Preparation method and application of quinoline-pyrrolopyrrole OLET polymer material

Abstract

The application belongs to the field of organic semiconductor polymer photoelectric materials, and solves the problem that most conjugated polymers are difficult to simultaneously realize high carrier mobility and strong light emitting performance through molecular design. The pyrrolopyrrolopyridine polymer based on quinoline side groups provided by the application can be used as channel material of organic field effect transistor (OFET), light emitting layer of organic light emitting diode (OLED) and active layer material of organic light emitting transistor (OLET), and has a structure as shown in Figure 1. The QDPP compound provided by the application has good thermal stability, balanced bipolar transmission characteristics and high photoluminescence quantum yield.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials, specifically relating to a series of methods for synthesizing materials with quinoline as a flanking group. The compounds possess both bipolar mobility and red light emission properties, and can be used in the fabrication of various organic semiconductor devices. Background Technology

[0002] Organic light-emitting transistors (OLETs), as optoelectronic devices integrating switching and light-emitting functions, have significant application prospects in flat panel displays, solid-state lighting, and optoelectronic integrated circuits. Their core structure typically achieves both carrier transport and electroluminescence simultaneously within an organic semiconductor layer. Currently, small-molecule organic semiconductor materials are widely studied in OLET devices, but their fabrication largely relies on vacuum evaporation processes, making large-area, low-cost manufacturing difficult.

[0003] Compared to small-molecule materials deposited in vacuum, solution-processable polymer semiconductor materials are easier to fabricate on a large scale using processes such as inkjet printing and roll-to-roll, offering significant advantages in integrated and flexible electronics. However, traditional polymer semiconductor materials often struggle to simultaneously possess both high carrier mobility and efficient light emission. Most high-mobility polymers exhibit low luminescence efficiency, while polymers with excellent luminescence properties typically have weak charge transport capabilities, limiting device performance and hindering the integration of high-efficiency, high-brightness optoelectronic functions. Therefore, developing polymer semiconductor materials that combine efficient charge transport and ideal light emission characteristics, and optimizing device structures to balance charge injection, transport, and recombination processes, has become a pressing technical challenge in this field.

[0004] Using pyrrolopyrroledione as the acceptor unit, a series of organic semiconductor materials based on this structure have been successfully prepared by modulating its flanking groups, such as TDPP monomers with thiophene flanking groups and PyDPP with pyridine flanking groups. These materials exhibit excellent electrical properties and good stability. In this invention, quinoline is selected as the flanking group of DPP in the main chain, which can significantly modulate the photoelectric properties of the copolymer. Compared with TDPP and PyDPP, QDPP achieves a wider band gap and stronger electron depletion. Notably, we coupled the two QDPP units with vinyl groups, which stabilized the planarity while effectively extending the intrachain conjugation. The series of polymer materials synthesized based on quinoline DPP have excellent photoelectric properties and can be applied in organic optoelectronic devices. Summary of the Invention

[0005] This invention addresses the low luminescence efficiency of existing high-mobility polymers by providing a series of polymer materials with high-mobility red light emission, along with their preparation methods and applications. The invention uses DPP as the main component and modifies its structure by introducing flexible alkyl chains to improve solubility; increasing the conjugation length by introducing auxochromes or chromophores such as aromatic rings to enhance the delocalization ability of its π-system electron cloud, thereby improving electron transport capability and fluorescence quantum efficiency; and modifying the molecular configuration and stacking by introducing substituent atoms with different electron-withdrawing capabilities onto the quinoline flanking groups, thus altering its optical and electrical properties and improving its application performance. A series of QDPP-like compounds are synthesized through molecular design.

[0006] A class of quinoline flanking pyrrolopyrrole polymer materials with high mobility and strong luminescence properties have the following general chemical formula:

[0007] 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 aforementioned polymer optoelectronic material.

[0008] The invention also provides a method for fabricating an organic field-effect transistor device, the method comprising the following steps: (1) Cleaning and treating the substrate: After peeling off the protective film from a polyethylene terephthalate (PET) sheet, it is ultrasonically cleaned twice with deionized water, then ultrasonically cleaned twice with isopropanol, and purged with nitrogen until the surface is clean before being placed in a mask for later use. (2) Fabricating the device: The entire operation is carried out in a glove box, using a mask with a W / L ratio of 4500 / 90, and a vacuum evaporation system is used to deposit the bottom electrode, depositing 24 nm of gold. A chloroform solution of the polymer prepared above is spin-coated onto the PET substrate at a speed of 1500 rpm for 50 seconds, followed by annealing for 10 minutes. The polymer layer is covered with a mask, and the polymer surface is patterned using oxygen plasma. A sodium chloride solution is dropped onto the surface of the treated device. (3) Testing and characterization: The obtained device is characterized using a source meter B2912A.

[0009] The beneficial effects of this invention are as follows: 1. The compound with quinoline as a flanking group provided by this invention has good physicochemical stability and high fluorescence quantum yield. The OFET device prepared with it as the channel material layer has high and balanced electron mobility, and the prepared organic light-emitting transistor device has high photoelectric conversion efficiency. 2. The preparation method of this invention has a simple synthetic route, mild reaction conditions, and high yield. Attached Figure Description

[0010] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0011] Figure 1 The hydrogen spectrum of 3,6-bis(6-bromoquinoline-2-yl)-2,5-bis(2-decylpentadecanyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione synthesized in Example 1.

[0012] Figure 2 The hydrogen spectrum of the synthesized 3,6-bis(6-bromoquinoline-2-yl)-2,5-bis(2-decylhexadecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione described in Example 1.

[0013] Figure 3 The hydrogen spectrum of the synthesized 3,6-bis(6-bromoquinoline-2-yl)-2,5-bis(2-decylheptadecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione described in Example 1.

[0014] Figure 4 The hydrogen spectrum of the synthesized 3,6-bis(6-bromo-7-methoxyquinoline-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione as described in Example 2.

[0015] Figure 5 The hydrogen spectrum of the synthesized 3,6-bis(6-bromo-7-fluoroquinoline-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione described in Example 2.

[0016] Figure 6 The 1H NMR spectrum of (E)-6,6'-(ethylene-1,2-diylbis(quinoline-6,2-diyl))bis(3-(6-bromoquinoline-2-yl)-2,5-bis(2-decyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) synthesized as described in Example 2. Figure 7 The concentration gradient UV-Vis spectrum, concentration gradient fluorescence spectrum, and output transfer characteristic curve of the organic field-effect transistor device are respectively the concentration gradient UV-Vis spectrum, concentration gradient fluorescence spectrum, and organic field-effect transistor device of the polymer materials described in Examples 1-4. Figure 8 shows the normalized concentration gradient UV-Vis spectra, normalized concentration gradient fluorescence spectra, and organic field-effect transistor output transfer characteristic curves of the three polymer materials QDPPR2-V, FQDPP-V, and QDED-PVP described in Examples 1-4, respectively. The figure shows that with increasing polymer concentration, both the UV absorption and fluorescence spectra exhibit varying degrees of redshift. The ratio of the 0-0 peak intensity to the 0-1 peak intensity changes significantly with increasing concentration, suggesting the formation of H aggregates in the first two materials and J aggregates in the third material. The output transfer characteristic curves in the two columns on the right show that all three synthesized polymers possess good output, transfer characteristics, and bipolar mobility, as shown in the table above. Detailed Implementation

[0017] Unless explicitly defined, all technical and scientific terms used in this application have the same meaning as commonly understood by those skilled in the art in relation to the subject matter. The invention is further illustrated below with reference to embodiments, but the invention is not limited to these examples.

[0018] Example 1: Taking the synthesis of compound QDPP-V as an example, its general structural formula is:

[0019] Step 1: Synthesis of 6-bromoquinoline nitrogen oxides

[0020] The starting material, 6-bromoquinoline (12.5 g, 60.0 mmol), was dissolved in DCM (240.0 mL) and cooled to 0 °C. Then, 3-chloroperbenzoic acid (15.5 g, 90.0 mmol) was added in small, repeated additions. The mixture was stirred and reacted overnight at room temperature. Then, Na₂CO₃ solution (10.0 M, 200.0 mL) was added, and the mixture was extracted with DCM. The organic layer was washed with water and dried over Na₂SO₄. Finally, the crude product was purified by silica gel column chromatography (PE:DCM = 1:1) to give a white solid compound, 6-bromoquinoline oxynitride (62.2%, 8.4 g). 1 H NMR (600 MHz, CDCl3): δ 8.56 (d, J = 9.3 Hz, 1H), 8.46 (d, J = 6.0 Hz, 1H), 7.98 (d, J = 2.1 Hz, 1H), 7.76 (dd, J = 9.3, 2.0 Hz, 1H), 7.59(d, J= 8.5 Hz, 1H), 7.28 (dd, J = 8.5, 6.0 Hz, 1H). 13 C NMR (151 MHz, CDCl3): δ140.47, 135.82, 133.77, 131.69, 130.18, 124.60, 123.33, 122.32, 121.83. HRMS(ESI + m / z: calcd. for [M+H] + , C9H7ONBr: 223.9706; found: 223.9704. Step 2: Synthesis of 6-bromoquinoline-2-carboxynitrile

[0021] 6-Bromoquinoline oxynitride (8.4 g, 37.4 mmol) was dissolved in acetonitrile (100.0 mL) under an argon atmosphere and cooled to 0 °C. Then, triethylamine (Et3N) (18.1 mL, 130.0 mmol) and TMSCN (16.3 mL, 130.0 mmol) were added sequentially. The suspension was stirred overnight at room temperature, followed by rotary evaporation to concentrate and remove the solvent. Finally, the crude product was purified by silica gel column chromatography (PE:EA = 4:1) to give the gray solid compound 6-bromoquinoline-2-carboxynitrile (93.8%, 8.1 g). 1 H NMR (600 MHz, DMSO- d 6 ): δ 8.60 (d, J = 8.5 Hz, 1H), 8.43 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 8.5 Hz, 1H), 8.06 - 8.01 (m, 2H). 13 C NMR (151 MHz, DMSO- d 6 ): δ146.55, 138.25, 135.25, 134.03, 131.78, 130.93, 130.30, 125.36, 123.52,118.03. HRMS (ESI + m / z: calcd. for [M+H] + C 10 H6BrN2: 232.9709; found:232.9710. Step 3: Synthesis of 3,6-bis(6-bromoquinoline-2-yl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione

[0022] Under an argon atmosphere, Na (1.2 g, 52.2 mmol) was added to a solution containing FeCl3 (5.3 mg). t The solution was stirred in 150.0 mL of AmOH and heated under reflux until all Na was consumed and dissolved. The solution was cooled to 90 °C, and 8.2 g (35.0 mmol) of 6-bromoquinoline-2-carboxynitrile was added, followed by dropwise addition of diisopropyl succinate (DIPS) (3.2 g, 15.8 mmol). The resulting mixture was stirred overnight at 100 °C. The mixture was then cooled to room temperature, and the reaction was quenched by adding a mixed solvent of MeOH (36.0 mL) and glacial acetic acid (26.0 mL), and stirred at 90 °C for 10 minutes. The precipitate was collected by filtration and washed three times with hot water and hot MeOH, respectively. A purple solid compound (61.5%, 5.9 g) was obtained. Step 4: Synthesis of 3,6-bis(6-bromoquinolin-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione

[0023] K₂CO₃ (2.2 g, 16.0 mmol) was added to a DMF (110.0 mL) solution containing 3,6-bis(6-bromoquinoline-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (2.2 g, 4.0 mmol). The reaction mixture was heated at 120 °C for 1 hour, followed by the dropwise addition of 1-bromo-2-decyltetradecane (6.7 g, 4.0 mmol). After stirring at 120 °C for another 3 hours, the reaction mixture was poured into water and extracted with DCM. The organic layer was washed with water, dried over Na₂SO₄, and then concentrated by rotary evaporation to remove the solvent. Finally, the crude product was purified by silica gel column chromatography (PE:EA = 10:1) to give a red solid (7.8%, 400 mg). 1 H NMR (600 MHz, CDCl3): δ 9.00 (d, J = 8.6 Hz, 2H), 8.24 (d, J = 8.7 Hz, 2H), 8.05 (d, J = 2.1 Hz, 2H), 7.98 (d, J= 8.9 Hz, 2H), 7.82 (dd, J = 9.0, 2.2 Hz, 2H), 4.49(d, J = 7.5 Hz, 4H), 1.63 - 1.56 (m, 2H), 1.28 - 1.05 (m, 80H), 0.88 - 0.82 (m, 12H). 13 C NMR (151 MHz, CDCl3): δ 162.72, 148.22, 146.06, 145.83, 135.90,133.83, 131.57, 129.90, 129.22, 124.83, 122.57, 112.99, 46.35, 38.37, 32.03,32.01, 31.48, 30.10, 29.81, 29.79, 29.77, 29.74, 29.67, 29.47, 29.46, 26.47,22.79, 14.23. + m / z: calcd. for [M+H] + C 72 H 109 Br2N4O2: 1221.6891; found: 1221.6899. The synthesis of 3,6-bis(6-bromoquinolin-2-yl)-2,5-bis(2-decylpentadecanyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione was performed using the same method as step 1 in step 4 above. 1 H NMR (600 MHz, CDCl3) δ 9.10 (d, J = 8.7Hz, 2H), 8.26 (d, J = 8.7 Hz, 2H), 8.06 (d, J = 2.2 Hz, 2H), 7.98 (d, J = 9.0 Hz,2H), 7.84 – 7.81 (m, 2H), 4.57 – 4.52 (m, 4H), 1.64 (dd, J = 10.0, 5.7 Hz, 4H),1.41 – 1.37 (m, 2H), 1.24 (s, 48H), 1.15 (s, 32H), 0.88 (d, J = 6.9 Hz, 10H), 0.86 (s, 2H).

[0024] The synthesis of 3,6-bis(6-bromoquinolin-2-yl)-2,5-bis(2-decylhexadecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione was performed using the same method as step 4 above. 1 H NMR (400 MHz, CDCl3) δ 9.19 (d, J = 8.7Hz, 2H), 8.24 (d, J = 8.8 Hz, 2H), 8.05 (s, 2H), 7.95 (d, J = 9.1 Hz, 2H), 7.82(d, J = 9.1 Hz, 2H), 4.45 (t, J = 7.6 Hz, 4H), 1.73 (s, 4H), 1.23 (s, 50H), 1.15 (s, 36H), 0.87 (s, 12H). 13 C NMR (101 MHz, CDCl3) δ 162.47, 148.04, 146.17,145.50, 135.85, 133.80, 131.67, 129.85, 129.19, 124.97, 122.64, 113.06,43.63, 37.33, 33.69, 32.03, 30.81, 30.19, 29.81, 29.77, 29.48, 27.33, 26.78,22.80, 14.25.

[0025] The synthesis of 3,6-bis(6-bromoquinolin-2-yl)-2,5-bis(2-decylheptadecyl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione was performed using the same method as step 4 above. 1 H NMR (600 MHz, ) δ 9.19 (d, J = 8.6 Hz, 2H), 8.24 (d, J = 8.7 Hz, 2H), 8.06 (d, J = 2.1 Hz, 2H), 7.94 (d, J = 8.9 Hz, 2H), 7.82(dd, J = 8.9, 2.2 Hz, 2H), 4.52 – 4.46 (m, 4H), 1.76 (p, J= 7.7 Hz, 4H), 1.55(dd, J = 14.5, 7.4 Hz, 4H), 1.38 (t, J = 7.7 Hz, 4H), 1.28 (s, 4H), 1.26 (s,12H), 1.24 (s, 50H), 1.18 (s, 16H), 0.88 (d, J = 6.8 Hz, 10H), 0.86 (s, 2H).

[0026] Step 5: Synthesis of a series of QDPP-V polymers

[0027] Synthesis of polymer QDPPL2-V: Trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), QDPPL2 (R = 2-decylpentadecane) (62.5 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (1.5 mL) and DMF (0.3 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer QDPP-V2 (86%, 48 mg). GPC (1,2,4-trichlorobenzene, 150 °C): M n = 27.9 kDa, M w = 67.0 kDa, PD = 2.40 Synthesis of polymer QDPPL3-V: Trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), QDPPL3 (R = 2-decylhexadecane) (63.9 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o-Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (1.5 mL) and DMF (0.3 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer QDPP-V3 (91%, 52 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n =41.9 kDa, M w = 84.7 kDa, PD = 2.40 Synthesis of polymer QDPPL4-V: trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), QDPPL4 (R being 2-decylheptadecane) (65.3 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (1.5 mL) and DMF (0.3 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer QDPP-V4 (80%, 48 mg) GPC (1,2,4-trichlorobenzene, 150 °C). M n =40.8 kDa, M w = 82.8 kDa, PD = 2.00 Example 2: Taking the synthesized polymers QDPP-V, FQDPP-V, MeOQDPP-V, and MeQDPP-V as examples, their structures are as follows:

[0028] Synthetic polymer FQDPP-V Step 1: Synthesis of 6-bromo-7-fluoroquinoline nitrogen oxides

[0029] The starting material, 6-bromo-7-fluoroquinoline (4.16 g, 20.0 mmol), was dissolved in DCM (80.0 mL) and cooled to 0°C. Then, 3-chloroperbenzoic acid (5.2 g, 30.0 mmol) was added in small, repeated additions. The mixture was stirred and reacted overnight at room temperature. KOH solution (10.0 M, 200.0 mL) was then added, and the mixture was extracted with DCM. The organic layer was washed with water and dried over Na₂SO₄. Finally, the crude product was purified by silica gel column chromatography (95%, 4.6 g). 1 H NMR (400 MHz, CDCl3) δ 8.51 (dd, J =6.1, 1.0 Hz, 1H), 8.08 (s, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.19 (dd, J = 8.4, 6.1Hz, 1H). 13 C NMR (151 MHz, CDCl3) δ 157.89, 141.88, 136.22, 132.21, 126.08, 124.92, 119.62, 116.96, 99.48. Step 2:

[0030] 6-Bromo-7-fluoroquinoline nitride (4.09 g, 16.9 mmol) was dissolved in acetonitrile (42 mL) under an argon atmosphere and cooled to 0 °C. Then, triethylamine (Et3N) (8.4 mL) and TMSCN (7.9 mL) were added sequentially. The suspension was stirred overnight at room temperature, followed by rotary evaporation to concentrate and remove the solvent. Finally, the crude product was purified by silica gel column chromatography (PE:EA = 4:1) to give the gray solid compound 6-bromo-7-fluoroquinoline-2-carboxynitrile (90%, 3.77 g). 1 H NMR (600 MHz, CDCl3) δ 8.25 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 7.1 Hz, 1H), 7.88 (d, J= 8.9 Hz, 1H), 7.71 (dd, J = 8.3, 1.0 Hz, 1H). Step 3:

[0031] Under an argon atmosphere, Na (0.77 g, 33.6 mmol) was added to a solution containing FeCl3 (5.3 mg). t The solution was stirred in 40 mL of AmOH and heated under reflux until all Na was consumed and dissolved. After cooling the solution to 90 °C, 6-bromo-7-fluoroquinoline-2-carboxynitrile (3.77 g, 15 mmol) was added, followed by dropwise addition of diisopropyl succinate (DIPS) (1.45 g, 7.15 mmol). The resulting mixture was stirred at 85 °C for 4–6 h. The mixture was then cooled to room temperature, and the reaction was quenched by adding a mixed solvent of MeOH (36.0 mL) and glacial acetic acid (26.0 mL), followed by stirring at 90 °C for 10 min. The precipitate was collected by filtration and washed three times with hot water and hot MeOH, respectively. A purple solid compound (28%, 1.17 g) was obtained. Step 4.

[0032] K₂CO₃ (1.11 g, 8.0 mmol) was added to a DMF (160.0 mL) solution containing 3,6-bis(6-bromo-7-fluoroquinoline-2-yl)pyrrolo[3,4-c]pyrrolo-1,4(2H,5H)-dione (1.17 g, 2.0 mmol). The reaction mixture was heated at 120 °C for 1 hour, followed by the dropwise addition of 1-bromo-2-decyltetradecane (3.34 g, 8.0 mmol). After stirring at 120 °C for another 3 hours, the reaction mixture was poured into water and extracted with DCM. The organic layer was washed with water, dried over Na₂SO₄, and concentrated by rotary evaporation to remove the solvent. The crude product was finally purified by silica gel column chromatography (PE:EA = 10:1) to give a red solid (13%, 320 mg). 1 H NMR (400 MHz, Chloroform- d ) δ 8.99 (d, J = 8.7 Hz, 2H), 8.28 (d, J = 8.7 Hz, 2H), 8.16 (d, J = 7.3 Hz, 2H), 7.81 (d, J = 9.2 Hz, 2H), 4.48 (d, J= 7.4 Hz, 4H), 1.28(s, 2H), 1.24 – 1.16 (m, 45H), 1.15 – 1.04 (m, 33H), 0.87 (dt, J = 7.1, 3.5 Hz, 12H). The synthesis processes of monomers MeOQDPP and MeQDPP are similar to those of FQDPP and QDPP mentioned above.

[0033] 1 H NMR (400 MHz, CDCl3) δ 8.75 (d, J = 8.5 Hz, 2H), 8.26 (d, J = 8.6 Hz,2H), 8.14 (s, 2H), 7.63 (s, 2H), 4.46 (d, J = 7.1 Hz, 4H), 4.09 (s, 6H), 2.07 –1.99 (m, 3H), 1.25 (s, 16H), 1.23 (s, 14H), 1.19 (s, 10H), 1.18 (s, 13H), 1.14 (s, 11H), 1.10 (s, 19H), 0.88 – 0.85 (m, 13H). Step 5: Synthesize polymer QDPP-V

[0034] Synthesis of polymer QDPP-V: Trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), QDPP (61.1 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o-Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer QDPP-V2 (86%, 48 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 20.2 kDa, M w = 43.4 kDa, PD = 2.14 Synthetic polymer FQDPP-V

[0035] Synthesis of polymer FQDPP-V: Trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), FQDPP (62.9 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer FQDPP-V (73%, 42 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 9.0 kDa, M w = 1.48 kDa, PD = 1.64 Synthetic polymer MeQDPP

[0036] Synthesis of polymer MeQDPP-V: Trans-1,2-bis(tributyltin)ethylene (27.9 mg, 0.046 mmol), MeQDPP (57.5 mg, 0.046 mmol), Pd2(dba)3 (1.68 mg, 0.0018 mmol), and P( o- Tol)3 (2.1 mg, 0.0069 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer MeQDPP-V (76%, 40 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 17.8 kDa, M w = 34.6 kDa, PD = 1.9 Synthetic polymer MeOQDPP

[0037] Synthesis of polymer FQDPP-V: Trans-1,2-bis(tributyltin)ethylene (30.3 mg, 0.05 mmol), FQDPP (64.1 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P( o-Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 12 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer FQDPP-V (82%, 48 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 30.3 kDa, M w = 60.4 kDa, PD = 2.0 Example 3: Polymerization of quinoline DPP and a series of donor units, with the following general structural formula:

[0038] Taking the synthetic polymers QDPP-T, FQDPP-T, MeOQDPP-T, and MeQDPP-T as examples

[0039] Synthesis of polymer QDPP-T: 2,5-bis(trimethyltinyl)thiophene (20.5 mg, 0.05 mmol), QDPP (61.1 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol) and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 8 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer FQDPP-V (82%, 48 mg) GPC (1,2,4-trichlorobenzene, 150 °C): Mn = 54.0 kDa, M w = 119.3 kDa, PD = 2.2

[0040] Synthesis of polymer FQDPP-T: 2,5-bis(trimethyltinyl)thiophene (13.0 mg, 0.032 mmol), QDPP (40.0 mg, 0.032 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol) and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 18 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer FQDPP-T (78%, 30 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 2.6 kDa, M w = 5.7 kDa, PD = 2.2

[0041] Synthesis of polymer MeQDPP-T: 2,5-bis(trimethyltinyl)thiophene (20.5 mg, 0.05 mmol), MeQDPP (62.5 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol) and P( o-Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 22 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer FQDPP-T (86%, 52 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 3.5 kDa, M w = 6.5 kDa, PD = 1.8

[0042] Synthesis of polymer MeOQDPP-T: 2,5-bis(trimethyltinyl)thiophene (20.5 mg, 0.05 mmol), MeOQDPP (64.1 mg, 0.05 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol) and P( o- Tol)3 (2.3 mg, 0.0075 mmol) was weighed into a Schlenk tube. Dissolved in anhydrous Tol (2.0 mL) and DMF (0.4 mL) under an argon atmosphere. After stirring at 120 °C for 22 hours, 2-bromothiophene (1.0 mL) was added for end-capping for 0.5 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the deep red polymer MeOQDPP-T (86%, 52 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 7.9 kDa, M w = 10.3 kDa, PD = 1.3

[0043] Synthesis of polymer QDPP-BTz: 4,4'-bis(butoxy)5,5'-bithiazole (15.6 mg, 0.05 mmol), MeOQDPP (61.0 mg, 0.05 mmol), Pd(OAc) (0.4 mg, 0.002 mmol), IAd (2.03 mg, 0.04 mmol), K2CO3 (6.9 mg, 0.05 mmol), and PivOH (5.1 mg, 0.05 mmol) were weighed into a Schlenk tube. Dissolved in anhydrous Mesitylene (1.0 mL) and DMF (1.0 mL) under an argon atmosphere. The reaction was stirred at 130 °C for 20 hours. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded the dark red polymer QDPP-BTz (83%, 52 mg) GPC (1,2,4-trichlorobenzene, 150 °C). M n = 14.2 kDa, M w = 20.2 kDa, PD = 1.4 Example 4: Polymerization of vinyl-bridged quinoline DPP and a series of donor units, with the following general structural formula:

[0044] Step 1: Stille coupling of quinoline DPP with vinyltin reagent

[0045] QDPP (1.53 g, 1.25 mmol))(PPh3)4Pd (0.0144 g, 0.0125 mmol) was added to a two-necked flask, and the mixture was purged three times with argon. Anhydrous and oxygen-free toluene (30 mL) was added as a solvent, and trans-1,2-bis(tributyltin)ethylene (0.15 g, 0.25 mmol) dissolved in toluene was added dropwise. The mixture was heated at 120 °C for 3 hours, and the reaction mixture was concentrated by rotary evaporation to remove the solvent. Finally, the crude product was purified by silica gel column chromatography (PE:EA = 3:2) to give a deep red solid (52%, 301 mg). 1 HNMR (600 MHz, CDCl3) δ 9.02 (dd, J = 8.5, 6.0 Hz, 4H), 8.25 (d, J= 8.6 Hz, 2H), 8.19 (d, J = 8.7 Hz, 2H), 8.05 (d, J = 8.7 Hz, 2H), 7.99 – 7.93 (m, 6H), 7.82 –7.77 (m, 4H), 7.36 (s, 2H), 4.52 (s, 8H), 1.69 (dt, J = 12.0, 6.3 Hz, 4H), 1.28– 1.23 (m, 40H), 1.22 – 1.17 (m, 77H), 1.15 – 1.11 (m, 43H), 0.86 (d, J = 4.4Hz, 12H), 0.84 (d, J = 3.4 Hz, 12H). 13 C NMR (101 MHz, CDCl3) δ 162.75, 162.65,148.25, 147.54, 147.42, 146.04, 136.61, 135.70, 133.67, 131.54, 130.44,129.81, 129.11, 128.50, 126.28, 124.90, 124.70, 122.44, 46.56, 38.39, 32.03,31.48, 30.17, 29.82, 29.77, 29.70, 29.48, 26.50, 22.79, 14.22. Step 2: Synthesis of polymers QDVD-T, QDVD-TVT, QDVD-P, and QDVD-PVP

[0046] Synthesis of polymer QDVD-T: 2,5-bis(trimethyltinyl)thiophene (10.2 mg, 0.025 mmol), QDVD (57.7 mg, 0.025 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and P(o-Tol)3 (2.3 mg, 0.0075 mmol) were weighed into a Schlenk tube. Dissolved in anhydrous Tol (1.5 mL) and DMF (0.3 mL) under an argon atmosphere. After stirring at 120 °C for 7 min, 2-bromothiophene (1.0 mL) was added for end-capping reaction for 0.5 h. After cooling to room temperature, the mixture was precipitated in MeOH. The crude polymer was collected by filtration and purified by Soxhlet extraction with MeOH, acetone, and Hexane sequentially. The remaining product was dissolved in chloroform under reflux. The chloroform solution was then concentrated by rotary evaporation and precipitated in MeOH. Drying under vacuum yielded a deep red polymer QDVD-T (94%, 53 mg) GPC (1,2,4-trichlorobenzene, 150 °C): M n = 54.9kDa, M w = 13.0 kDa, PD = 2.4

[0047] Synthesis of polymer QDVD-TVT: The specific steps are the same as those for polymer QDVD-T. The reaction time was 18 min (46%, 27 mg). GPC (1,2,4-trichlorobenzene, 150 °C): M n = 15.8 kDa, M w = 57.7kDa, PD = 3.6

[0048] Synthesis of polymer QDVD-P: The specific steps are the same as those for polymer QDVD-T. The reaction time was 32 min (62.5%, 35 mg). GPC (1,2,4-trichlorobenzene, 150 °C): M n = 21.9 kDa, M w = 75.1kDa, PD = 3.4

[0049] Synthesis of polymer QDVD-PVP: The specific steps are the same as those for polymer QDVD-T. The reaction time was 1 h (54%, 32 mg). GPC (1,2,4-trichlorobenzene, 150 °C): M n = 18.6 kDa, M w = 39.1 kDa, PD = 2.1 Example 5: The high-mobility, strongly luminescent quinoline-pyrrole organic small molecules prepared in Examples 1-4 were subjected to UV-Vis and fluorescence spectroscopy tests, as well as fluorescence quantum yield tests. Taking the material QDVD-T from Example 4 as an example, a two-sided transparent UV quartz cuvette was selected, and a concentration gradient solution with chloroform as solvent was prepared. The UV-Vis absorption spectra at different concentrations were tested. A 5 mg / mL film was dropped onto a quartz plate, and the UV-Vis absorption spectrum in the solid state was tested. A four-sided transparent fluorescent quartz cuvette was selected, and a solution with the same concentration gradient as that used in the UV-Vis absorption spectroscopy tests was added. The fluorescence emission spectrum and fluorescence quantum yield were then tested.

[0050] Example 6: To evaluate the charge transport performance of semiconductor materials, devices with top-gate / bottom-contact structures were fabricated using the materials from Examples 1-4. The bottom electrode (drain, D; source, S) was deposited using a vacuum evaporation system on a mask with a channel width / length (W / L) of 4500 / 90 mm, sequentially depositing 3 nm of Cr and 24 nm of Au. A polymer solution was then spin-coated onto a PET substrate at 1200 rpm and annealed at 150 °C for 10 minutes in a sealed environment. A polymethyl methacrylate (PMMA) dielectric layer solution was spin-coated onto the polymer layer at 2500 rpm and annealed at 95 °C for 15 minutes in an open environment. The annealed PET sheet was then placed in a mask for top electrode deposition, depositing 100 nm of Al as the gate (G). OFET characteristics were tested in an environment using a Keithley 4200 semiconductor characterization system. Typical output and transfer curves are shown below. Figure 7 As shown The mobility and fluorescence quantum yield measured in Examples 1-4 are shown in the table below.

[0051] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A class of pyrrolopyrrole small molecule monomers with quinoline and isoquinoline as flanking groups, characterized in that... It has the structure shown in Figures I and II below.

2. A class of vinyl-bridged pyrrolopyrrole small molecule monomers with quinoline as flanking groups, characterized in that... It has the structures shown in III and IV below.

3. A pyrrolopyrrole polymer with quinoline and isoquinoline as flanking groups, and its application in organic semiconductor devices such as organic light-emitting transistors (OLETs), characterized in that... It has the following structures as shown in V and VI.

4. A pyrrolopyrrole polymer with quinoline and isoquinoline as flanking groups, and its application in organic semiconductor devices such as organic light-emitting transistors (OLETs), characterized in that... It has the following structures as shown in VII, VIII, IX, and X.

5. The synthesis of monomers I and II according to claim 1, characterized in that... The process includes steps one and two. Specific steps: The monomer of the following formula is dissolved in DMF along with solid K₂CO₃, and the chain-up reaction is carried out under alkaline conditions. The synthesis of monomers III and IV according to claim 2 is characterized by comprising steps three and four, respectively. Specific steps: The quinoline DPP monomer undergoes a Stille coupling reaction with trans-1,2-bis(tri-n-butyltin)ethylene in the presence of a tetra(triphenylphosphine)palladium catalyst.

6. The polymer molecule synthesis V and VI according to claim 3, characterized in that... This includes steps one and two. The specific steps are as follows: Monomers I and II undergo a Stille coupling reaction with an organotin reagent in the presence of tris(o-methylphenyl)phosphine ligand and tris(dibenzylacetone)dipalladium catalyst. The polymer molecule synthesis VII, VIII, IX, and X according to claim 4 is characterized by comprising steps three, four, five, and six. The specific steps are as follows: monomers I, II, III, and IV undergo a Stille coupling reaction with an organotin reagent in the presence of a tris(o-methylphenyl)phosphine ligand and a tris(dibenzylacetone)dipalladium catalyst.

7. The application of the quinoline DPP compound according to any one of claims 1-4, characterized in that, The compound is used to prepare organic field-effect transistor channel materials, organic light-emitting diode light-emitting layer materials, and organic light-emitting transistor semiconductor layers.

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