Conjugated radical polymers with π-magnetization and bipolar semiconductor properties, their preparation and applications

Abstract

This invention belongs to the field of optoelectronic materials, and specifically discloses a conjugated free radical polymer with π-magnetization and bipolar semiconductor properties, having the general structure of Formula 1. Formula 1 shows that the conjugated free radical polymer of this invention exhibits interesting optoelectronic properties, such as enhanced near-infrared absorption, abundant redox activity, and an extremely narrow band gap. Benefiting from its spin delocalization properties and more ordered solid-state stacking characteristics, one of the conjugated free radical polymer materials exhibits a very rare weak room-temperature ferromagnetic phenomenon and excellent bipolar charge transport characteristics, and has extraordinary potential as a pure organic magnetic semiconductor.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic functional materials, specifically to a class of conjugated free radical polymers. Background Technology

[0002] Radical polymers (RPs), polymers with multiple radical centers, have attracted widespread attention due to their unique optoelectronic and magnetic properties compared to closed-shell polymers. Introducing radicals into the conjugated backbone of RPs is particularly attractive because they can effectively delocalize unpaired electrons on the conjugated backbone, resulting in interchain interactions of radicals via spatial and intrachain interactions via bond spin and / or charge transfer. Ideally, by controlling these intramolecular and intermolecular interactions of radical centers, RPs can simultaneously possess two properties, such as polymer π-electron magnetization and semiconductor properties, thus providing the organic magnetic semiconductor materials long sought by the scientific community, which are highly needed for emerging organic spintronics and magnetic, optical, and electronic applications. However, most RPs currently constructed are from non-conjugated backbones with localized radicals (exhibiting limited intramolecular / intermolecular electronic correlations between their radical centers), while RPs with delocalized unpaired electrons (i.e., conjugated radical polymers) remain largely unexplored, with only a few examples reported. Furthermore, a major challenge in this field is the synthesis of stable RPs with continuous radical introduction. The most common method—post-polymerization oxidation of polymers containing free radical precursors—often results in spin defects due to incomplete free radical transformation during the oxidation process.

[0003] Therefore, there is an urgent need to design new conjugated radical polymers and synthetic strategies, especially those that can achieve easily achievable structures and properties, in order to advance the creation of novel conjugated radical polymers with spin delocalization properties and more advanced material properties. Summary of the Invention

[0004] The primary objective of this invention is to provide a novel class of conjugated free radical polymers with π-magnetization and bipolar semiconductor properties.

[0005] The second objective of this invention is to provide a novel method for preparing conjugated free radical polymers.

[0006] A third objective of this invention is to provide an application of the aforementioned conjugated free radical polymer in the preparation of functional materials such as semiconductors and / or magnetization.

[0007] A fourth objective of this invention is to provide a functional material comprising or made from the conjugated free radical polymer.

[0008] A conjugated radical polymer with π-magnetization and bipolar semiconductor properties, having the general structural formula of Formula 1:

[0009]

[0010] In Formula 1, R1 and R2 are individually selected from -Cl, -Br, -I, -CN, Cl-C 24 Alkyl, C3-C 24 cycloalkyl, C1-C 24 Alkoxy, halogenated C1-C 24 Alkyl, halogenated C3-C 24 cycloalkyl or halogenated C3-C 24 alkoxy or aryl;

[0011] The Y is O, S, Se; the R3 and R4 are individually C6 to C6. 30 Alkyl groups. Further, the alkyl groups...

[0012] The value of n is 5 to 50.

[0013] This invention provides a novel class of conjugated free radical polymer materials, which exhibit excellent stability, readily yield gram-scale products, and display various optoelectronic properties, such as enhanced near-infrared absorption, abundant redox activity, and an extremely narrow band gap. Due to strong spin delocalization and spin-spin interactions within the molecule, these free radical polymers exhibit π-magnetization properties, even weak ferromagnetism at room temperature, while simultaneously possessing bipolar semiconductor properties, demonstrating potential applications as purely organic magnetic semiconductors.

[0014] In this invention, R1 is a phenyl, a substituted phenyl, or a five-membered heterocyclic aryl group.

[0015] The substituents of the substituted phenyl group include at least one of C1-C6 alkyl, C1-C6 alkoxy, and halogen.

[0016] In this invention, R2 is -H, -Cl, -Br, -I, or -CN.

[0017] In this invention, X is S; R3 and R4 are individually C1 to C1. 25 Alkyl groups. Furthermore, R3 and R4 can be the same substituent, and further can be... Ra can be C1 to C 20 Straight-chain alkyl groups (which may further be C5-C6) 15 (linear alkyl groups).

[0018] In this invention, n can be 15 to 30.

[0019] This invention also provides a method for preparing the conjugated free radical polymer described above, wherein the compound described in Formula 2 and the compound described in Formula 3 are coupled and polymerized to obtain:

[0020]

[0021] In Equations 2 and 3, R1, R2, R3, R4, and Y are the same as in Equation 1; X is a halogen, and R5 is an alkyltin group.

[0022] In this invention, X can be Br.

[0023] In this invention, the structure of the alkyltin group in R5 is, for example, as follows: The R can be, for example, a C1 to C5 alkyl group.

[0024] In this invention, during the coupling polymerization process, the molar ratio of Formula 2 and Formula 3 is 1:0.5 to 1.5; more specifically, it can be 1:0.9 to 1.1.

[0025] In this invention, the coupling polymerization process is carried out under the catalysis of a catalyst; the catalyst includes at least one of tris(o-methylphenyl)phosphine and tris(dibenzylacetone)dipalladium; further, the catalyst includes tris(o-methylphenyl)phosphine and tris(dibenzylacetone)dipalladium in a molar ratio of 3 to 4:1.

[0026] Preferably, the catalyst is used in an equivalent amount of 0.1 to 0.5 eqv, more preferably 0.3 to 0.35 eqv.

[0027] In this invention, the coupling polymerization process is carried out in a hydrophobic solvent;

[0028] Preferably, the hydrophobic solvent includes at least one of toluene, chlorobenzene, and xylene;

[0029] Preferably, the temperature of the coupling polymerization process is 100–150°C.

[0030] In this invention, the coupling polymerization time can be adjusted as needed, for example, it can be 5 to 60 hours.

[0031] The present invention also provides an application of the aforementioned conjugated free radical polymer for the preparation of bipolar transport semiconductors and / or magnetic materials.

[0032] The novel polymer structure described in this invention combines excellent semiconductor and magnetization effects.

[0033] The present invention also provides a functional material comprising, or prepared from, the conjugated free radical polymer described above;

[0034] Preferably, the functional material is a bipolar transport semiconductor material and / or a material with magnetic properties.

[0035] Beneficial effects

[0036] The conjugated radical polymer material provided by this invention is characterized by being obtained through the direct polymerization of diradical monomers, minimizing intramolecular defects and thus endowing the conjugated radical polymer with unique properties. The polymer described in this invention exhibits good stability, readily yields gram-scale products, and displays various optoelectronic properties, such as enhanced near-infrared absorption, abundant redox activity, and an extremely narrow band gap. For example, the strong spin delocalization and spin-spin interactions within the polymer can exhibit π-magnetization properties, even weak ferromagnetism at room temperature, while simultaneously possessing excellent bipolar charge transport characteristics, with maximum hole and electron mobilities reaching 0.41 and 0.38 cm⁻¹, respectively. 2 V -1 s -1 This demonstrates its extraordinary potential as a purely organic magnetic semiconductor. Attached Figure Description

[0037] Figure 1 This is the temperature-varying 1H NMR spectrum of SDBr-H prepared in Example 1;

[0038] Figure 2 The temperature-dependent proton NMR spectrum of SDBr-CN prepared in Example 2 is shown.

[0039] Figure 3 This is the mass spectrometry of the formula SDBr-H obtained in Example 1;

[0040] Figure 4 This is the mass spectrometry of the SDBr-CN prepared in Example 2;

[0041] Figure 5 These are the single-crystal structures of SDBr-H and SDBr-CN obtained in Examples 1 and 2;

[0042] Figure 6 The molecular weight test results are for the RPH prepared in Example 1;

[0043] Figure 7 The molecular weight test results are for the RPCs prepared in Example 2;

[0044] Figure 8 Thermogravimetric analysis of RPH and RPC obtained in Examples 1 and 2;

[0045] Figure 9 The UV absorption and CV test curves of SDBr-H, SDBr-CN, RPH and RPC prepared in Examples 1 and 2 are shown.

[0046] Figure 10This is a magnetic test diagram of the RPH obtained in Example 1;

[0047] Figure 11 This is a magnetic test diagram of the RPC obtained in Example 2;

[0048] Figure 12 These are the OFET device structure diagrams of RPH and RPC obtained in Examples 1 and 2;

[0049] Figure 13 This is a semiconductor performance test diagram of the RPH prepared in Example 1;

[0050] Figure 14 This is a semiconductor performance test diagram of the RPC obtained in Example 2. Detailed Implementation

[0051] Example 1: Synthesis of polymer RPH:

[0052]

[0053] Compound 1 (1.99 g, 8.1 mmol), K₂CO₃ (2.58 g, 18.7 mmol), and DMF (50 mL) were added to a 100 mL two-necked flask. The mixture was purged with argon for 30 min, and then compound 2 (3.21 g, 17.0 mmol) was added. The mixture was then heated under reflux and stirred for 2 h to complete the reaction. After cooling to room temperature, the reaction was quenched with water (20 mL), and the solution was extracted with ethyl acetate (200 mL). The collected organic layer was further washed with water (50 mL) and brine (50 mL). The organic solvent was dried over anhydrous Na₂SO₄. After filtration, the solvent was removed under vacuum, and the solid residue was purified by silica gel column chromatography (petroleum ether / CH₂Cl₂ = 4:1) to give compound 3 as a pale yellow solid in 82% (3.88 g). 1 H NMR (400MHz, CDCl3) δ (ppm): 7.55 (s, 4H), 7.22 (d, J = 8.2Hz, 2H), 7.15 (d, J = 8.3Hz, 2H), 7. 01(s,4H),6.79(d,J=8.2Hz,2H),6.63(d,J=8.4Hz,2H),5.35(s,2H),2.38-2.04(m,18H). 13C NMR (100MHz, CDCl3) δ (ppm): 138.67, 138.15, 137.01, 136.17, 136.02, 136.00, 133.72, 133.01, 131.39 ,129.24,128.93,128.41,127.91,125.11,124.30,120.27,45.03,20.98.HRMS(MALDI-TOF)m / z:Calcd for C 44 H 35 Br2S2[M] + 788.0605; Found:788.0606(error=0.1ppm).

[0054] Compound 3 (993 mg, 1.7 mmol), FeCl3·6H2O (92 mg, 0.34 mmol), and Ac2O (1.40 g, 13.7 mmol) were dissolved in mesitylene (10 mL) and the solution was transferred to a 100 mL double-necked flask. After purging with argon for 30 minutes, the mixture was heated and stirred at 100 °C for 2 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate (200 mL) and brine. The organic layer was collected and dried over anhydrous sodium sulfate. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography (petroleum ether / CH2Cl2 = 4:1) to give a pale solid compound 4 in 89% (1.19 g) yield. 1 H NMR (400MHz, CDCl3) δ (ppm): 7.55 (s, 4H), 7.22 (d, J = 8.2Hz, 2H), 7.15 (d, J = 8.3Hz, 2H), 7. 01(s,4H),6.79(d,J=8.2Hz,2H),6.63(d,J=8.4Hz,2H),5.35(s,2H),2.38-2.04(m,18H). 13 C NMR (100MHz, CDCl3) δ (ppm): 138.67, 138.15, 137.01, 136.17, 136.02, 136.00, 133.72, 133.01, 131.39 ,129.24,128.93,128.41,127.91,125.11,124.30,120.27,45.03,20.98.HRMS(MALDI-TOF)m / z:Calcd for C 44 H 35 Br2S2[M] + 788.0605; Found:788.0606(error=0.1ppm).

[0055] Compound 4 (1.03 g, 1.3 mmol) and m-CPBA (1.35 g, 7.8 mmol) were dissolved in CH₂Cl₂ (20 mL) in a 100 mL double-necked flask. The mixture was then stirred at room temperature for 2 hours. The reaction solution was extracted with CH₂Cl₂ (200 mL) and washed with brine. The organic layer was collected and dried over anhydrous sodium sulfate. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography (petroleum ether / CH₂Cl₂ = 1:2) to give compound 5 as a white solid in 81% (898 mg) yield. 1 H NMR (400MHz, CDCl3) δ (ppm): 8.40 (s, 2H), 8.34 (s, 2H), 7.68 (d, J = 8.4Hz, 2H), 7.54 (d, J = 8.5Hz, 2H), 7.10(s,2H),7.04(d,J=8.2Hz,2H),6.96(s,2H),5.86(s,2H),2.44(s,6H),2.39(s,6H),1.37(s,6H). 13 C NMR (100MHz, CDCl3) δ (ppm): 140.46, 139.70, 138.57, 138.49, 138.15, 137.53, 137.46, 136.61, 136.59, 135.74, 131.50, 131.47, 1 31.20,129.72,129.68,128.86,128.84,126.49,121.95,121.93,121.63,77.02,41.38,21.43,20.99.HRMS(MALDI-TOF)m / z:Calcd forC 44 H 35 Br2S2O4[M] + 852.0401; Found:852.0395(error=-0.7ppm).

[0056] Take a 100 mL double-necked flask and dissolve compound 5 (426 mg, 0.5 mmol) in anhydrous THF (20 mL). After purging with argon for 30 min, add t-BuOK (112 mg, 1.0 mmol) under argon atmosphere, stir at room temperature for 30 min, then add tetrachlorobenzoquinone (191 mg, 1.5 mmol), and continue the reaction for 2 h. Filter the reaction solution to remove t-BuOK and collect the filtrate. Remove the solvent under vacuum, and purify the residue by silica gel column chromatography (petroleum ether / CH2Cl2 = 1:1.5) to obtain a blue-green solid, SDBr-H, in 86% (366 mg) yield. HRMS (MALDI-TOF) m / z: Calcd for C 44 H 33 Br2S2O4[M]+ 850.0245; Found:850.0241 (error=-0.5ppm).

[0057] SDBr-H (300 mg, 0.351 mmol), 2,5-bis(2-octyldodecyl)-3,6-bis(5-(trimethylstanyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrolo-1,4-dione (417 mg, 0.351 mmol), Pd2(dba)3 (18 mg, 0.025 mmol), and P(o-tol)3 (30 mg, 0.09 mmol) were dissolved in anhydrous toluene (15 mL). The mixture was subjected to a freeze-pump-thaw cycle three times, and then stirred at 110 °C under argon for 8 h. After cooling to room temperature, the reaction mixture was poured into 200 mL of acetone. After stirring for 30 min, the solution was filtered, and the polymer solid was collected. Then, it was purified by Soxhlet extraction with acetone, petroleum ether, and chloroform under argon. After removing the solution, precipitation with acetone yielded a dark blue film, with a polymer RPH yield of 96% (525 mg). The weight-average molecular weight was 193.4 kDa, the number-average molecular weight was 69.5 kDa, and the polymer molecular weight distribution index was 3.16.

[0058] Example 2: Synthesis of polymer RPC:

[0059] The chemical synthesis is as follows:

[0060]

[0061] Compound 7 was synthesized using the same method as compound 3 in Example 1, with a yield of 91%. 1 H NMR (400MHz, CDCl3) δ (ppm): 10.24 (s, 1H), 8.11 (s, 1H), 7.71 (s, 1H), 7.64 (d, J = 6.5Hz, 1H) ,7.57(d,J=8.4Hz,2H),7.48(d,J=7.8Hz,1H),7.38(t,J=7.9Hz,1H),6.97(d,J=7.1Hz,1H). 13 C NMR (100MHz, CDCl3) δ (ppm): 189.21, 148.68, 137.59, 136.69, 135.90, 133.68, 133.34, 132.47,131.97,131.62,128.33,123.87,117.45,109.19.HRMS(MALDI-TOF)m / z:Calcd forC 14 H8BrNOS[M] +316.9510; Found: 316.9503 (error=-2.2ppm).

[0062] Compound 8 was synthesized using the same method as compound 4 in Example 1, with a yield of 75%. 1 H NMR (600MHz, CDCl3) δ (ppm): 7.52 (d, J = 2.1Hz, 1H), 7.45 (s, 2H), 7.19 (dd, J1 = 8.4Hz, J2 = 2. 1Hz,1H),7.02(s,2H),6.99(s,1H),6.63(d,J=8.4Hz,1H),5.31(s,1H),2.39-1.81(m,9H). 13 C NMR (150MHz, CDCl3) δ (ppm): 138.07, 137.77, 137.73, 137.66, 134.96, 131.93, 131.68, 130.89, 130.12 ,129.98,129.14,128.39,126.60,120.77,118.88,110.06,44.86,20.96.HRMS(MALDI-TOF)m / z:Calcd for C 23 H 17 BrNS[M] + 419.0343; Found: 419.0339 (error=-1.0ppm).

[0063] Compound 9 was synthesized using the same method as compound 5 in Example 1, with a yield of 87%. 1 H NMR (400MHz, CDCl3) δ (ppm): 8.32-8.30 (m, 2H), 7.81 (d, J = 8.1Hz, 1H), 7.57 (dd, J1 = 8.5, J2 = 2.1Hz, 1H), 7.21 (s,1H),7.12(s,1H),6.97(s,1H),6.83(d,J=8.5Hz,1H),5.81(s,1H),2.41(s,3H),2.40(s,3H),1.32(s,3H). 13C NMR (100MHz, CDCl3) δ (ppm): 142.29, 139.78, 139.06, 138.75, 138.45, 136.87, 136.70, 136.21, 131.83, 131.54, 131.25, 1 30.10,130.06,129.76,126.73,124.53,122.01,117.27,116.61,41.32,21.38,20.97,20.92.HRMS(MALDI-TOF)m / z:Calcd for C 23 H 17 BrNSO2[M] + 451.0241; Found: 451.0247 (error=1.3ppm).

[0064] Take a 100 mL double-necked flask and dissolve compound 9 (500 mg, 1.1 mmol) in anhydrous THF (20 mL). After purging with argon for 30 min, add t-BuOK (247 mg, 2.2 mmol) under argon atmosphere, stir at room temperature for 30 min, then add tetrachlorobenzoquinone (421 mg, 3.3 mmol), and continue the reaction for 2 h. Filter the reaction solution to remove t-BuOK and collect the filtrate. Remove the solvent under vacuum, and purify the residue by silica gel column chromatography (petroleum ether / CH2Cl2 = 1:1.5) to obtain a blue-green solid, SDBr-CN, in 84% (366 mg) yield. HRMS (MALDI-TOF) m / z: Calcd for C 46 H 31 Br2N2S2O4[M] + 900.0150; Found:900.0153(error=0.3ppm).

[0065] SDBr-CN (300 mg, 0.333 mmol), 2,5-bis(2-octyldodecyl)-3,6-bis(5-(trimethylstanyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (330 mg, 0.333 mmol), Pd2(dba)3 (18 mg, 0.015 mmol), and P(o-tol)3 (30 mg, 0.09 mmol) were dissolved in anhydrous toluene (15 mL). The mixture was subjected to a freeze-pump-thaw cycle three times, and then stirred at 110 °C under argon for 24 h. After cooling to room temperature, the reaction mixture was poured into 200 mL of acetone. After stirring for 30 min, the solution was filtered, and the polymer solid was collected. Then, it was purified by Soxhlet extraction with acetone, petroleum ether, and chloroform under argon. After removing the solution, precipitation with acetone yielded a dark blue film with a polymer RPC yield of 97% (522 mg). The weight-average molecular weight was 58.5 kDa, the number-average molecular weight was 29.7 kDa, and the polymer molecular weight distribution index was 1.97.

[0066] In this invention, the structures of SDBr-H and SDBr-CN were confirmed using variable-temperature nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, UV-Vis-NIR absorption spectroscopy, and single-crystal structure analysis. These were then used as monomers to synthesize the polymers RPH and RPC. The molecular weight and thermal stability of the polymers were characterized using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The results showed that both polymers were successfully synthesized and exhibited good thermal stability, with thermal stability temperatures exceeding 300℃. Figure 9 The UV-Vis-NIR absorption spectra (a and b) and cyclic voltammetry curves (c and d) of toluene solutions of compounds SDBr-H and SDBr-CN, and polymers RPH and RPC in Examples 1 and 2 are shown in Table 1. The related photophysical properties are also shown in Table 1. Electronic absorption spectroscopy results show that the maximum absorption wavelengths of compounds SDBr-H and SDBr-CN are 632 nm and 648 nm, respectively, with the absorption range broadened to 800 nm. After polymerization, the absorption spectra of polymers RPH and RPC are significantly broadened compared to the monomers SDBr-H and SDBr-CN, with maximum absorption wavelengths of 972 nm and 1043 nm, respectively, and a redshift wavelength exceeding 300 nm. Their sideband absorption is close to 1600 nm, according to formula E... g =1240 / λ to calculate (Eg is the optical band gap, λ is the maximum absorption sideband value of the thin film) to obtain the minimum optical band gap. It is 0.77 eV.

[0067] Depend on Figure 9It is evident that the diradical monomers exhibit triple quasi-reversible redox peaks. Specifically, SDBr-CN (0.91 / –0.31 / –0.68 eV) shows a redox potential shifting towards the anolyte compared to SDBr-H (0.72 / –0.68 / –0.89 eV), due to the introduction of the strongly electron-deficient cyano group in the open-shell molecule. The highest occupied orbital (HOMO) / lowest unoccupied orbital (LUMO) energy levels of SDBr-H and SDBr-CN, calculated from the first redox potential of the molecules, are –5.52 / –4.12 eV and –5.71 / –4.49 eV, respectively. Due to the introduction of multiple radicals, the polymers RPH and RPC exhibit more complex redox behavior, with HOMO / LUMO energy levels of –5.40 / –4.26 eV (RPH) and –5.38 / –4.54 eV (RPC), respectively.

[0068] Figure 10 For the magnetic testing of polymer RPH in Example 1, the temperature-dependent electron spin resonance (VT-ESR) of its toluene solution showed that the signal intensity increased with decreasing temperature, suggesting it may possess a doublet ground state. Superconducting quantum interference device (SQUID) testing showed that, under a magnetic field strength of 0.1 T, within a temperature range of 2–400 K, the solid-state magnetic response of polymer RPH decreased with increasing temperature, exhibiting paramagnetism. Subsequently, at 300 K, the magnetic susceptibility of RPH was tested as a function of magnetic field strength; the test curve showed significant hysteresis, indicating its weak ferromagnetism.

[0069] Figure 11 For the magnetic testing of polymer RPC in Example 2, the VT-ESR test trend of its toluene solution is similar to that of RPH, indicating that it may have a doublet ground state. Meanwhile, SQUID testing shows that under a magnetic field strength of 0.1T, in a temperature range of 2–400K, the solid-state magnetic response of polymer RPC decreases with increasing temperature, exhibiting paramagnetism.

[0070] This invention employs a top-gate-bottom-contact (TGBC) device structure to study the thin-film semiconductor properties of conjugated radical polymers RPH and RPC. A schematic diagram of the device structure is shown below. Figure 12 As shown. The specific steps are as follows:

[0071] First, the polyethylene terephthalate (PET) substrate was cleaned with deionized water and ethanol, and then dried under a nitrogen stream. Using a shadow mask technique, a 30 nm Au film was deposited on the PET substrate surface as the source / drain (S / D) electrode, with a channel length (L) of 50 μm and a channel width (W) of 4200 μm. Polymers RPH and RPC were first stirred for 5 hours and then dissolved in an HPLC-grade anhydrous chlorobenzene (CB) solution (80 °C, 6 mg / mL), followed by aging in a glove box filled with N2 for at least 12 hours. The polymer film was then spin-coated onto a substrate with gold electrodes (1800 rpm / 60 s), followed by thermal annealing at 160 °C for 30 minutes in a glove box. Finally, polymethyl methacrylate (PMMA, Mw = 996 kDa, Ci ≈ 3.5 nF cm⁻¹) was spin-coated onto the substrate. –2 ) n-butyl acetate solution (80 mg / mL) –1 A 900nm PMMA dielectric layer was deposited on the active layer surface and annealed at 90°C for 30 minutes to remove organic solvents. Finally, an 80nm Ag gate was vacuum deposited. Device data were measured using a Keithley 4200A-SCS parameter analyzer. The saturation mobility was calculated using the transistor equation: I DS =(W / 2L)C i μ(V G -V T ) 2 C i V represents the capacitance of the gate dielectric; G and V T These represent the gate voltage and the threshold voltage, respectively.

[0072] Figure 13 The test curves show the field-effect transistor device with polymer RPH as the semiconductor active layer prepared in Example 1 of this invention. This device exhibits bipolar transport performance, with a maximum and average hole mobility of 0.41 / 0.35 cm⁻¹. 2 V – 1 s – 1 The maximum and average electron mobilities are 0.38 and 0.32 cm⁻¹, respectively. 2 V – 1 s – 1 .

[0073] Figure 14 The test curves for the field-effect transistor device with polymer RPC as the semiconductor active layer prepared in Example 2 of this invention are shown. This device exhibits bipolar transport performance, with a maximum and average hole mobility of 1.6 / 1.0 × 10⁻⁶. -4 cm2 V – 1 s – 1 The maximum and average electron mobilities are 2.1 and 1.7 × 10⁻⁶, respectively. -3 cm 2 V – 1 s – 1 .

Claims

1. A conjugated radical polymer with π-magnetization and bipolar semiconductor properties, characterized in that, It has the general formula of Equation 1: In Formula 1, R1 and R2 are individually selected from -Cl, -Br, -I, -CN, Cl-C 24 Alkyl, C3-C 24 cycloalkyl, C1-C 24 Alkoxy, halogenated C1-C 24 Alkyl, halogenated C3-C 24 cycloalkyl or halogenated C3-C 24 alkoxy or aryl; The Y is O, S, Se; the R3 and R4 are individually C6 to C6. 30 Alkyl groups; The value of n is 5 to 50.

2. The conjugated free radical polymer according to claim 1, characterized in that, R1 is a phenyl, a substituted phenyl, or a five-membered heterocyclic aryl group; The substituents of the substituted phenyl group include at least one of C1-C6 alkyl, C1-C6 alkoxy, and halogen.

3. The conjugated free radical polymer according to claim 1, characterized in that, R2 can be -H, -Cl, -Br, -I, or -CN.

4. The conjugated free radical polymer according to claim 1, characterized in that, X is S; R3 and R4 are individually C1 to C1. 25 Alkyl groups.

5. A method for preparing the conjugated free radical polymer according to any one of claims 1 to 4, characterized in that, The compound described in Formula 2 and the compound in Formula 3 were coupled and polymerized to obtain: In Equations 2 and 3, R1, R2, R3, R4, and Y are the same as in Equation 1; X is a halogen, and R5 is an alkyltin group.

6. The preparation method according to claim 5, characterized in that, During the coupling polymerization process, the molar ratio of Formula 2 and Formula 3 is 1:0.5 to 1.

5.

7. The preparation method according to claim 5, characterized in that, During the coupling polymerization process, the coupling polymerization is carried out under the catalysis of a catalyst; the catalyst includes at least one of tris(o-methylphenyl)phosphine and tris(dibenzylacetone)dipalladium; Preferably, the catalyst is used in an equivalent amount of 0.1 to 0.5 eqv, more preferably 0.3 to 0.35 eqv.

8. The preparation method according to claim 5, characterized in that, The coupling polymerization process is carried out in a hydrophobic solvent; Preferably, the hydrophobic solvent includes at least one of toluene, chlorobenzene, and xylene; Preferably, the temperature of the coupling polymerization process is 100–150°C.

9. The application of the conjugated free radical polymer according to any one of claims 1 to 4, characterized in that, It can be used to prepare bipolar transport semiconductors and / or magnetic materials.

10. A functional material, characterized in that, The product comprises the conjugated free radical polymer according to any one of claims 1 to 4, or is prepared by means of the conjugated free radical polymer; Preferably, the functional material is a bipolar transport semiconductor material and / or a magnetic material.

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