Aza-fused ring perylene diimide parent nucleus, derivative, preparation method and application of aza-fused ring perylene diimide parent nucleus and derivative

Abstract

The invention discloses an aza-fused ring perylene diimide mother nucleus, a derivative and a preparation method and application of the aza-fused ring perylene diimide mother nucleus and the derivative. The structural general formula of the aza-fused ring perylene diimide mother nucleus is as follows: # imgabs0 #, wherein R1 is alkyl with the carbon number of 1-30. In the nitrogen-doped fused ring perylene diimide mother nucleus structure provided by the invention, the LUMO energy level of the perylene diimide structure can be obviously reduced by introducing the nitrogen-doped fused ring, the formation of an induced hydrogen bond is facilitated, and the intermolecular interaction is enhanced. In addition, simple oxidation and amidation reactions are carried out on the aza fused ring, additional imide sites and alkyl chains can be derived, and light absorption / redox double activity is enhanced. The aza-fused ring perylene diimide parent nucleus and the derivative thereof are reported for the first time, the structure is simple, the synthetic route is simple and efficient, the application potential of the aza-fused ring perylene diimide parent nucleus and the derivative thereof in organic photoelectric devices is verified, and a simple and effective technical route is provided for preparation of novel efficient perylene diimide semiconductor materials.

Description

Technical Field

[0001] The present invention relates to the technical field of organic optoelectronic materials, and particularly to a nitrogen-containing fused-ring perylene diimide mother nucleus, derivatives thereof, and a preparation method and application thereof. Background Art

[0002] In recent years, organic semiconductor materials have shown broad application prospects in the fields of flexible electronics, wearable devices, organic optoelectronic devices, etc. Compared with traditional inorganic semiconductors, organic semiconductors have the following advantages: First, the molecular structure has strong designability, and the optoelectronic properties can be adjusted through chemical synthesis; Second, they have intrinsic flexibility and deformability, which are suitable for applications such as flexible displays and electronic skins; Third, organic semiconductors can be solution-processed, with low cost and suitable for large-area preparation. These characteristics make them an important development direction for future electronics and optoelectronic technologies.

[0003] As a class of classic organic semiconductor materials, perylene diimide derivatives have excellent optoelectronic properties and solution-processability, and have received extensive attention in the fields of organic field-effect transistors (OFETs), organic solar cells (OPV), and photo-charging batteries. Due to the planar conjugated molecular structure of perylene diimide, it is beneficial to carrier migration and shows good semiconductor characteristics in OFETs devices. In addition, perylene diimide also has strong visible light absorption ability and efficient electron transport ability, and can be used as a photoactive layer in photo-charging batteries and organic photovoltaic devices.

[0004] Efficient perylene diimide derivatives need to have structural characteristics such as adjustable side chains, functionalized perylene cores, and strong intermolecular interactions. However, currently, such perylene diimide derivatives usually have complex structures and long synthetic routes. Therefore, developing efficient building blocks and simplifying the synthetic routes of such materials are of great significance for realizing their applications in the fields of OFET, OPV, and photo-charging batteries. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical deficiencies, and propose a nitrogen-containing fused-ring perylene diimide mother nucleus, derivatives thereof, and a preparation method and application thereof, so as to solve the technical problems that efficient perylene diimide derivatives in the prior art usually have complex structures and long synthetic routes.

[0006] In the first aspect, the present invention provides a nitrogen-containing fused-ring perylene diimide mother nucleus, and its structural general formula is as follows: ; wherein, R 1 is an alkyl group with 1 to 30 carbon atoms.

[0007] In the second aspect, the present invention provides a preparation method of a nitrogen-containing fused-ring perylene diimide mother nucleus, including the following steps: Compound I-1 and compound I-2 are subjected to a condensation reaction under acid-catalyzed conditions, and then a photocyclization reaction occurs under the catalytic conditions of iodine and light to obtain intermediate I-3; The intermediate I-3 is subjected to a carbon-carbon coupling reaction under the action of a palladium catalyst to obtain a nitrogen-containing fused-ring perylene diimide nucleus; wherein, The general structural formula of compound I-1 is: ; The general structural formula of compound I-2 is: ; The general structural formula of intermediate I-3 is: .

[0008] In a third aspect, the present invention provides a nitrogen-containing fused-ring perylene diimide derivative, and its general structural formula is as follows: ; Wherein, R 1 and R 2 are each independently an alkyl group having 1 to 30 carbon atoms.

[0009] In a fourth aspect, the present invention provides a method for preparing a nitrogen-containing fused-ring perylene diimide derivative, comprising the following steps: The nitrogen-containing fused-ring perylene diimide nucleus is subjected to an oxidation reaction under the conditions of potassium dichromate and acetic acid to obtain intermediate I-4; The intermediate I-4 and an alkylamine are dissolved in a fourth solvent for an amidation reaction to obtain a nitrogen-containing fused-ring perylene diimide derivative; wherein, The general structural formula of intermediate I-4 is: .

[0010] In a fifth aspect, the present invention provides the application of the above-mentioned nitrogen-containing fused-ring perylene diimide nucleus or nitrogen-containing fused-ring perylene diimide derivative in organic optoelectronic devices.

[0011] Compared with the prior art, the beneficial effects of the present invention include: In the azafused perylene diimide parent nucleus structure provided by the present invention, introducing an azafused ring can significantly reduce the LUMO energy level of the perylene diimide structure, which helps to induce the formation of hydrogen bonds and enhance the intermolecular interaction. In addition, by performing simple oxidation and amidation reactions on the azafused ring, additional imide sites and alkyl chains can be derived, enhancing the dual activities of light absorption / redox. The azafused perylene diimide parent nucleus and its derivatives provided by the present invention are reported for the first time. They have a simple structure and a simple and efficient synthetic route, and the application potential in organic optoelectronic devices is verified, providing a simple and effective technical route for the preparation of novel and efficient perylene diimide-based semiconductor materials. Description of the Drawings

[0012] Figure 1 is a schematic structural diagram of the bottom-gate top-contact device in Example 3 of the present invention; Figure 2 is the 1H NMR spectrum of Compound 1 in Example 1 of the present invention; Figure 3 is the 1H NMR spectrum of Compound 2 in Example 2 of the present invention; Figure 4 is the ultraviolet-visible (UV-vis) absorption spectrum of the thin film made of Compound 1 and Compound 2 in Examples 1-2 of the present invention; Figure 5 are the cyclic voltammograms of Compound 1 and Compound 2 in Examples 1-2 of the present invention; Figure 6 is the AFM morphology diagram of the thin film made of Compound 1 in Example 1 of the present invention at different annealing temperatures; Figure 7 is the AFM morphology diagram of the thin film made of Compound 2 in Example 2 of the present invention at different annealing temperatures; Figure 8 are the transfer curve and output curve of the OFET device made of Compound 1 in Example 1 of the present invention; Figure 9 are the transfer curve and output curve of the OFET device made of Compound 2 in Example 2 of the present invention. Detailed Embodiments

[0013] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0014] In the first aspect, the present invention provides an azafused perylene diimide parent nucleus, and its structural general formula is as follows: ; In the general formula (I), R1 is an alkyl group with 1 to 30 carbon atoms, preferably an alkyl group with 10 to 20 carbon atoms, and more preferably an alkyl group with 14 to 20 carbon atoms.

[0015] In a second aspect, the present invention provides a method for preparing a nitrogen-containing fused polycyclic perylene diimide mother nucleus, comprising the following steps: S1. Condense compound I-1 and compound I-2 under acid catalysis, and then carry out a photocyclization reaction under the catalysis of iodine and light to obtain intermediate I-3; S2. Carry out a carbon-carbon coupling reaction on intermediate I-3 under the action of a palladium catalyst to obtain a nitrogen-containing fused polycyclic perylene diimide mother nucleus. The specific synthesis process is as follows: .

[0016] In this embodiment, in step S1, the molar ratio of compound I-1 to compound I-2 is 1:(0.9 - 1.1), and further 1:1.

[0017] In this embodiment, in step S1, the acid is trifluoromethanesulfonic acid.

[0018] In this embodiment, in step S1, the dosage ratio of compound I-1 to the acid is 400 - 600 mg:1 mL.

[0019] In this embodiment, in step S1, a first solvent is further added during the condensation reaction.

[0020] Among them, the first solvent is dichloromethane (DCM).

[0021] Among them, the dosage ratio of compound I-1 to the first solvent is 4 - 6 mg:1 mL.

[0022] In this embodiment, in step S1, the temperature of the condensation reaction is room temperature, and the time of the condensation reaction is 1 - 3 h.

[0023] In this embodiment, in step S1, after the condensation reaction, it further includes: removing the first solvent.

[0024] Among them, the first solvent is removed by a rotary evaporator.

[0025] In this embodiment, in step S1, the mass ratio of compound I-1 to iodine is 1:(0.3 - 0.5).

[0026] In this embodiment, in step S1, a second solvent is further added during the photocyclization reaction.

[0027] Among them, the second solvent is toluene.

[0028] Among them, the dosage ratio of compound I-1 to the second solvent is (1 to 1.5) mg: 1 mL.

[0029] In this embodiment, in step S1, the time of the photocyclization reaction is 20 to 40 min, and the light source is an incandescent lamp of 100 to 500 W.

[0030] In this embodiment, in step S1, after the photocyclization reaction is completed, it further includes: removing the second solvent and then separating and purifying through a silica gel chromatography column, and finally obtaining intermediate I-3 through recrystallization.

[0031] Among them, the rotary evaporator is used to remove the second solvent.

[0032] Among them, the eluent is a mixed solvent of petroleum ether and dichloromethane.

[0033] Furthermore, the volume ratio of petroleum ether to dichloromethane is 1:2.

[0034] Among them, the recrystallization solvent is a mixed solvent of dichloromethane and methanol.

[0035] In this embodiment, in step S2, the palladium catalyst is Pd 2 (dba) 3 , and the Chinese name is tris(dibenzylideneacetone)dipalladium.

[0036] In this embodiment, in step S2, the molar ratio of intermediate I-3 to the palladium catalyst is 1: (0.08 to 0.12), and further 1:0.1.

[0037] In this embodiment, in step S2, during the carbon-carbon coupling reaction, a third solvent and cesium fluoride are further added.

[0038] Among them, the third solvent is tetrahydrofuran (THF).

[0039] Among them, the dosage ratio of intermediate I-3 to the third solvent is (30 to 40) mg: 1 mL.

[0040] Among them, the molar ratio of intermediate I-3 to cesium fluoride is 1: (2 to 4).

[0041] In this embodiment, in step S2, the temperature of the carbon-carbon coupling reaction is 70 to 90 °C, and the time of the carbon-carbon coupling reaction is 3 to 5 h.

[0042] In this embodiment, in step S2, after the carbon-carbon coupling reaction is completed, it further includes: After the reaction system is cooled to room temperature, water is added, and then the crude product is obtained through extraction, washing, and drying; The crude product is separated and purified through a silica gel chromatography column, and then the nitrogen heterocyclic fused perylene diimide nucleus is obtained through recrystallization.

[0043] Among them, the extractant is dichloromethane.

[0044] Among them, the washing solution is saturated brine and distilled water.

[0045] Among them, drying includes: drying with anhydrous sodium sulfate and removing the solvent using a rotary evaporator.

[0046] Among them, the eluent is a mixed solvent of petroleum ether and dichloromethane.

[0047] Furthermore, the volume ratio of petroleum ether to dichloromethane is 1:2.

[0048] Among them, the recrystallization solvent is a mixed solvent of dichloromethane and methanol.

[0049] In a third aspect, the present invention provides a nitrogen heterocyclic fused perylene diimide derivative, and its structural general formula is as follows: ; In general formula (II), R 1 and R 2 are each independently an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 10 to 20 carbon atoms, and more preferably an alkyl group having 14 to 20 carbon atoms.

[0050] In a third aspect, the present invention provides a preparation method of a nitrogen heterocyclic fused perylene diimide derivative, including the following steps: A1. Oxidize the nitrogen heterocyclic fused perylene diimide parent nucleus under the conditions of potassium dichromate and acetic acid to obtain intermediate I-4 (perylene diimide naphthalenedicarboxylic anhydride); A2. Dissolve intermediate I-4 and alkylamine in a fourth solvent for amidation reaction to obtain a nitrogen heterocyclic fused perylene diimide derivative. The specific synthesis process is as follows: .

[0051] In this embodiment, in step A1, the molar ratio of the nitrogen heterocyclic fused perylene diimide parent nucleus to potassium dichromate is 1:(3 - 5).

[0052] In this embodiment, in step A1, the dosage ratio of the nitrogen heterocyclic fused perylene diimide parent nucleus to acetic acid is (20 - 25) mg:1 mL.

[0053] In this embodiment, in step A1, the temperature range of the oxidation reaction is 120 - 140 °C, and the time of the oxidation reaction is 8 - 12 h.

[0054] In this embodiment, in step A1, after the oxidation reaction, it further includes: after the reaction system is cooled to room temperature, it is pickled, washed with water, washed with alcohol, and dried to obtain a crude product.

[0055] Among them, the acid used for pickling is a hydrochloric acid solution with a mass fraction of 10 - 30%.

[0056] Among them, the alcohol used for alcohol washing is methanol.

[0057] In this embodiment, in step A2, the molar ratio of intermediate I-4 to alkylamine is 1:(0.9 - 1.1), and further 1:1.

[0058] In this embodiment, in step A2, the fourth solvent is ethylene glycol.

[0059] In this embodiment, in step A2, the dosage ratio of intermediate I-4 to the fourth solvent is (7 - 9) mg:1 mL.

[0060] In this embodiment, the temperature of the amidation reaction is 140 - 150 °C, and the time of the amidation reaction is 5 - 7 h.

[0061] In this embodiment, after the amidation reaction, it further includes: Cooling the reaction system to room temperature and then adding water, and then obtaining a crude product through extraction, washing, and drying; Separating and purifying the crude product through a silica gel chromatography column, and then obtaining the azafused-ring perylene diimide derivative through recrystallization.

[0062] Among them, the extractant is dichloromethane.

[0063] Among them, the washing solution is saturated brine and distilled water.

[0064] Among them, drying includes: drying with anhydrous sodium sulfate and removing the solvent using a rotary evaporator.

[0065] Among them, the eluent is a mixed solvent of petroleum ether and dichloromethane.

[0066] Furthermore, the volume ratio of petroleum ether to dichloromethane is 1:3.

[0067] Among them, the recrystallization solvent is a mixed solvent of dichloromethane and methanol.

[0068] Fifth aspect, the present invention provides the application of the above-mentioned azafused-ring perylene diimide parent nucleus or azafused-ring perylene diimide derivative in organic optoelectronic devices.

[0069] In this embodiment, the above-mentioned azafused-ring perylene diimide parent nucleus or azafused-ring perylene diimide derivative is applied as the semiconductor layer of an organic optoelectronic device.

[0070] In this embodiment, the organic optoelectronic device is an organic field effect transistor device.

[0071] Example 1: Synthesis method of compound 1 The structural formula of Compound 1 is as follows:

[0072] The synthesis method of the above Compound 1 is carried out according to the following synthetic route: (1) Synthesis of i-3:

[0073] In an air environment, raw material I-1 (261 mg, 1 mmol) and i-2 (966 mg, 1 mmol) were added to a 100 mL two-necked round-bottom flask. Dichloromethane (48 mL) and trifluoromethanesulfonic acid (0.5 mL) were added thereto, and then the mixture was stirred on a stirrer at room temperature for 2 h. After monitoring by TLC plate that there was no remaining raw material in the reaction, the organic solvent was removed by a rotary evaporator. The remaining solid was dissolved in 200 mL of toluene and iodine (100 mg) was added. The reaction mixture was pumped into a photoreactor for photocyclization reaction for 30 min, and the light source was a 300 W incandescent lamp. After monitoring by TLC plate that there was no remaining raw material in the reaction, the organic solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated and purified by a silica gel chromatography column (the eluent was V(petroleum ether):V(dichloromethane)=1:2), and then recrystallized with a mixed solvent of dichloromethane and methanol to obtain a red solid i-3, with a weight of 990 mg and a yield of 82%.

[0074] (2) Synthesis of Compound 1:

[0075] In a nitrogen atmosphere, raw material i-3 (1.21 g, 1 mmol) was added to a 100 mL two-necked round-bottom flask. Tris(dibenzylideneacetone)dipalladium (113.7 mg, 0.1 mmol), cesium fluoride (455.7 mg, 3 mmol), and tetrahydrofuran (36 mL) were added thereto. The round-bottom flask was placed in an oil bath and stirred at 80 °C for 4 h. The reaction was stopped after monitoring by TLC plate that there was no remaining raw material in the reaction. After the reaction system was cooled to room temperature, an appropriate amount of water was added, and the mixture was extracted with dichloromethane and washed three times with saturated brine and distilled water. After drying with anhydrous sodium sulfate, the organic solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated and purified by a silica gel chromatography column (the eluent was V(petroleum ether):V(dichloromethane)=1:2), and then recrystallized with a mixed solvent of dichloromethane and methanol to obtain a green solid target Compound 1, with a weight of 754.8 mg and a yield of 67%.

[0076] Example 2: Synthesis method of Compound 2 The structural formula of Compound 2 is as follows:

[0077] The synthesis method of the above compound 2 is as follows: (1) Synthesis of i-4:

[0078] In an air environment, compound 1 (1.13 g, 1 mmol) was added to a 100 mL two-necked round-bottom flask. Glacial acetic acid (52 mL) and potassium dichromate (632 mg, 4 mmol) were added thereto, and then the round-bottom flask was placed in an oil bath and heated under reflux at 120 °C for 10 h. The reaction was stopped after monitoring by TLC plate showed no remaining raw materials. After cooling to room temperature, the reaction mixture was poured into dilute hydrochloric acid (mass fraction 20%) and stirred for 30 minutes and then filtered by suction. It was washed three times with water and methanol, and dried to obtain a crude product. Without purification, it was directly subjected to the next reaction.

[0079] (2) Synthesis of compound 2:

[0080] In an air environment, raw material i-4 (1.17 g, 1 mmol) was added to a 250 mL two-necked round-bottom flask. Ethylene glycol (150 mL) and alkylamine (297.6 mg, 1 mmol) were added thereto, and then the round-bottom flask was placed in an oil bath and stirred at 145 °C for 6 h. The reaction was stopped after monitoring by TLC plate showed no remaining raw materials. When the reaction system cooled to room temperature, an appropriate amount of water was added, and it was extracted with dichloromethane and washed three times with saturated brine and distilled water. After drying with anhydrous sodium sulfate, the organic solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated and purified by a silica gel chromatographic column (eluent: V(petroleum ether):V(dichloromethane)=1:3), and then recrystallized with a mixed solvent of dichloromethane and methanol to obtain the target compound 2 as a dark red solid, with a weight of 1.15 g and a yield of 79%.

[0081] Example 3: Preparation of organic field effect transistor (1) This example provides a preparation method of an OFET, and its device structure is as Figure 1 shown. Among them, the gate silicon substrate was purchased commercially and was a heavily doped silicon wafer containing a 300 nm silicon dioxide layer (with an area of 1.3 square centimeters). The silicon substrate was ultrasonically cleaned in an aqueous solution containing a detergent for 15 minutes, washed in deionized water for 10 minutes, and ultrasonically cleaned in acetone and isopropyl alcohol for 15 minutes; after drying, it was treated with a piranha solution (concentrated H 2 SO 4 :H 2 O 2Soak in a solution of ethanol and acetone (volume ratio = 7:3, v / v) for 30 minutes, ultrasonically clean several times with deionized water, and dry with nitrogen for later use. Finally, treat the surface of the silicon substrate with OTS reagent, dry it in vacuum at 120 °C for 2 hours, ultrasonically clean it with toluene and isopropanol for 15 minutes, and dry it for later use.

[0082] (2) Prepare chloroform solutions of Compound 1 and Compound 2 with a concentration of 5 mg / mL respectively. Spin-coat them on the surface of the above-mentioned silicon substrate by a spin coater to prepare a semiconductor layer thin film. The spin-coating speed is 3000 rpm and the time is 60 s. Anneal at 120 °C for 10 minutes to remove the chloroform solvent and adjust the film morphology. (3) Evaporate gold on the surface of the semiconductor thin film by vacuum evaporation to prepare source and drain electrodes (vacuum degree: 5×10 - 4 Pa; evaporation rate: 0.01 nm / s; film thickness: 30 nm), and the device fabrication is completed.

[0083] Performance Testing 1. Conduct nuclear magnetic resonance tests on the above-mentioned Compound 1 and Compound 2. The test results are shown in Figures 2 - 3 .

[0084] 2. In a nitrogen atmosphere, prepare chloroform (CF) solutions of Compound 1 and Compound 2 with a concentration of 20 mg / mL respectively. Take 30 μL of the solution and drop-coat it on a quartz substrate, and then spin-coat the quartz substrate at a speed of 3000 rpm for 90 s to obtain a sample thin film. Conduct ultraviolet-visible spectroscopy tests on the above-mentioned thin film. The test results are shown in Figure 4 .

[0085] 3. Use a CHI660E electrochemical workstation to record cyclic voltammograms (CV). Use a glassy carbon electrode as the working electrode, a platinum wire as the counter electrode, and an Ag / AgCl electrode as the reference electrode. Use a dichloromethane solution of 0.1 M Bu 4 NPF 6 (tetrabutylammonium hexafluorophosphate) as the electrolyte. Dissolve a small amount of Compound 1 and Compound 2 in this electrolyte, use ferrocene (Fc / Fc + ) as the internal standard, and the scanning rate is 100 mV / s. Conduct tests in a nitrogen environment at room temperature. The test results are shown in Figure 5 .

[0086] 4. In a nitrogen atmosphere, compounds 1 and 2 were respectively formulated into chloroform (CF) solutions with a concentration of 20 mg / mL. 30 μL of the solution was taken and dropped onto a silicon substrate covered with a 300 nm silica film, and then the silicon substrate covered with a 300 nm silica film was spin-coated at a speed of 3000 rpm for 90 seconds to obtain a sample film. After annealing the above film at different annealing temperatures for 10 minutes, AFM tests were carried out, and the test results are shown in Figures 6 - 7 .

[0087] 5. The performance of the OFET devices made of compounds 1 and 2 in Examples 1 - 2 of the present invention was tested by a Keithley 4200SCS semiconductor analyzer. The source-drain voltage was 70 V, and the gate voltage was 0 - 70 V. The test results are shown in Figures 8 - 9 .

[0088] Please refer to Figures 2 - 3 , Figures 2 - 3 which is the hydrogen spectrum diagram of compounds 1 and 2 in Examples 1 - 2 of the present invention. It can be seen from Figures 1 - 2 that compounds 1 - 2 were successfully synthesized.

[0089] Please refer to Figure 4 , Figure 4 which is the ultraviolet-visible (UV-vis) absorption spectrum diagram of the film made of compounds 1 and 2 in Examples 1 - 2 of the present invention. It can be seen from Figure 4 that by calculating from the starting peak position, the optical energy gaps of compounds 1 and 2 are 1.85 and 2.04 eV respectively, indicating that the above compounds are suitable for use as the organic semiconductor layer of OFET.

[0090] Please refer to Figure 5 , Figure 5 which is the cyclic voltammogram of compounds 1 and 2 in Examples 1 - 2 of the present invention. It can be seen from Figure 5 that compound 2 obviously has more redox peaks, which can bring more electrochemically active sites; at the same time, by calculating with relevant formulas, the LUMO energy levels of compounds 1 and 2 are -3.72 and -3.78 eV respectively.

[0091] Please refer to Figures 6 - 7 , Figures 6 - 7 which is the AFM morphology diagram of the film made of compounds 1 and 2 in Examples 1 - 2 of the present invention at different annealing temperatures. It can be seen from Figures 6 - 7 that through annealing treatment, the film morphology of compounds 1 and 2 can be significantly adjusted.

[0092] Please refer to Figures 8 - 9 , Figures 8 - 9are the transfer curves and output curves of OFET devices made from Compound 1 and Compound 2 in Embodiments 1 - 2 of the present invention. Through Figures 8 - 9 it can be seen that the on / off ratio of the OFET device based on Compound 1 is 10 5 , and the electron mobility is 0.165 cm 2 V -1 s -1 ; the on / off ratio of the OFET device based on Compound 2 is 10 2 , and the electron mobility is 7.80×10 -6 cm 2 V -1 s -1 , indicating that both Compound 1 and Compound 2 exhibit good carrier mobilities in OFET devices. Among them, the electron mobility of Compound 1 reaches 0.165 cm 2 V -1 s -1 , and the on / off ratio reaches 10 5 , further indicating that Compound 1 is an effective structural unit for developing high-performance perylene diimide semiconductor materials.

[0093] To more clearly demonstrate the performance advantages of the azafused perylene diimide core and its derivatives provided by the present invention, the performances of Compound 1 and Compound 2 and other perylene diimide compounds reported in the existing literature are summarized in Table 1.

[0094] Table 1

[0095] It can be seen from Table 1 that both Compound 1 and Compound 2 of the present application have significantly lower LUMO energy levels, which is beneficial for better matching with the work functions of the source and drain electrode metals, and thus obtaining higher electron transport performance and air stability.

[0096] The specific embodiments of the present invention described above do not constitute a limitation to the protection scope of the present invention. Any other corresponding changes and deformations made according to the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. An aza-fused ring and perylene diimide mother core, characterized in that: The general structure is as follows: ； Here, R1 is an alkyl group having 1 to 30 carbon atoms.

2. A method for preparing the aza-fused ring perylene diimide mother core as claimed in claim 1, characterized in that: The following steps are involved: Compound I-1 and compound I-2 are subjected to a condensation reaction under acid-catalyzed conditions, followed by a photocyclization reaction under catalytic conditions of iodine and light to obtain intermediate I-3; The intermediate I-3 is subjected to a carbon-carbon coupling reaction under the action of a palladium catalyst to obtain an aza-fused ring and perylene diimide mother core; wherein, The general structural formula of the compound I-1 is: ； The general structural formula of the compound I-2 is: ； The general structural formula of the intermediate I-3 is: 。 3. The method for preparing the aza-fused ring perylene diimide mother core according to claim 2, characterized in that: The molar ratio of compound I-1 to compound I-2 is 1:(0.9-1.1); and / or, The acid is trifluoromethanesulfonic acid; and / or, The dosage ratio of the compound I-1 to the acid is 400-600 mg:1 mL; and / or, The mass ratio of the compound I-1 to the iodine element is 1:(0.3-0.5); and / or, The condensation reaction temperature is room temperature, and the condensation reaction time is 1 to 3 hours; and / or, The photocyclization reaction time is 20-40 minutes, and the light source is a 100-500W incandescent lamp.

4. The method for preparing the aza-fused ring perylene diimide mother core according to claim 3, characterized in that: During the condensation reaction, a first solvent is added, and the first solvent is dichloromethane, and the dosage ratio of the compound I-1 to the first solvent is 4-6 mg: 1 mL; and / or, During the photocyclization reaction, a second solvent is added, and the second solvent is toluene. The dosage ratio of the compound I-1 to the second solvent is (1-1.5) mg: 1 mL.

5. The method for preparing the aza-fused ring perylene diimide mother core according to claim 2, characterized in that: The palladium catalyst is Pd2(dba)3; and / or, The molar ratio of the intermediate I-3 to the palladium catalyst is 1:(0.08-0.12); and / or, The temperature of the carbon-carbon coupling reaction is 70-90° C., and the time of the carbon-carbon coupling reaction is 3-5 hours.

6. The method for preparing the aza-fused ring perylene diimide mother core according to claim 5, characterized in that: During the carbon-carbon coupling reaction, a third solvent and cesium fluoride are also added; wherein, The third solvent is tetrahydrofuran; and / or, The usage ratio of the intermediate I-3 to the third solvent is (30-40) mg: 1 mL; and / or, The molar ratio of the intermediate I-3 to cesium fluoride is 1:(2-4).

7. An aza-fused ring perylene diimide derivative, characterized in that: The general structure is as follows: ； Here, R1 and R2 are each independently an alkyl group having 1 to 30 carbon atoms.

8. A method for preparing the aza-fused ring perylene diimide derivative as claimed in claim 7, characterized in that: The following steps are involved: The nitrogen-fused ring and perylene diimide mother core is subjected to oxidation reaction under the conditions of potassium dichromate and acetic acid to obtain intermediate I-4; The intermediate I-4 and alkylamine are dissolved in a fourth solvent to carry out an amidation reaction to obtain an aza-fused ring and perylene diimide derivative; wherein, The general structural formula of the intermediate I-4 is: 。 9. The method for preparing the aza-fused ring perylene diimide derivative according to claim 8, characterized in that: The molar ratio of the aza-fused-ring perylene diimide mother core to potassium dichromate is 1:(3-5); and / or, The ratio of the nitrogen-fused ring perylene diimide mother core to acetic acid is (20-25) mg: 1 mL; and / or, The molar ratio of the intermediate I-4 to the alkylamine is 1:(0.9-1.1); and / or, The fourth solvent is ethylene glycol; and / or, The usage ratio of the intermediate I-4 to the fourth solvent is (7-9) mg: 1 mL; and / or, The temperature range of the oxidation reaction is 120-140°C, and the time of the oxidation reaction is 8-12h; and / or, The temperature of the amidation reaction is 140-150° C., and the time of the amidation reaction is 5-7 hours.

10. Use of the aza-fused perylene diimide core according to claim 1 or the aza-fused perylene diimide derivative according to claim 7 in an organic optoelectronic device.

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