenium-fused perylene imide dimers (denoted as compound 9):

[0129]

[0130] The specific synthesis steps are as follows:

[0131] (1) Add 53 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of acetylene-linked selenium-fused perylene anhydride dimer;

[0132] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0133] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 60 mg of alkyne-linked tertiary amine-substituted selenium-fused perylene imide dimer, with a yield of 89%.

[0134] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.82 (s, 2H), 8.73 (s, 2H), 8.33 (d, 2H), 7.89 (s, 2H) ),7.62(d,2H),4.13-4.04(m,8H),2.34-2.28(m,8H),2.25(d,24H),1.44(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 165.1, 159.4, 153.2 151.8,146.6,141.1,138.6,134.2,133.8,132.7,129.0,126.1,125.7,124 .2,123.9,122.8,93.3,58.7,56.4,47.0,26.0; MS(MALDI-TOF(P),100%)m / z calcd for C 70 H 58 N8O8Se2:1298.2,found:1298.3.

[0135] Preparation method of alkyne-linked tertiary amine-substituted thiofused perylene imide dimers (denoted as compound 10):

[0136]

[0137] The specific synthesis steps are as follows:

[0138] (1) Add 59 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of thiol-linked perylene-fused perylene anhydride dimer;

[0139] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0140] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 61 mg of thiamide-substituted tertiary amine-linked perylene imide dimer, with a yield of 88%.

[0141] 1H NMR (CDCl3, 400MHz, 298K): δ = 9.52 (s, 2H), 8.93 (s, 2H), 8.33 (d, 2H), 7.25 (s, 2H) ),7.14(d,2H),4.52-4.34(m,8H),2.34-2.28(m,8H),2.13(d,24H),1.34(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 158.6, 147.3, 137.8, 130.9, 129.2, 125.7, 124.3, 112.3, 57.3, 56.4, 45.3, 25.3; MS (MALDI-TOF (P), 100%) m / z calcd for C 78 H 58 N8O8S2:1202.4, found:1202.3.

[0142] Preparation method of alkyne-linked quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 11) (reaction with haloalkanes):

[0143]

[0144] The specific synthesis steps are as follows:

[0145] (1) Add 95 mg (20 eq) of bromoethane to a reaction flask containing 50 mg (1 eq) of alkyne-linked tertiary amine-substituted perylene imide dimer;

[0146] (2) Add 8 ml of tetrahydrofuran and 4 ml of N,N-dimethylformamide to the mixture prepared in step (1), and stir in the dark at room temperature;

[0147] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 52 mg of red powdery alkyne-linked quaternary ammonium salt-substituted perylene imide dimer with a yield of 76%.

[0148] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 9.84-9.76 (m, 4H), 9.0 (d, 2H), 8.52 (d, 2H), 8.27-8.22 (m, 6H),4.41(m,8H),3.15-3.08(m,32H),2.80-2.74(m,8H),2.25(d,8H),1.26-1.17(m,12H); 13C NMR (DMSO--d6, 101MHz, 298K): δ=165.4,164.2,163.6,163.0,143.4,143.1,139.0,138.6,135.8,134.4,127.6,127.1,125.2, 124.8,124.4,96.7,95.5,65.5,63.0,63.1,45.1,43.5,39.1,38.9,38.6,24.6,23.2,21.5,7.88; MS(MALDI-TOF(P),100%)m / z calcd for C 70 H 62 N8O8:1578.2, found:1578.5.

[0149] Preparation method of alkyne-linked quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 12) (oxidation with hydrogen peroxide):

[0150]

[0151] The specific synthesis steps are as follows:

[0152] (1) 50 mg (1 eq) of alkyne-linked tertiary amine-substituted perylene imide dimer was loaded into a reaction flask;

[0153] (2) Under nitrogen protection, inject 30 mg (20 eq) of hydrogen peroxide and 5 ml of anhydrous ethanol into the mixture prepared in step (1), and stir at 80 °C.

[0154] (3) After reacting for 3 hours, the mixture was cooled and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 37 mg of red powdery alkyne-linked quaternary ammonium salt-substituted perylene imide dimer, with a yield of 70%.

[0155] 1 H NMR (D2O, 400MHz, 298K): δ = 9.72-8.16 (m, 14H), 4.47-3.96 (m, 8H), 3.43-2.58 (m, 32H), 2.01-1.74 (m, 8H); MS (MALDI-TOF (P), 100%) m / z calcd for C 70 H 62 N8O 12 :1206.4,found:1206.8.

[0156] Preparation method of alkyne-linked quaternary ammonium salt-substituted selenium-fused perylene imide dimers (designated as compound 13) (reaction with haloalkanes):

[0157]

[0158] The specific synthesis steps are as follows:

[0159] (1) Add 41 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (1 eq) of alkyne-linked tertiary amine-substituted double-sided selenium atom-fused perylene imide dimer.

[0160] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0161] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 54 mg of quaternary ammonium salt-substituted double-sided selenium atom-fused perylene imide dimer, with a yield of 81%.

[0162] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 9.12 (s, 2H), 8.77 (s, 2H), 8.24 (d, 2H), 7.35 (s, 2H), 7.11(d,2H),4.21-4.11(m,8H),2.56-2.39(t,36H),2.23(m,8H),1.25-1.14(m,16H); 13 CNMR(DMSO-d6,101MHz,298K): δ=162.3,158.7,141.3,140.2,139.8,138.6, 125.7,123.3,91.2,60.8,52.1,10.8,18.6,7.5; MS(MALDI-TOF(P),100%)m / z calcd forC 78 H 78 Br4N8O8Se2:1734.1,found:1734.2.

[0163] Preparation method of alkyne-linked quaternary ammonium salt-substituted thiofused perylene imide dimers (designated as compound 14) (reaction with haloalkanes):

[0164]

[0165] The specific synthesis steps are as follows:

[0166] (1) Add 455 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (leq) of alkyne-linked tertiary amine-substituted double sulfur atom fused perylene imide dimer.

[0167] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0168] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 54 mg of perylene imide dimer substituted with double sulfur atom quaternary ammonium salt, with a yield of 79%.

[0169] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 8.82 (s, 2H), 8.36 (s, 2H), 8.14 (d, 2H), 7.52 (s, 2H), 7.38(d,2H),4.58–4.46(m,8H),2.34-2.12(t,36H),2.05(m,8H),1.12-1.04(m,16H); 13 CNMR(DMSO-d6,101MHz,298K): δ=162.2,156.5,149.3,138.3,131.2,129.5,129 .2,128.4,122.3,92.3,61.6,53.3,44.5,18.4,7.5; MS(MALDI-TOF(P),100%)m / z calcd forC 78 H 78 Br4N8O8S2:1638.2,found:1638.3.

[0170] Example 3

[0171] This embodiment provides a method for preparing perylene imide dimers with benzene-bridged tertiary amines or quaternary ammonium salts, and the synthetic route is shown below:

[0172] Method 1 for preparing benzene-bridged tertiary amine-substituted perylene imide dimers (denoted as compound 15):

[0173]

[0174] The specific synthesis steps are as follows:

[0175] (1) Add 60 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of benzo[i]perylene anhydride dimer;

[0176] (2) Inject 20 ml of N,N-dimethylformamide into the mixture prepared in step (1) and stir at 130 °C;

[0177] (3) After reacting for 24 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 63 mg of solid benzene-bridged tertiary amine-substituted perylene imide dimer, with a yield of 91%.

[0178] Method 2 for preparing benzene-bridged tertiary amine-substituted perylene imide dimers (denoted as compound 15):

[0179]

[0180] The specific synthesis steps are as follows:

[0181] (1) Add 6.5 mg (0.5 eq) of 1,4-phenyldiboronic acid and 9 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of monobromosubstituted perylene imide;

[0182] (2) Under nitrogen protection, inject 2.5 mL of saturated sodium carbonate solution and 5 mL of tetrahydrofuran into the mixture prepared in step (1), and stir at 80 °C.

[0183] (3) After reacting for 12 hours, the mixture was cooled and poured into water. It was then extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 81 mg of solid benzene-bridged tertiary amine-substituted perylene imide dimer, with a yield of 87%.

[0184] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.51-8.47 (m, 6H), 8.17-8.12 (m, 6H), 7.85 (s, 2H), 7.34 (s,4H),4.13-4.08(m,8H),2.35-2.29(m,8H),2.17-2.08(m,24H),1.82-1.79(m,8H); 13 CNMR (CDCl3, 101MHz, 298K): δ = 159.6, 159.4, 159.3, 140.9, 140.5, 137.7, 1 36.4,135.7,135.3,135.1,134.5,134.2,133.9,133.2,132.7,132.5,131.4 ,130.9,129.3,128.3,127.2,126.9,126.6,126.1,124.4,59.7,59.3,59.0, 58.4,56.4,48.1,47.2,46.8,46.3,26.5,26.3; MS(MALDI-TOF(P),100%)m / z calcd for C 74 H6N8O8:1194.5, found:1193.9.

[0185] TGA testing showed that its thermal decomposition temperature is greater than 387℃, indicating that it has good chemical stability.

[0186] Preparation method of benzene-bridged tertiary amine-substituted selenium-fused perylene imide dimers (designated as compound 16):

[0187]

[0188] The specific synthesis steps are as follows:

[0189] (1) Add 50 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of benzene-bridged selenium-fused perylene anhydride dimer;

[0190] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0191] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 58 mg of benzene-bridged tertiary amine-substituted selenium-fused perylene imide dimer, with a yield of 87%.

[0192] 1 H NMR (CDCl3, 400MHz, 298K): δ = 9.32 (s, 2H), 8.63 (s, 2H), 8.43 (d, 2H), 7.85 (s, 2H), 7.72 (d, 2H) ),7.33(d,2H),7.12(d,2H),4.13-4.04(m,8H),2.34-2.28(m,8H),2.25(d,24H),1.44(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 158.4, 146.6, 140.9, 138.6, 137.4, 134.2, 129.3, 129.2, 12 8.2,127.2,126.6,124.2,123.1,8.7,56.4,47.0,26.3; MS(MALDI-TOF(P),100%)m / zcalcd for C 74 H 62 N8O8Se2:1350.3,found:1350.6.

[0193] Preparation method of benzene-bridged quaternary ammonium salt-substituted perylene imide dimers (designated as compound 17) (reaction with haloalkanes):

[0194]

[0195] The specific synthesis steps are as follows:

[0196] (1) Add 46 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (1 eq) of benzene-bridged tertiary amine-substituted peryleneimide dimer.

[0197] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0198] (3) After 3 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 49 mg of purple powder and solid quaternary ammonium salt-substituted perylene imide dimer, with a yield of 72%.

[0199] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 8.78-8.73 (m, 8H), 8.27 (d, 4H), 8.06 (s, 2H), 7.87 (m, 2H), 7.32(s,2H),4.21-4.17(m,8H),3.57-3.53(m,40H),2.24-2.18(m,8H),1.29-1.27(t,12H); 13 C NMR (DMSO-d6, 101MHz, 298K): δ = 162.4, 161.2, 159.7, 159.5, 159.3 145.6, 145.4, 145.3, 14 2.1,141.9,141.5,140.9,140.4,140.3,140.1,138.2,138.0,137.9,137.5,137.4,132.7, 131.4,130.9,130.5,129.6,129.2,128.5,128.1,127.2,126.3,125.6,124.7,124.5,123. 5,67.8,65.3,61.5,60.4,52.3,42.6,42.3,40.1,20.2,9.85; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 86 Br4N8O8:1630.3,found:1630.5.

[0200] Preparation method of benzene-bridged quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 18) (oxidation with hydrogen peroxide):

[0201]

[0202] The specific synthesis steps are as follows:

[0203] (1) Add 50 mg (1 eq) of benzene-bridged tertiary amine-substituted perylene imide dimer and 25 mL of ethanol to the reaction flask;

[0204] (2) Under nitrogen protection, slowly add 28 mg (20 eq) of hydrogen peroxide to the mixture from step (1) and stir at 80 °C;

[0205] (3) After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed by vacuum distillation. The crude product was purified to obtain 43 mg of purple solid quaternary ammonium salt-substituted perylene imide dimer, with a yield of 82%.

[0206] 1 H NMR (D2O, 400MHz, 298K): δ = 8.54-8.03 (m, 8H), 7.56-7.21 (m, 10H), 3.72-3.04 (m, 48H); MS (MALDI-TOF (P), 100%) m / z calcd for C 74 H 66 N8O 12 :1258.5,found:1259.1.

[0207] Preparation method of benzene-bridged quaternary ammonium salt-substituted selenium-fused perylene imide dimers (designated as compound 19) (reaction with haloalkanes):

[0208]

[0209] The specific synthesis steps are as follows:

[0210] (1) Add 40 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (1 eq) of benzene-bridged selenium-fused peryleneimide dimer.

[0211] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0212] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 51 mg of benzene-bridged quaternary ammonium salt-substituted selenium-fused perylene imide dimer, with a yield of 77%.

[0213] 1H NMR (DMSO-d6, 400MHz, 298K): δ = 8.82 (s, 2H), 8.36 (s, 2H), 8.14 (d, 2H), 7.52 (s, 2H), 7.38 (d, 2H), 7.22(d,2H),7.12(d,2H),4.62-4.56(m,8H),2.14-2.08(t,36H),1.92(m,8H),1.56-1.35(m,16H); 13 C NMR (DMSO-d6, 101MHz, 298K): δ = 156.6, 155.3, 146.2, 138.6, 137.5, 135.6, 134.7, 134.2, 1 29.2,128.3,128.1,122.6,120.3,60.2,56.8,41.4,25.6,8.7; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 82 Br4N8O8Se2:1784.13,found:1784.25.

[0214] Example 4

[0215] This embodiment provides a method for preparing thiophene-bridged tertiary amine or quaternary ammonium salt-substituted perylene imide dimers, and the synthetic route is shown below:

[0216] Method 1 for preparing thiophene-bridged tertiary amine-substituted perylene imide dimers (denoted as compound 20):

[0217]

[0218] The specific synthesis steps are as follows:

[0219] (1) Add 121 mg (20 eq) of an amine with a tertiary amine-substituted end group to a reaction flask containing 50 mg (1 eq) of thiophene-bridged tertiary amine-substituted perylene anhydride dimer;

[0220] (2) Inject 20 ml of N,N-dimethylformamide into the mixture prepared in step (1) and stir at 130 °C;

[0221] (3) After reacting for 13 hours, the mixture was cooled, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified to obtain 60 mg of orange-red powder of thiophene-bridged tertiary amine-substituted perylene imide dimer, with a yield of 87%.

[0222] Method 2 for preparing thiophene-bridged tertiary amine-substituted perylene imide dimers (denoted as compound 20):

[0223]

[0224] The specific synthesis steps are as follows:

[0225] (1) Add 13 mg (0.4 eq) of 2,5-bis(trimethyltinyl)thiophene and 9 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of tertiary amine-substituted monobromoperylimide.

[0226] (2) Under nitrogen protection, inject 10 ml of toluene and 5 ml of N,N-dimethylformamide into the mixture prepared in step (1), and stir at 110°C.

[0227] (3) After reacting for 24 hours, the mixture was cooled and poured into water. It was then extracted with dichloromethane, the extract was concentrated, the solvent was removed, and the crude product was separated and purified to obtain 78 mg of thiophene-bridged tertiary amine-substituted perylene imide dimer in purple-red powder form, with a yield of 83%.

[0228] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.73-8.64 (m, 8H), 8.28-8.23 (m, 4H), 7.93 (d, 2H), 7.57-7 .51(t,2H),4.38-4.33(m,8H),2.55-2.49(m,8H),2.36-2.27(m,24H),1.85-1.80(m,8H); 13 CNMR (CDCl3, 101MHz, 298K): δ=167.4,165.8,165.4,165.0,164.9,163.6,148.4,145.8,137.6,135.5,135.2,134.1,126.6 ,126.4,125.3,123.4,76.3,75.4,64.7,63.6,63.2,62.4,59.3,58.3,47.2,46.7,28.5,27.6; MS(MALDI-TOF(P),100%)m / z calcdfor C 72 H 64 N8O8S:1200.4, found:1200.8.

[0229] TGA testing showed that its thermal decomposition temperature is greater than 380℃, indicating that it has good chemical stability.

[0230] Preparation method of thiophene-bridged tertiary amine-substituted thio-fused perylene imide dimers (denoted as compound 21):

[0231]

[0232] The specific synthesis steps are as follows:

[0233] (1) Add 55 mg (10 eq) of an amine with a tertiary amine end group to a reaction flask containing 50 mg (1 eq) of thiophene-bridged thio-fused perylene anhydride dimer;

[0234] (2) Inject 20 ml of DMF into the mixture prepared in step (1) and stir at 130 °C;

[0235] (3) After reacting for 20 hours, the mixture was cooled to room temperature, extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 60 mg of thiophene-bridged tertiary amine-substituted sulfur-fused perylene imide dimer, with a yield of 88%.

[0236] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.92 (s, 2H), 8.53 (s, 2H), 8.42 (d, 2H), 7.95 (s, 2H), 7.62 (d,2H),7.35(d,2H),4.13-4.04(m,8H),2.34-2.28(m,8H),2.25(d,24H),1.44(m,8H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 158.4, 146.6, 140.9, 138.6, 137.4, 134.2, 129.3, 129.2, 128.2,127.2,126.6,124.2,,123.1,8.7,56.4,47.0,26.3; MS(MALDI-TOF(P),100%)m / z calcd for C 72 H 60 N8O8S3:1260.4, found:1260.6.

[0237] Preparation method of thiophene-bridged quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 22) (reaction with haloalkanes):

[0238]

[0239] The specific synthesis steps are as follows:

[0240] (1) Add 91 mg (20 eq) of bromoethane to a reaction flask containing 50 mg of thiophene-bridged tertiary amine-substituted perylene imide dimer;

[0241] (2) Add 8 ml of tetrahydrofuran and 4 ml of N,N-dimethylformamide to the mixture prepared in step (1) and stir in the dark at room temperature;

[0242] (3) After 2 days of reaction, the solvent was removed by vacuum distillation, and the crude product was separated and purified to obtain 52 mg of dark red powder of thiophene-bridged quaternary ammonium salt-substituted perylene imide dimer, with a yield of 76%.

[0243] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 8.68-8.65 (d, 2H), 8.35-8.32 (m, 4H), 8.17-8.12 (m, 8H), 7.55 (s, 2H) ),4.41-4.25(m,8H),2.57-2.42(m,16H),2.43-2.36(m,24H),1.84-1.78(m,8H),1.27-1.22(m,12H); 13 C NMR (DMSO-d6, 101MHz, 298K): δ = 163.5, 163.2.160.7, 144.2, 142.1, 142.0, 137.6, 137.3, 132.9, 131.5, 131.2, 130.8, 12 8.8,128.4,126.5,124.3,76.8,75.6,68.9,68.4,60.7,60.2,58.7,58.2,27.3,27.1,10.8; MS(MALDI-TOF(P),100%)m / z calcd for C 80 H 84 Br4N8O8S:1636.2,found:1636.5.

[0244] Preparation method of thiophene-bridged quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 23) (oxidation with hydrogen peroxide):

[0245]

[0246] The specific synthesis steps are as follows:

[0247] (1) 50 mg of thiophene-bridged tertiary amine-substituted perylene imide dimer was loaded into a reaction flask;

[0248] (2) Under nitrogen protection, inject 28 mg (20 eq) of hydrogen peroxide and 10 ml of anhydrous ethanol into the reaction flask of step (1), and stir at 80 °C.

[0249] (3) After reacting for 3 hours, the mixture was cooled and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 38 mg of red powder thiophene-bridged quaternary ammonium salt-substituted perylene imide dimer, with a yield of 72%.

[0250] 1H NMR (D2O, 400MHz, 298K): δ = 8.56-8.47 (m, 8H), 8.16-8.04 (m, 8H), 4.39-4.32 (m,8H),3.05-2.94(m,32H),2.26-2.23(m,8H);MS(MALDI-TOF(P),100%)m / z calcd forC 80 H 84 Br4N8O8S:1264.4,found:1264.7.

[0251] Preparation method of thiophene-bridged quaternary ammonium salt-substituted sulfur-fused perylene imide dimers (designated as compound 24) (reaction with haloalkanes):

[0252]

[0253] The specific synthesis steps are as follows:

[0254] (1) Add 43 mg (10 eq) of bromoethane, 25 mL of N,N-dimethylformamide, and 12 mL of tetrahydrofuran to a reaction flask containing 50 mg (leq) of thiophene-bridged tertiary amine-substituted thiosulfate-fused perylene imide dimer.

[0255] (2) Stir the mixture prepared in step (1) at room temperature under dark conditions;

[0256] (3) After 2 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 53 mg of thiophene-bridged quaternary ammonium salt-substituted sulfur-fused perylene imide dimer, with a yield of 80%.

[0257] 1 H NMR (DMSO-d6, 400MHz, 298K): δ = 9.12 (s, 2H), 8.77 (s, 2H), 8.24 (d, 2H), 7.80 (s, 2H), 7.35 (s ,2H),7.11(d,2H),3.21-3.01(m,8H),2.38-2.29(t,36H),2.15(m,8H),1.15-1.04(m,16H); 13 C NMR (DMSO-d6, 101MHz, 298K): δ = 160.1, 138.2, 137.3, 132.4, 130.9, 130.8, 129. 2,128.4,125.3,61.2,60.5,49.7,38.2,18.6,7.8; MS(MALDI-TOF(P),100%)m / z calcd for C 80 H 80Br4N8O8S3:1696.20,found:1696.18.

[0258] Example 5

[0259] This embodiment provides a method for preparing perylene diimide dimers containing two nitrogen atoms and linked by a single bond, the synthetic route of which is shown below:

[0260] Method 1 for preparing a single-bonded perylene imide dimer containing two nitrogen atoms and substituted with tertiary amines (denoted as compound 25):

[0261]

[0262] The specific synthesis steps are as follows:

[0263] (1) Add 102 mg (10 eq) of a tertiary amine containing two nitrogen atoms to a reaction flask containing 50 mg (1 eq) of single-bonded perylene anhydride dimer;

[0264] (2) Inject 25 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0265] (3) After reacting for 3 days, the mixture was cooled to room temperature and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 79 mg of solid perylene imide dimer with two nitrogen atoms in a single bond and substituted with tertiary amines. The yield was 92%.

[0266] Method 2 for preparing a single-bonded perylene imide dimer containing two nitrogen atoms and substituted with tertiary amines (denoted as compound 25):

[0267]

[0268] The specific synthesis steps are as follows:

[0269] (1) Add 47 mg (1 eq) of monobromo-substituted perylene imide monomer and 8 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of tertiary amine-substituted perylene imide monomer containing two nitrogen atoms.

[0270] (2) Under nitrogen protection, inject 5 mL of saturated sodium carbonate solution and 15 mL of tetrahydrofuran into the mixture prepared in step (1), and stir at 70 °C.

[0271] (3) After reacting for 12 hours, the mixture was cooled and poured into water. It was then extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 71 mg of a purple-red powder of a single-bonded tertiary amine-substituted perylene imide dimer, with a yield of 85%.

[0272] 1H NMR (CDCl3, 400MHz, 298K): δ=8.57-8.54(m,8H),8.23(d,2H),8.17(s,2H),7.85(s,2H),4.16- 4.13(m,16H),2.81-2.78(m,16H),2.38-2.36(m,8H),2.17-2.14(d,24H),1.62-1.58(m,20H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 161.7, 161.5, 161.1, 160.5, 160.4, 160.2, 140.4,140.1,139.8,135.3,135.2,1135.1,132.4,132.2,131.7,130.9,1 30.7,130.5,130.2,129.7,129.4,126.5,126.1,124.5,123.4,122.9,60 .2,59.6,59.3,47.3,46.8,46.3,29.6,26.5; MS(MALDI-TOF(P),100%)m / z calcd for C 80 H 90 N 12 O8:1346.7,found:1346.6.

[0273] TGA testing showed that its thermal decomposition temperature is greater than 392℃, indicating that it has good chemical stability.

[0274] Preparation method of a single-bonded selenium-fused perylene imide dimer compound containing two nitrogen atoms and substituted with tertiary amines (denoted as compound 26):

[0275]

[0276] The specific synthesis steps are as follows:

[0277] (1) Add 169 mg (20 eq) of a tertiary amine containing two nitrogen atoms to a reaction flask containing 50 mg (1 eq) of a single-bonded selenium-fused perylene imide dimer;

[0278] (2) Inject 10 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0279] (3) After three days of reaction, the mixture was cooled and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 73 mg of selenium-fused perylene imide dimer with two nitrogen atoms in a single bond tertiary amine substituted by a single bond, with a yield of 91%.

[0280] 1H NMR (CDCl3, 400MHz, 298K): δ = 8.92 (s, 2H), 8.43 (s, 2H), 8.37 (d, 2H), 7.52 (s, 2H), 7.13 (d, 2H), 4 .25-4.18(t,8H),3.25-2.55(m,24H),2.05-1.93(m,24H),1.68-1.38(m,16H),1.28-1.19(m,4H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 159.7, 138.6, 134.2, 134.1, 133.8, 128.8, 128.6, 125.6 ,125.3,124.8,123.9,56.8,55.9,35.6,34.5,28.7,23.5; MS(MALDI-TOF(P),100%)m / z calcd for C 80 H 86 N 12 O8Se2:1502.5,found:1502.8.

[0281] Preparation method of a single-bonded tertiary amine-substituted thiofused perylene imide dimer compound containing two nitrogen atoms:

[0282]

[0283] The specific synthesis steps are as follows:

[0284] (1) Add 189 mg (20 eq) of a tertiary amine containing two nitrogen atoms to a reaction flask containing 50 mg (1 eq) of a single-bonded sulfur-fused perylene anhydride dimer;

[0285] (2) Inject 10 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0286] (3) After three days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 75 mg of thiofused perylene imide dimer with two nitrogen atoms in a single bond tertiary amine substituted by a single bond, with a yield of 90%.

[0287] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.91 (s, 2H), 8.53 (s, 2H), 8.35 (d, 2H), 7.62 (s, 2H), 7.73 (d, 2H), 4 .15-4.08(t,8H),3.35-2.38(m,24H),2.15-2.03(m,24H),1.78-1.58(m,16H),1.25-1.15(m,4H); 13C NMR (CDCl3, 101MHz, 298K): δ = 158.7, 138.6, 135.2, 134.1, 133.5, 129.8, 128.6, 127.6 ,125.3,124.4,123.1,59.8,58.9,36.6,33.5,29.7,25.5; MS(MALDI-TOF(P),100%)m / z calcd for C 80 H 86 N 12 O8S2:1406.6,found:1406.3.

[0288] Example 6

[0289] This embodiment provides a method for preparing alkyne-linked perylene imide dimers containing two nitrogen atoms and substituted with tertiary amines. The synthetic route is shown below:

[0290] Method 1 for preparing a perylene-linked, two-nitrogen, tertiary amine-substituted perylene imide dimer (denoted as compound 28):

[0291]

[0292] The specific synthesis steps are as follows:

[0293] (1) Add 197 mg (20 eq) of a tertiary amine containing two nitrogen atoms to a reaction flask containing 50 mg (1 eq) of alkyne-linked perylene anhydride dimer;

[0294] (2) Inject 10 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0295] (3) After three days of reaction, the mixture was cooled and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 79 mg of purple powder-like perylene-linked tertiary amine-substituted perylene imide dimer containing two nitrogen atoms, with a yield of 93%.

[0296] Method 2 for preparing a perylene-linked, two-nitrogen, tertiary amine-substituted perylene imide dimer (denoted as compound 28):

[0297]

[0298] The specific synthesis steps are as follows:

[0299] (1) Add 9 mg (0.4 eq) of bis(trimethyltin)acetylene and 8 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of a tertiary amine-substituted monobromoperyleneimide containing two nitrogen atoms.

[0300] (2) Under nitrogen protection, inject 10 ml of toluene and 2 ml of N,N-dimethylformamide into the mixture prepared in step (1), and stir at 110°C.

[0301] (3) After reacting for 24 hours, the mixture was cooled, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was purified by silica gel column chromatography to obtain 73 mg of red powdery perylene-linked tertiary amine-substituted perylene imide dimer containing two nitrogen atoms, with a yield of 80%.

[0302] 1 H NMR (CDCl3, 400MHz, 298K): δ = 9.78-9.72 (m, 6H), 8.45 (d, 2H), 8.26-8.11 (t, 6H), 4.45-4. 34(m,8H),2.87-2.77(m,24H),2.55-2.44(m,24H),2.17-2.10(m,8H),1.92-1.84(m,12H); 13 C NMR (CDCl3, 101MHz, 298K): δ=162.4,162.0,155.6,154.7,153.4,149.2,147.0,146.3,146.1,143.3,136.5,134.5,133.9,130.6,12 5.5,124.1,123.6,123.2,121.5,97.4,97.2,68.5,65.8,58.2,56.7,48.6,46.7,45.4,38.8,36.9,28.3; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 90 N 12 O8:1370.7,found:1370.1.

[0303] TGA testing showed that its thermal decomposition temperature is greater than 380℃, indicating that it has good chemical stability.

[0304] Preparation method of a selenium-fused perylene imide dimer compound containing two nitrogen atoms and substituted with a tertiary amine (designated as compound 29):

[0305]

[0306] The specific synthesis steps are as follows:

[0307] (1) Add 150 mg (20 eq) of a tertiary amine containing two nitrogen atoms to a reaction flask containing 50 mg (1 eq) of acetylene-linked selenium-fused perylene anhydride dimer;

[0308] (2) Inject 10 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0309] (3) After three days of reaction, the mixture was cooled and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 73 mg of tertiary amine-substituted selenium fused perylene imide dimer with two nitrogen atoms, with a yield of 92%.

[0310] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.89 (s, 2H), 8.43 (s, 2H), 8.26 (d, 2H), 7.52 (s, 2H), 7.33 (d, 2H), 4 .09-4.02(t,8H),3.25-2.18(m,24H),2.16-1.92(m,24H),1.68-1.38(m,16H),1.35-1.15(m,4H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 156.7, 148.6, 138.2, 135.1, 133.8, 128.8, 127.6, 126.6 ,125.4,123.4,123.1,58.8,58.7,35.6,33.8,28.7,24.5; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 86 N 12 O8Se2:1527.5,found:1527.4.

[0311] Example 7

[0312] This embodiment provides a method for preparing single-bonded quaternary ammonium salt-substituted perylene imide dimers, the synthetic route of which is shown below:

[0313] Method 1 for preparing a single-bonded quaternary ammonium salt-substituted perylene imide dimer (denoted as compound 30):

[0314]

[0315] The specific synthesis steps are as follows:

[0316] (1) Add 143 mg (10 eq) of a quaternary ammonium salt-substituted amine with a sulfonate end group to a reaction flask containing 50 mg (1 eq) of single-bonded perylene anhydride dimer;

[0317] (2) Inject 25 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0318] (3) After reacting for 3 days, the mixture was cooled to room temperature and the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 83 mg of solid perylene imide dimer with sulfonate-terminated quaternary ammonium salts and single bonded end groups, with a yield of 81%.

[0319] Method 2 for preparing single-bonded quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 30):

[0320]

[0321] The specific synthesis steps are as follows:

[0322] (1) Add 48 mg (1 eq) of monobromo-substituted quaternary ammonium salt perylene imide with sulfonate end groups and 7 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of monoboron ester-substituted quaternary ammonium salt perylene imide with sulfonate end groups.

[0323] (2) Under nitrogen protection, inject 5 mL of saturated sodium carbonate solution and 15 mL of tetrahydrofuran into the mixture prepared in step (1), and stir at 70 °C.

[0324] (3) After reacting for 12 hours, the mixture was cooled and poured into water. It was then extracted with dichloromethane, concentrated, and the crude product was separated and purified to obtain 67 mg of a purple-red powder of a single-bonded tertiary amine-substituted perylene imide dimer, with a yield of 78%.

[0325] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.47 (d, 4H), 8.25 (s, 2H), 7.93-7, 91 (m, 6H), 7.74 (s, 2H), 4. 35-4.32(m,8H),2.56-2.53(m,16H),2.31-2.27(m,24H),1.81(d,8H),1.55-1.51(m,16H); 13C NMR (CDCl3, 101MHz, 298K): δ = 159.7, 159.3, 159.0, 142.5, 142.1, 139.6, 139.4, 139.1 ,138.5,137.2,136.8,136.4,136.3,135.7,130.4,129.6,129.4,129.1,128.7,128.4 ,128.2,127.5,126.3,125.9,125.6,124.7,124.2,123.6,123.4,123.1,62.4,62.1,5 8.7,58.3,57.4,45.4,43.2,41.7,40.2,25.8,21.6; MS(MALDI-TOF(P),100%)m / zcalcd for C 80 H 86 N8O 20 S4: 1606.5, found: 1606.8.

[0326] TGA testing showed that its thermal decomposition temperature is greater than 380℃, indicating that it has good chemical stability.

[0327] Preparation method of single-bonded quaternary ammonium salt-substituted selenium-fused perylene imide dimers (denoted as compound 31):

[0328]

[0329] The specific synthesis steps are as follows:

[0330] (1) Add 239 mg (20 eq) of a quaternary ammonium salt-substituted amine with a sulfonate end group to a reaction flask containing 50 mg (1 eq) of single-bonded selenium-fused perylene anhydride dimer;

[0331] (2) Inject 20 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0332] (3) After 3 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 81 mg of a selenium-fused perylene imide dimer compound with a sulfonate quaternary ammonium salt substituted with a single bond end group, with a yield of 86%.

[0333] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.82 (s, 2H), 8.73 (s, 2H), 8.33 (d, 2H), 7.89 (s, 2H), 7.62 (d,2H),4.36-4.27(m,8H),2.95-2.84(m,40H),1.97-1.93(m,8H),1.75-1.68(m,16H); 13C NMR (CDCl3, 101MHz, 298K): δ = 161.5, 156.2, 152.5, 149.6, 144.8, 138.2, 137.3, 133.4, 132.5, 130. 2,126.7,125.6,90.5,85.5,60.9,56.3,55.4,45.9,35.8,23.3; MS(MALDI-TOF(P),100%)m / zcalcd for C 80 H 82 N8O 20 S4Se2:1762.29,found:1762.73.

[0334] Example 8

[0335] This embodiment provides a method for preparing two alkyne-linked quaternary ammonium salt-substituted perylene imide dimers, and the synthetic route is shown below:

[0336] Method 1 for preparing alkyne-linked quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 32):

[0337]

[0338] The specific synthesis steps are as follows:

[0339] (1) Add 277 mg (20 eq) of a quaternary ammonium salt-substituted amine with a sulfonate end group to a reaction flask containing 50 mg (1 eq) of alkyne-linked perylene anhydride dimer;

[0340] (2) Inject 20 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0341] (3) After 3 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 87 mg of red powder perylene-substituted quaternary ammonium salt dimer compound with sulfonate-linked end groups. The yield was 86%.

[0342] Method 2 for preparing alkyne-linked quaternary ammonium salt-substituted perylene imide dimers (denoted as compound 32):

[0343]

[0344] The specific synthesis steps are as follows:

[0345] (1) Add 8 mg (0.4 eq) of bis(trimethyltin)acetylene and 7 mg (0.1 eq) of tetratriphenylphosphine palladium to a reaction flask containing 50 mg (1 eq) of quaternary ammonium salt-substituted monobromoperylene imide with sulfonate end group;

[0346] (2) Add 15 ml of toluene and 3 ml of N,N-dimethylformamide to the mixture prepared in step (1) and stir at 110°C;

[0347] (3) After reacting for 24 hours, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 71 mg of a red powder of perylene-terminated quaternary ammonium salt-substituted perylene imide dimer with sulfonate groups, with a yield of 77%.

[0348] 1 H NMR (CDCl3, 400MHz, 298K): δ = 9.77-9.73 (m, 6H), 8.36 (d, 2H), 8.23-8.18 (m, 6H) ,4.43-4.37(m,8H),2.96-2.84(m,40H),1.95-1.92(m,8H),1.80-1.76(m,16H); 13 C NMR (CDCl3, 101MHz, 298K): δ=167.8,166.7,158.2,154.7,148.2,145.2,136.7,135.7,134.1,133.4,131.5,129.2 ,128.1,126.2,96.8,96.2,78.6,78.0,64.8,58.7,57.8,57.2,27.5,25.6,20.2,12.7; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 86 N8O 20 S4:1630.4, found:1630.7.

[0349] TGA testing showed that its thermal decomposition temperature is greater than 376℃, indicating that it has good chemical stability.

[0350] Preparation method of alkyne-linked quaternary ammonium salt-substituted selenium-fused perylene imide dimers (denoted as compound 33):

[0351]

[0352] The specific synthesis steps are as follows:

[0353] (1) Add 233 mg (20 eq) of a quaternary ammonium salt-substituted amine with a sulfonate end group to a reaction flask containing 50 mg (1 eq) of acetylene-linked selenium-fused perylene anhydride dimer;

[0354] (2) Inject 20 ml of methanol into the mixture prepared in step (1) and stir at 65°C;

[0355] (3) After 3 days of reaction, the solvent was removed by vacuum distillation. The crude product was separated and purified to obtain 79 mg of a selenium-fused perylene imide dimer compound with sulfonate-terminated quaternary ammonium salts and alkyne-linked end groups, with a yield of 85%.

[0356] 1 H NMR (CDCl3, 400MHz, 298K): δ = 8.92 (s, 2H), 8.74 (s, 2H), 8.23 ​​(d, 2H), 7.92 (s, 2H), 7.52 (d,2H),4.16-4.07(m,8H),2.85-2.74(m,40H),1.87-1.83(m,8H),1.65-1.38(m,16H); 13 C NMR (CDCl3, 101MHz, 298K): δ = 162.5, 159.2, 153.5, 148.6, 145.8, 137.2, 133.5, 133.4, 131.5, 130. 3,125.7,125.6,91.5,83.5,60.7,58.3,54.4,35.9,35.8,20.3,8.95; MS(MALDI-TOF(P),100%)m / z calcd for C 82 H 82 N8O 20 S4Se2:1786.29,found:1786.73.

[0357] Experimental Example 1

[0358] This experimental example tests the application of perylene diimide dimers substituted with tertiary amines or quaternary ammonium salts as cathode interface materials in organic solar cells.

[0359] Perylene diimide dimers with single-bonded and alkyne-linked tertiary amines or quaternary ammonium salts substituted with monomers and alkynes obtained in Examples 1 and 2 were used as cathode interface materials for organic solar cells. PM6 was used as the donor material for the organic photoelectric layer, and L8-BO as the acceptor material. A bulk heterojunction organic solar cell device structure was constructed, with the structure being ITO / 2PACz / BHJ / CILs / Ag. CILs and 2PACz served as the electron transport interface material and hole transport interface material, respectively. The solar cell device parameters are shown in Table 1. The solvent used was chloroform, and the light source was AM 1.5G (100mW cm⁻¹). -2 ).

[0360] Table 1 - Solar Cell Device Parameters

[0361]

[0362]

[0363] Photovoltaic conversion efficiency (PCE) is a key indicator of the performance of organic solar cells, representing the percentage of incident light energy converted into electrical energy. Under constant light intensity, PCE is proportional to V. OC J SC To improve the efficiency of photovoltaic devices, including FF, we need to focus on improving these three parameters: PCE. ave This is the average value of 25 devices. Open-circuit voltage V OC This is the voltage of a solar cell when the positive and negative electrodes are open-circuited under illumination, i.e., the maximum output voltage of the solar cell. Besides being affected by the energy levels of the active material, the open-circuit voltage is also influenced by factors such as the microstructure of the active layer, the donor / acceptor ratio, the interface characteristics between the active layer and the electrode, and temperature. OC It also has some impact. Short-circuit current density J SC Jsc is the current per unit area of ​​a solar cell when the positive and negative electrodes are short-circuited under illumination, i.e., the maximum output current density of the cell. The value of Jsc is closely related to the light absorption capacity of the active layer, the generation of photogenerated charge, and the mobility of charge carriers. The fill factor FF is defined as the maximum output power P of the solar cell. max With V OC and J SC The ratio of the products. FF is mainly related to the carrier mobility of the active material, the carrier transport and recombination, the morphology and thickness of the active layer, and the contact resistance of each interface.

[0364] As can be seen from Table 1, the perylene diimide dimer compounds substituted with tertiary amines or quaternary ammonium salts described in this invention, as interface materials for the electron transport layer of organic solar cells, can effectively and efficiently transport electrons, resulting in a certain degree of improvement in the current of the prepared organic solar cell devices. This indicates that the organic solar cell devices prepared based on the perylene diimide dimer compounds substituted with tertiary amines or quaternary ammonium salts described in this invention have a high photocurrent density Jsc and achieve high photoelectric conversion efficiency, thus providing a new development idea for the development of high-performance organic solar cells.

[0365] Experiment Example 2

[0366] This experimental example tests the application of perylene diimide dimers substituted with tertiary amines or quaternary ammonium salts as described in the method of this invention as electron (cathode) transport interface materials (ETL) in perovskite solar cells.

[0367] Perylene diimide dimers with single-bonded and alkyne-linked tertiary amines or quaternary ammonium salts substituted with monomers and alkynes obtained in Examples 1 and 2 were used as the electronic layer interface materials for perovskite solar cells. The device structure adopted ITO / Me-4PACz / PVSK / ETL / BCP / Ag, and the precursor solution was FA.0.90 MA 0.05 Cs 0.05 The PbI3 precursor solution and device parameters are shown in Table 2.

[0368] Table 2 - Parameters of Perovskite Solar Cell Devices

[0369]

[0370]

[0371] As can be seen from Table 2, this type of ETL material can also improve the current value when applied to perovskite solar cells. Perovskite solar cells achieve higher photoelectric conversion efficiency, providing a new perspective for designing high-efficiency and high-stability perovskite solar cells, and making an important contribution to the scientific progress of the perovskite solar cell field.

[0372] This invention is not limited to the preferred embodiments described above. Anyone can derive other products in various forms under the guidance of this invention. However, regardless of any changes in shape or structure, any technical solution that is the same as or similar to this application falls within the protection scope of this invention.

Claims

1. A perylene diimide dimer compound substituted with a tertiary amine or quaternary ammonium salt, characterized in that, The structure is shown in equation (I) or equation (II): Wherein: R1 is selected from substituted alkyl groups or substituted heteroalkyl groups containing tertiary amines or quaternary ammonium salts. Where R2 is one of the following structures: C1 and C1' represent the corresponding C on the benzene ring; Among them, the three R3s mentioned above are all selected from any one of S, Se, N, and O, and the three R3s may be the same or different.

2. A perylene diimide dimer compound substituted with a tertiary amine or quaternary ammonium salt according to claim 1, characterized in that, R1 can be one of the following structures: For example, n = 1-15, etc.

3. A method for preparing perylene diimide dimers substituted with tertiary amines or quaternary ammonium salts as described in claim 1 or 2, characterized in that, Preparation method 1: 1) The perylene anhydride dimer represented by formula (a1) or formula (a2) and the amine R1-NH2 represented by formula (a3) ​​involved in R1 are loaded into the reactor; 2) Under inert gas protection, add organic solvent to the reactor in step 1), and stir and heat the solution to 50-180°C for 0.5-72 hours. 3) The amine-substituted perylene imide dimer compound is obtained through post-treatment; 4) If the corresponding compound is quaternary ammonium salt substituted: The amine-substituted perylene imide dimer obtained in 3) and the haloalkane are loaded into the reactor. Under inert gas protection, organic solvent and THF (tetrahydrofuran) solvent are injected and reacted at room temperature for two days to obtain the corresponding quaternary ammonium salt substituted perylene imide dimer. 5) If the corresponding compound is substituted with a nitrogen-oxygen quaternary ammonium salt: Add hydrogen peroxide to the ethanol solution of the amine-substituted perylene imide dimer obtained in 3), under inert gas protection, and react at 80°C for 3 hours to obtain the corresponding nitrogen-oxygen quaternary ammonium salt-substituted perylene imide dimer.

4. The preparation method according to claim 3, characterized in that, R1-NH2 has the following structure: The equivalent of the compound represented by formula (a1) or formula (a2) is 2 to 50, preferably 5 to 40, of the amine R1-NH2 represented by formula (a3) ​​involved in R1; the equivalent of the haloalkane is 2 to 50, preferably 5 to 40; and the equivalent of the hydrogen peroxide is 2 to 50, preferably 5 to 40. The organic solvent mentioned in steps 2) and 4) is one of the following: The alkaline solvent is selected from: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), pyridine, ethylenediamine, ammonia, triethylamine, and dimethyl sulfoxide. The acidic solvents are selected from: propionic acid, glacial acetic acid, formic acid, sulfuric acid, and phosphoric acid. Neutral solvents are selected from: benzene, toluene, chlorobenzene, o-xylene, p-xylene, m-trimethylbenzene, pseudotrimethylbenzene, tetrahydrofuran, and 1,4-dioxane.

5. A method for preparing perylene diimide dimers substituted with tertiary amines or quaternary ammonium salts as described in claim 1 or 2, characterized in that, Preparation method two: 1) The R2 compound of formula (b1) and dibromo-substituted, or the R2 compound of formula (b3) and diboronic acid or ditin-substituted, or the compound of formula (b1) and (b3) is loaded into the reactor; 2) Under inert gas protection, palladium catalyst, base, organic solvent and water are added to the reactor in step 1) via Suzuki or Stille reaction, and the mixture is heated to 50-180°C and reacted for 5-48 hours. 3) Cooling to room temperature yields amine-substituted perylene imide dimers; 4) If the corresponding compound is quaternary ammonium salt substituted: The amine-substituted perylene imide dimer obtained in 3) and the haloalkane are loaded into the reactor. Under inert gas protection, organic solvent and THF (tetrahydrofuran) solvent are injected and reacted at room temperature for two days to obtain the corresponding quaternary ammonium salt substituted perylene imide dimer. 5) If the corresponding compound is substituted with a nitrogen-oxygen quaternary ammonium salt: Add hydrogen peroxide to the ethanol solution of the amine-substituted perylene imide dimer obtained in 3), under inert gas protection, and react at 80°C for 3 hours to obtain the corresponding nitrogen-oxygen quaternary ammonium salt-substituted perylene imide dimer.

6. The method according to claim 5, characterized in that, The dibromo-substituted R2 compounds are shown in formula (b2), and the diboronic acid or ditin-substituted R2 compounds are shown in formula (b4): The equivalent of the compound represented by formula (b1) or formula (b3) is 1, and the equivalent ratio of the compounds represented by formulas (b2) and (b4) involved in R2 is 0.2 to 0.5, preferably 0.3 to 0.5; the equivalent ratio of the palladium catalyst is 0.05 to 0.2, preferably 0.05 to 0.1; the equivalent ratio of the base is 2 to 50, preferably 5 to 10; the equivalent ratio of the haloalkane is 2 to 50, preferably 5 to 40; and the equivalent ratio of hydrogen peroxide is 2 to 50, preferably 5 to 40. The organic solvents mentioned in 2) and 4) are selected from the following: The alkaline solvent is selected from: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), pyridine, ethylenediamine, ammonia, triethylamine, and dimethyl sulfoxide; The acidic solvents are selected from: propionic acid, glacial acetic acid, formic acid, sulfuric acid, and phosphoric acid; Neutral solvents are selected from: benzene, toluene, chlorobenzene, o-xylene, p-xylene, m-trimethylbenzene, pseudotrimethylbenzene, tetrahydrofuran, and 1,4-dioxane; The palladium reagent mentioned is selected from: tetratriphenylphosphine palladium, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; When the organic solvent used in step 2) is an acidic, alkaline, or neutral solvent, an alkali needs to be added; the alkali reagent is: sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, dipotassium hydrogen phosphate, or disodium hydrogen phosphate.

7. The application of the perylene diimide dimer compound substituted with a tertiary amine or quaternary ammonium salt as described in claim 1 or 2, in organic solar cells and perovskite solar cells.

8. The application according to claim 7, for use in electronic transport interface materials.

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