Preparation method and application of N-N bidentate ligand containing penta-fused ring conjugated structure

Abstract

The invention belongs to the technical field of preparation of organic photoelectric materials, and particularly relates to preparation of a penta-fused ring-containing N-N bidentate ligand and application of the penta-fused ring-containing N-N bidentate ligand in preparation of a polymer photoelectric material. The N-N bidentate ligand provided by the invention has a larger conjugate area and more modification sites, and when electron donating groups are introduced to the modification sites, the large conjugate area and the electron donating groups act together, so that the catalytic activity of a cuprous catalyst in a direct arylation polymerization reaction is improved, and the catalytic activity of the cuprous catalyst in the direct arylation polymerization reaction is improved. Further, the polymer photoelectric material is successfully prepared. The prepared polymer photoelectric material can be used for preparing organic photoelectric devices. According to the N-N bidentate ligand provided by the invention, the preparation cost of a polymer photoelectric material can be reduced, the use of toxic catalysts and intermediates is reduced, and the N-N bidentate ligand has important application value in the technical field of organic photoelectric material preparation.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric material preparation, and in particular to the preparation of a NN bidentate ligand containing a penta-fused ring, and the application of the ligand in the preparation of polymer photoelectric materials. Background Art

[0002] Organic semiconductor polymers have the characteristics of intrinsic flexibility and are considered to be materials with great potential for preparing flexible electronic devices. At present, organic semiconductor polymers have been applied in many fields including organic photovoltaic cells (OPV), organic light-emitting diodes (OLED), organic field effect transistors (OFET), organic electrochemical transistors (OECT), etc., and have shown unique advantages and excellent performance. However, the preparation of organic semiconductor polymers is relatively complicated, usually using Stille reaction, Suzuki reaction, Negishi reaction or Kumada reaction. These preparation methods require the preparation of expensive or toxic intermediates, which increases the reaction cost. In recent years, the emergence of direct aromatic polymerization (DArP) has provided a solution to this problem. Through transition metal catalysis, the polymerization reaction of aromatic substrates containing active hydrogen and aromatic substrates containing halogens is achieved without the preparation of additional intermediates. However, the catalysts used in most direct aromatic polymerization reactions are expensive and toxic palladium catalysts, which undoubtedly violates the original intention of this preparation method. Copper catalysts are cheap and readily available, and have good bioaffinity. Using them to replace palladium catalysts will make the preparation method of direct arylation polymerization greener and more reliable (BC Thompson, et al., Polym. Chem. 2020, 11 , 630.). However, the main problem of copper catalysts is their low activity, which limits their application in direct arylation polymerization. In previous studies, researchers found that the ligand is closely related to the activity of copper catalysts (D. Ma, et al., Angew. Chem. Int. Ed. 2017, 56 , 16136.), so the design of efficient ligands is of great significance for the preparation of polymer optoelectronic materials via direct arylation polymerization. Summary of the invention

[0003] In order to solve the above technical problems, the present invention proposes a preparation method and application of a NN bidentate ligand. The present invention is reasonably designed, and the prepared ligand has a significant effect on improving the activity of monovalent copper catalysts, and a polymer optoelectronic material with a large molecular weight and a high yield is synthesized through a copper-catalyzed direct aromatic polymerization reaction.

[0004] The present invention is achieved through the following technical solutions.

[0005] The present invention provides a NN bidentate ligand containing a penta-fused ring, which is characterized by having a structure as shown in the following formula I.

[0006]

[0007] Where R 1 -R 10 The structure of the group is independently selected from any one of hydrogen atom, halogen, linear or branched alkyl or alkoxy group having 1 to 30 carbon atoms, aryl group, nitro group, amino group, methylamino group, dimethylamino group, carboxyl group and ester group.

[0008] Or R in Formula I 1 -R 10 Any adjacent positions are connected to form a ring through several covalent bonds.

[0009] Preferably, R 1 -R 10 At least one of them is selected from methyl, tert-butyl or methoxy.

[0010] Preferably, R 4 and R 7 At least one of them is selected from methyl, tert-butyl or methoxy.

[0011] Preferably, R 4 and R 7 Both were selected as methoxy.

[0012] According to one or more embodiments, the present invention provides a NN bidentate ligand containing a penta-fused ring, selected from any one of the chemical structures shown below.

[0013]

[0014]

[0015] The present invention also provides a method for preparing the compound shown in formula I, which comprises the following steps.

[0016]

[0017] Under an inert atmosphere, nickel chloride hexahydrate, triphenylphosphine and zinc powder are added to a reaction vessel, DMF is added as a reaction solvent, and the mixture is heated to 50° C. with stirring. After 2 hours, two identical or different substrates represented by formula III and formula IV are added, and the reaction is continued for 8 hours. The substrates represented by formula III and formula IV are coupled to obtain the intermediate product V shown.

[0018] The intermediate product V is dried and added to a reaction vessel, ethylene glycol dimethyl ether is added as a reaction solvent, potassium chips are added, and stirred at room temperature for 16 hours, so that the intermediate product V undergoes a reduction cyclization reaction; anhydrous tetrahydrofuran is added and stirred for 4 hours, and after oxidation in the air, the compound shown in formula I is separated by column chromatography.

[0019] The present invention also provides a method for preparing a polymer photoelectric material. The method adopts copper-catalyzed direct arylation polymerization as a polymerization method and adopts a NN bidentate ligand containing a penta-fused ring as shown in formula I to promote the reaction.

[0020] The present invention also provides a polymer optoelectronic material prepared by the above method, wherein the polymer optoelectronic material is a carrier transport material.

[0021] The present invention also provides an organic field effect transistor device, the device structure comprising a substrate, a channel material, a source electrode, a drain electrode, and an electrolyte solution, wherein the channel material is the above-mentioned polymer photoelectric material.

[0022] The present invention also provides a method for preparing an organic field effect transistor device, and the preparation method comprises the following steps.

[0023] (1) Cleaning and processing the substrate: After removing the protective film from the polyethylene terephthalate (PET) sheet, ultrasonically clean it twice with secondary water, then ultrasonically clean it twice with isopropyl alcohol, blow nitrogen gas until the surface is clean, and place it in the mask plate for later use.

[0024] (2) Device preparation: The entire operation was carried out in a glove box. A mask plate with a W / L ratio of 4500 / 90 was used. A vacuum evaporation system was used to evaporate the bottom electrode. 24 nm gold was evaporated. The chloroform solution of the polymer prepared above was spin-coated on the PET substrate at a speed of 1500 rpm for 50 seconds and annealed for 10 minutes. The polymer layer was covered with a mask plate, and the polymer surface was patterned using oxygen plasma. Sodium chloride solution was dripped on the surface of the treated device.

[0025] (3) Test characterization: The resulting device was characterized using a source instrument B2912A. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the H NMR spectrum of compound II-2.

[0027] Figure 2 This is the H NMR spectrum of compound II-5.

[0028] Figure 3 This is the H NMR spectrum of compound II-8.

[0029] Figure 4This is the H NMR spectrum of compound II-15.

[0030] Figure 5 The schematic diagram of the structure of an organic field effect transistor device shown in the present invention is a top-gate bottom-contact device structure.

[0031] Figure 6 It is the general structural formula of the NN bidentate ligand containing a five-fused ring conjugated structure of the present invention. DETAILED DESCRIPTION

[0032] Various exemplary embodiments of the present invention are now described in detail. The features of the present invention are described below. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

[0033] Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.

[0034] Many modifications and changes may be made to the particular embodiments of the invention described herein without departing from the scope or spirit of the invention, and the description and examples are intended to be exemplary only.

[0035] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0036] Unless otherwise specified, the raw materials used in the present invention are purchased from the market.

[0037] The present invention provides a NN bidentate ligand containing a penta-fused ring, which has the following general structural formula.

[0038]

[0039] Where R 1 -R 10 The structure of the group is independently selected from any one of hydrogen atom, halogen, straight chain or branched alkyl or alkoxy with 1 to 30 carbon atoms, aryl, nitro, amino, methylamino, dimethylamino, carboxyl, and ester group; or R in Formula I 1 -R 10 Any adjacent positions are connected to form a ring through several covalent bonds.

[0040] The preparation method of the NN bidentate ligand containing a penta-fused ring comprises the following steps.

[0041] Under an inert atmosphere, two identical or different substrates represented by formula III and formula IV are added to a reaction container, DMF is added as a reaction solvent, and the mixture is heated to 50° C. and stirred. Under the catalytic action of nickel chloride hexahydrate, triphenylphosphine and zinc powder, the substrates represented by formula III and formula IV are coupled to obtain the intermediate product V shown. The intermediate product V is dried and added to a reaction container, ethylene glycol dimethyl ether is added as a reaction solvent, potassium chips are added, and the mixture is stirred at room temperature, so that the intermediate product V undergoes a reduction cyclization reaction. Anhydrous tetrahydrofuran is added, and the mixture is oxidized in air to obtain the compound represented by formula I.

[0042] The technical solution of the present invention is further described below in conjunction with specific examples. In the following examples, the preparation and application of preferred ligands II-2, II-5, II-8, and II-15 are used as examples for experiments. Example

[0043] Example 1: The synthetic route of compound II-2 is as follows.

[0044]

[0045] Step 1: Add zinc powder (0.65 g, 10.0 mmol), nickel chloride hexahydrate (2.38 g, 10.0 mmol), and triphenylphosphine (10.49 g, 40.0 mmol) to a 100 mL two-necked flask, pump argon three times, add N,N-dimethylformamide (50 mL) under argon protection to dissolve, heat to 50°C, and stir for 2 hours. Add compound II-2A (1.78 g, 10.0 mmol) under argon protection and continue to react for 8 hours. Pour the reaction solution into dilute ammonia water, stir in the air for 30 minutes, and then filter. Use a mixed solution of dichloromethane and methanol as the eluent, and separate the filtered solid by column chromatography to obtain product II-2B (white powder, yield 75%).

[0046] 1 H NMR (600 MHz, Chloroform- d )δ 7.83 (d, J = 8.3 Hz, 2H), 7.66 – 7.60(m, 4H), 7.52 (d, J = 8.5 Hz, 2H), 7.36 – 7.31 (m, 2H), 2.79 (s, 6H).

[0047] 13 C NMR (151 MHz, Chloroform- d) δ 157.96, 150.92, 137.62, 130.39, 127.24, 126.58, 126.40, 126.13, 119.23, 24.40.

[0048] HRMS (ESI)calcd for C 20 H 17 N 2 + ([M+H] + ): 285.1313, found: 285.1322.

[0049] Step 2: Add the product II-2B (0.57 g, 2.0 mmol) from step 1 to a 100 mL two-necked bottle, pump argon three times, add ethylene glycol dimethyl ether (16 mL) under argon protection to dissolve, and add potassium chips (0.94 g, 24.0 mmol) after II-2B is completely dissolved. Stir at room temperature for 16 hours. After the reaction is completed, remove the remaining potassium chips, add anhydrous tetrahydrofuran (30 mL), and stir in the air for 4 hours. Vacuum rotary evaporation to remove the solvent, use a mixed solution of dichloromethane and methanol as the eluent, and separate the remaining solid by column chromatography to obtain product II-2 (yellow powder, yield 55%).

[0050] 1 H NMR (600 MHz, Chloroform- d ) δ 8.26 – 8.23 ​​(m, 2H), 7.70 – 7.66 (m,4H), 7.51 (s, 2H), 2.90 (s, 6H).

[0051] 13 C NMR (151 MHz, Chloroform- d ) δ 153.93, 149.88, 138.03, 130.86, 130.65, 126.89, 123.40, 121.35, 120.49, 24.77.

[0052] HRMS (ESI)calcd for C 20 H 15 N 2 + ([M+H] + ): 283.1157, found: 283.1153.

[0053] Example 2: The synthetic route of compound II-5 is as follows.

[0054]

[0055] Step 1: Add zinc powder (0.65 g, 10.0 mmol), nickel chloride hexahydrate (2.38 g, 10.0 mmol), and triphenylphosphine (10.49 g, 40.0 mmol) to a 100 mL two-necked flask, pump argon three times, add N,N-dimethylformamide (50 mL) under argon protection to dissolve, heat to 50°C, and stir for 2 hours. Add compound II-5A (1.78 g, 10.0 mmol) under argon protection and continue to react for 8 hours. Pour the reaction solution into dilute ammonia water, stir in the air for 30 minutes, and then filter. Use a mixed solution of dichloromethane and methanol as the eluent, and separate the filtered solid by column chromatography to obtain product II-5B (white powder, yield 75%).

[0056] 1 H NMR (600 MHz, Chloroform- d ) δ 8.65 (d, J = 5.7 Hz, 2H), 7.73 – 7.69(m, 4H), 7.62 (d, J = 8.6 Hz, 2H), 7.30 – 7.27 (m, 2H), 2.53 (S, 6H).

[0057] 13 C NMR (151 MHz, Chloroform- d ) δ 157.91, 142.10, 140.83, 137.26, 129.90, 127.12, 126.33, 125.85, 120.62, 22.06.

[0058] HRMS (ESI)calcd for C 20 H 17 N 2 + ([M+H] + ): 285.1313, found: 285.1320.

[0059] Step 2: Add the product II-5B (0.57 g, 2.0 mmol) from step 1 to a 100 mL two-necked bottle, pump argon three times, add ethylene glycol dimethyl ether (16 mL) under argon protection to dissolve, and add potassium chips (0.94 g, 24.0 mmol) after II-5B is completely dissolved. Stir at room temperature for 16 hours. After the reaction is completed, remove the remaining potassium chips, add anhydrous tetrahydrofuran (30 mL), and stir in the air for 4 hours. Vacuum rotary evaporation to remove the solvent, use a mixed solution of dichloromethane and methanol as the eluent, and separate the remaining solid by column chromatography to obtain product II-5 (yellow powder, yield 65%).

[0060] 1 H NMR (600 MHz, Chloroform- d ) δ 8.76 (d, J = 5.5 Hz, 2H), 8.05 (s,2H), 7.53 (d, J = 5.5 Hz, 2H), 7.50 (s, 2H), 2.58 (s, 6H).

[0061] Example 3: The synthetic route of compound II-8 is as follows.

[0062]

[0063] Step 1: Add zinc powder (1.30 g, 20.0 mmol), nickel chloride hexahydrate (4.76 g, 20.0 mmol), and triphenylphosphine (20.98 g, 80.0 mmol) to a 250 mL two-necked flask, pump argon three times, add N,N-dimethylformamide (100 mL) to dissolve under argon protection, heat to 50°C, and stir for 2 hours. Add compound II-8A (3.88 g, 20.0 mmol) under argon protection and continue to react for 8 hours. Pour the reaction solution into dilute ammonia water, stir in the air for 30 minutes, and then filter. Use a mixed solution of dichloromethane and methanol as the eluent, and separate the filtered solid by column chromatography to obtain product II-8B (colorless viscous liquid, yield 50%).

[0064] 1 H NMR (600 MHz, Chloroform- d ) δ 8.66 (d, J = 5.7 Hz, 2H), 7.78 – 7.71(m, 6H), 7.40 – 7.36 (m, 2H), 3.13 – 3.05 (m, 2H), 1.33 (d,J = 6.9 Hz, 12H).

[0065] 13 C NMR (151 MHz, Chloroform- d ) δ 157.99, 151.40, 142.04, 137.45, 127.71, 127.35, 126.75, 123.12, 120.95, 34.55, 23.72.

[0066] HRMS (ESI)calcd for C 24 H 25 N 2 + ([M+H] + ): 341.1939, found: 341.1934.

[0067] Step 2: Add the product II-8B (1.02 g, 3.0 mmol) from step 1 to a 100 mL two-necked bottle, pump and fill with argon three times, add ethylene glycol dimethyl ether (24 mL) under argon protection to dissolve, and add potassium chips (1.41 g, 36.0 mmol) after II-8B is completely dissolved. Stir at room temperature for 16 hours. After the reaction is completed, remove the remaining potassium chips, add anhydrous tetrahydrofuran (60 mL), and stir in the air for 4 hours. Vacuum rotary evaporation to remove the solvent, use a mixed solution of dichloromethane and methanol as the eluent, and separate the remaining solid by column chromatography to obtain product II-8 (yellow powder, yield 75%).

[0068] 1 H NMR (600 MHz, Chloroform- d ) δ 8.79 (d, J = 5.5 Hz, 2H), 8.25 (d, J =1.4 Hz, 2H), 7.62 – 7.60 (m, 4H), 3.19 (p, J = 6.9 Hz, 2H), 1.44 (d, J = 6.9 Hz,12H).

[0069] 13 C NMR (151 MHz, Chloroform- d) δ 151.69, 150.30, 144.92, 137.84, 130.94, 124.03, 123.84, 122.30, 121.69, 34.92, 23.87.

[0070] HRMS (ESI)calcd for C 24 H 23 N 2 + ([M+H] + ): 339.1783, found: 339.1787.

[0071] Example 4: The synthetic route of compound II-15 is as follows.

[0072]

[0073] Step 1: Add zinc powder (0.65 g, 10.0 mmol), nickel chloride hexahydrate (2.38 g, 10.0 mmol), and triphenylphosphine (10.49 g, 40.0 mmol) to a 100 mL double-necked flask, pump argon three times, add N,N-dimethylformamide (50 mL) under argon protection to dissolve, heat to 50°C, and stir for 2 hours. Add compound II-15A (1.94 g, 10.0 mmol) under argon protection and continue to react for 8 hours. Pour the reaction solution into dilute ammonia water, stir in the air for 30 minutes, and then filter. Use a mixed solution of dichloromethane and methanol as the eluent, and separate the filtered solid by column chromatography to obtain product II-15B (white powder, yield 75%).

[0074] 1 H NMR (600 MHz, Chloroform- d ) δ 8.61 (d, J = 5.7 Hz, 2H), 7.68 (d, J =5.7 Hz, 2H), 7.64 (d, J = 9.2 Hz, 2H), 7.16 (d, J = 2.5 Hz, 2H), 7.11 – 7.07 (m, 2H), 3.96 (s, 6H).

[0075] 13 C NMR (151 MHz, Chloroform- d) δ 160.97, 157.62, 142.62, 139.11, 129.21, 123.71, 120.67, 120.44, 104.44, 55.64.

[0076] HRMS (ESI)calcd for C 20 H 17 N 2 O 2 + ([M+H] + ): 317.1212, found: 317.1218.

[0077] Step 2: Add the product II-15B (0.63 g, 2.0 mmol) of step 1 to a 100 mL two-necked bottle, pump argon three times, add ethylene glycol dimethyl ether (16 mL) under argon protection to dissolve, and add potassium chips (0.94 g, 24.0 mmol) after II-15B is completely dissolved. Stir at room temperature for 16 hours. After the reaction is completed, remove the remaining potassium chips, add anhydrous tetrahydrofuran (30 mL), and stir in the air for 4 hours. Vacuum rotary evaporation to remove the solvent, use a mixed solution of dichloromethane and methanol as the eluent, and separate the remaining solid by column chromatography to obtain product II-15 (yellow powder, yield 75%).

[0078] 1 H NMR (600 MHz, Chloroform-d) δ 8.73 (d, J = 5.4 Hz, 2H), 7.81 (s, 2H), 7.55 (d, J = 5.5 Hz, 2H), 7.08 (s, 2H), 4.00 (s, 6H).

[0079] 13 C NMR (151 MHz, Chloroform- d ) δ 159.37, 156.84, 145.73, 139.86, 132.49, 130.43, 120.95, 114.97, 105.52, 55.75.

[0080] HRMS (ESI)calcd for C 20 H 15 N 2 O 2 + ([M+H] +): 315.1055, found: 315.1059. Practical Examples

[0081] Practical Example 1: Synthesis method of polymer transport materials.

[0082] The polymer carrier transport material was prepared by direct arylation polymerization catalyzed by monovalent copper, and the NN bidentate ligands II-2, II-5, II-8, and II-15 prepared in Examples 1, 2, 3, and 4 were used to improve the catalytic activity of cuprous iodide. The synthesis route of polymer P1 is as follows.

[0083]

[0084] The synthesis method of polymer P1 is as follows: iodinated bithiophene monomer S1 (65.4 mg, 0.10 mmol), active hydrogen-containing bithiazole monomer S2 (31.2 mg, 0.10 mmol), cuprous iodide (1.9 mg, 0.01 mmol), NN bidentate ligand (0.01 mmol), potassium phosphate (84.9 mg, 0.40 mmol) were added to a 25 mL schlenk reaction tube, argon was pumped three times, N-methylpyrrolidone (1.5 mL) was added with a syringe, and the reaction was heated to 140°C for 24 hours. After the reaction was completed, the temperature was cooled to room temperature, 15 mL of methanol was added for precipitation, the solid was filtered and washed with distilled water and methanol, and the remaining solid was treated with a Soxhlet extractor and vacuum dried to obtain polymer P1. Depending on the selected NN bidentate ligand, their masses are II-2 (2.8 mg), II-5 (2.8 mg), II-8 (3.4 mg), and II-15 (3.1 mg), respectively.

[0085] Practical Example 2: Preparation method of organic field effect transistor.

[0086] (1) Cleaning and processing the substrate: After removing the protective film from the polyethylene terephthalate (PET) sheet, ultrasonically clean it twice with secondary water, then ultrasonically clean it twice with isopropyl alcohol, blow nitrogen gas until the surface is clean, and place it in the mask plate for later use.

[0087] (2) Device preparation: The entire operation was carried out in a glove box. A mask with a W / L ratio of 4500 / 90 was used. A vacuum evaporation system was used to evaporate the bottom electrode. 24 nm gold was evaporated. The chloroform solution of polymer P1 was spin-coated on the PET substrate at a speed of 1500 rpm for 50 seconds and annealed at 135°C for 10 minutes. The polymer layer was covered with a mask, and the polymer surface was patterned using oxygen plasma. Sodium chloride solution was dripped on the surface of the treated device.

[0088] (3) Test characterization: The resulting device was characterized using a source instrument B2912A.

Claims

1. A NN bidentate imine compound containing five fused rings, characterized in that Its structure is as shown in the following formula I.

2. Where R1-R 10 The structure of the group is independently selected from any one of hydrogen atom, halogen, straight chain or branched alkyl or alkoxy with 1 to 30 carbon atoms, aryl, nitro, amino, methylamino, dimethylamino, carboxyl, and ester group; or R1-R 10 Any adjacent positions are connected to form a ring through several covalent bonds.

3. The compound according to claim 1, characterized in that The compound represented by formula I is any one of the following formulas II-1 to II-50, but is not limited to the following compounds:

4. The method for preparing the compound of structure I according to claim 1, characterized in that The following steps are involved: Under an inert atmosphere, two identical or different substrates represented by formula III and formula IV are added to a reaction container, DMF is added as a reaction solvent, and the mixture is heated to 50° C. and stirred. Under the catalytic action of nickel chloride hexahydrate, triphenylphosphine and zinc powder, the substrates represented by formula III and formula IV are coupled to obtain the intermediate product V shown. The intermediate product V is dried and added to a reaction container, ethylene glycol dimethyl ether is added as a reaction solvent, potassium chips are added, and the mixture is stirred at room temperature, so that the intermediate product V undergoes a reduction cyclization reaction. Anhydrous tetrahydrofuran is added, and the mixture is oxidized in air to obtain the compound represented by formula I.

5. Use of the NN bidentate ligand molecule containing five fused rings as claimed in claim 1 in the preparation of polymer optoelectronic materials.

6. The use according to claim 5, characterized in that: In the preparation process, a copper-catalyzed direct arylation polymerization reaction is used as a synthesis method of the material.

7. The synthesis method according to claim 6, characterized in that In a copper-catalyzed direct arylation polymerization reaction, the NN biligand molecule containing five fused rings as claimed in claim 1 is used as a ligand in the reaction.

8. An organic electrochemical transistor device, characterized in that: include: A bottom electrode, a top electrode, an electrolyte solution, and a polymer channel material, wherein the channel material is a polymer photoelectric material prepared by the synthesis method according to claim 6.

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