A Polymer Fluorescent Material Based on Axially Chiral Bidentate Fragment, Its Preparation Method and Application

Abstract

The present invention discloses a polymer fluorescent material based on a novel axially chiral double donor fragment, its preparation method and application. The compounds of the present invention are shown as any one of Formula 1 and Formula 2; wherein Ar represents a chromophore unit having two connection sites. The polymer fluorescent material is prepared according to the following method: S1, the compound shown as Formula A1 or Formula A2 reacts with p-bromoiodobenzene to obtain the compound shown as Formula B1 or Formula B2; S2, the compound shown as Formula B1 or Formula B2 reacts with isopropyl alcohol pinacol borate to obtain the compound shown as Formula C1 or Formula C2; S3, the compound shown as Formula C1 or Formula C2 reacts with the corresponding double-site chromophore Ar to obtain the product. The synthesis method of the polymer obtained in the present invention is simple, the product yield is high, and it can be prepared in large quantities. It can be used in the preparation of organic light-emitting diode devices. The organic light-emitting diode devices prepared based on all the compounds in the present invention have obvious electroluminescence circular polarization properties. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a polymer fluorescent material based on a novel axially chiral bis-donor fragment, its preparation method and application, belonging to the field of organic electroluminescent materials and devices. Background Art

[0002] CPEL (Circularly Polarized Electroluminescence) is an important application means of circularly polarized luminescence, and has extensive potential applications in the fields of biosensing imaging, information storage encryption, chiral sensing, asymmetric synthesis and 3D imaging, etc. CPEL can often be realized by processing chiral polymer fluorescent molecules into CP-OLED (Circularly Polarized Polymer Light-emitting diodes), that is, circularly polarized light-emitting diodes; currently, examples of realizing CPEL in this way have been widely reported and have attracted the close attention of researchers in related fields. At present, the most direct and effective way to prepare CP-OLED devices is still to use luminescent molecules that already have chirality and circularly polarized luminescence properties as the luminescent layer raw materials of the devices and select appropriate other transport layer materials to improve the efficiency and the electrochromic asymmetry factor. In order to improve the performance of these devices, a key point in the design is still to ensure the high quantum yield and high photo-induced asymmetry factor of the luminescent material itself, so a class of molecular designs that can effectively ensure the above data is needed. At present, the design of chiral red light molecules still lacks necessary theoretical support. The reason is that red fluorescent molecules, especially thermally activated delayed fluorescence molecules, often require large conjugated lumophore structures, and the chiral induction effect using externally added non-fluorescent active chiral groups is poor, and it is relatively difficult to combine backbone chirality with such lumophores in synthesis; however, the practical application of CPEL urgently demands highly efficient chiral red light molecules. Therefore, designing a general scheme to design a series of chiral red light molecules has very practical significance for the development of the CPEL field. Summary of the Invention

[0003] The purpose of the present invention is to provide a fluorescent material based on a novel axially chiral bis-donor fragment. The fluorescent material has good thermal stability, chemical stability and solubility, has obvious circularly polarized luminescence properties, and the OLED device prepared with this as the luminescent layer guest material can exhibit obvious CPEL properties.

[0004] The polymer provided by the present invention is shown in Formula 1 or Formula 2;

[0005]

[0006] In each formula, Ar represents a chromophore having two connection sites;

[0007] n represents the degree of polymerization of the polymer, which is 10 to 18;

[0008] The number average molecular weight of the polymer is 9000-21000, and the weight average molecular weight is 16000-43000.

[0009] In Formula 1 and Formula 2, Ar represents an aza-fused ring having two connection sites and its derivatives, and its specific structure is a didehydrogenated atomic group of any structure in the following formula:

[0010]

[0011] Preferably, the polymer is represented by any one of the formulas R-BITPAP01 to R-BITPAP15 and S-BITPAP01 to S-BITPAP15:

[0012]

[0013]

[0014] The present invention further provides a method for preparing the polymer, comprising the following steps:

[0015] S1, the compound represented by formula A1 or the compound represented by formula A2 reacts with p-bromoiodobenzene to obtain the compound represented by formula B1 or the compound represented by formula B2;

[0016] S2, reacting the compound represented by formula B1 or the compound represented by formula B2 with isopropyl pinacol borate to obtain the compound represented by formula C1 or the compound represented by C2;

[0017] S3, the compound represented by formula C1 or the compound represented by formula C2 reacts with the corresponding double-site chromophore Ar to obtain the compound represented by formula 1 or the compound represented by formula 2;

[0018]

[0019] In the above preparation method, in step S1, the reaction is carried out in the presence of tris(dibenzylideneacetone)dipalladium-chloroform adduct, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide;

[0020] The molar ratio of the tris(dibenzylideneacetone) dipalladium-chloroform adduct, the tri-tert-butylphosphine tetrafluoroborate, the sodium tert-butoxide and the compound represented by formula A1 or the compound represented by formula A2 is 0.05-0.10:0.15-0.30:6-8:1, preferably 0.05:0.15:8:1;

[0021] The molar ratio of the compound represented by formula A1 or the compound represented by formula A2 to the p-bromoiodobenzene is 1:6 to 8, preferably 1:6;

[0022] The reaction is carried out in toluene that has been dried;

[0023] The temperature of the reaction is 100 to 120 °C, and the time of the reaction is 12 to 36 hours, such as reacting for 24 hours at 110 °C.

[0024] In the above preparation method, in step S2, the reaction is carried out in the presence of n-butyllithium;

[0025] The molar ratio of the n-butyllithium to the compound represented by formula B1 or the compound represented by formula B2 is 2.1 to 2.5:1, preferably 2.5:1;

[0026] The molar ratio of the compound represented by formula B1 or the compound represented by formula B2 to the isopropanol pinacol borate is 1:3 to 3.5, preferably 1:3;

[0027] The reaction is carried out in tetrahydrofuran that has been deoxygenated and dried;

[0028] The temperature of the reaction is -78 °C to -50 °C, and the time of the reaction is 12 to 36 hours.

[0029] In the above preparation method, in step S3, the reaction is carried out in the presence of tetrakis(triphenylphosphine)palladium, sodium carbonate, phenylboronic acid, and bromobenzene;

[0030] The molar ratio of the tetrakis(triphenylphosphine)palladium, the sodium carbonate, the phenylboronic acid, the bromobenzene to the compound represented by formula C1 or the compound represented by formula C2 is 0.10 to 0.30:6.0 to 15.0:0.25 to 1:0.25 to 1:1, preferably 0.15:10:0.5:0.5:1;

[0031] The molar ratio of the compound represented by formula C1 or the compound represented by formula C2 to the two-site chromophore Ar is 1:0.95 to 1.05, with 1.00 being the best;

[0032] The reaction is carried out in a mixed solvent of dioxane and water;

[0033] The temperature of the reaction is 90 to 100 °C, and the time of the reaction is 48 to 96 hours, with 72 hours being the best.

[0034] The polymer provided by the present invention can be used to prepare an organic light-emitting diode device;

[0035] Among them, the polymer is used as the light-emitting layer material of the organic light-emitting diode device.

[0036] The present invention also provides an organic light-emitting diode device, wherein the light-emitting layer of the organic light-emitting diode device uses a light-emitting material containing the polymer;

[0037] The layers of the organic light-emitting diode device are composed as follows:

[0038] For the polymer shown in Formula 1 or the polymer shown in Formula 2, according to different wavelengths, the light-emitting layer is composed of the polymer shown in Formula 1 or the polymer shown in Formula 2 blended with mCP, TPBi:POT2T or CBP:POT2T; the hole transport layer is PEDOT:PSS; the electron transport layer is TmPYPb or TPBi; the electron injection layer and the cathode material are LiF / Al; different materials will be added as a blocking layer during the preparation of some compounds; the above materials are all commercially available known materials, and the technologies used are all existing public technologies.

[0039] The present invention has the following advantages:

[0040] (1) The preparation method provided by the present invention is simple to operate, has a high product yield, and has strong guidance and universality for the design and synthesis of chiral red light molecules;

[0041] (2) The fluorescent material based on the novel axially chiral double donor fragment of the present invention has good thermal stability and chemical stability, has a high quantum yield and obvious photoluminescence circular polarization properties;

[0042] (3) The fluorescent material based on the novel axially chiral double donor fragment of the present invention has good photophysical properties in the doped film mixed with the host, and the doped films of most molecules of the present invention can exhibit thermally activated delayed fluorescence properties and can be used for the preparation of OLED devices;

[0043] (4) The OLED device prepared with the polymer of the present invention as the light-emitting layer has a high external quantum efficiency and obvious circularly polarized electroluminescence properties, and the device has many advantages such as low turn-on voltage, low efficiency roll-off, and stable electroluminescent spectrum. Description of the Drawings

[0044] Figure 1 It is a schematic structural diagram of the organic light-emitting diode prepared by the present invention. Detailed Embodiments

[0045] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0046] The materials, reagents, etc. used in the following examples can be obtained from commercial channels unless otherwise specified.

[0047] Example 1. Preparation of the compound shown in Formula R-BITPAP01

[0048]

[0049] (1) Under argon protection, 5.00 g (11.5 mmol) of compound A1, 19.52 g (69.0 mmol) of p-bromoiodobenzene, 595 mg (0.58 mmol) of tris(dibenzylideneacetone)dipalladium-chloroform adduct, 500 mg (1.73 mmol) of tri-tert-butylphosphine tetrafluoroborate, 8.83 g (92.0 mmol) of sodium tert-butoxide and 120 mL of dried toluene were added to a 250 mL double-necked round-bottom flask in sequence, and the mixture was reacted at 110° C. for 24 hours. After the reaction system was cooled to room temperature (same as at 25° C.), a large amount of water and dichloromethane were added thereto for extraction, and the combined organic phase was washed with a saturated sodium chloride solution (150 mL×2), and the washed organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic solvent was removed by distillation to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (4:1) as the eluting solvent to obtain 6.98 g of a white solid, namely B1, with a yield of 82%.

[0050] The structural confirmation data of B1 are as follows: HR-MS (APCI): m / z calcd for.C 44 H 31 Br2N2[M+H] + 745.0825, found 745.0838.

[0051] (2) Under argon protection, 2.34 g (3.15 mmol) of compound B1 and 35 mL of deoxygenated and dried tetrahydrofuran were added to a 100 mL double-necked round-bottom flask in sequence. After cooling to -78°C, 3.28 mL of 2.4 M n-butyl lithium in n-hexane solution was slowly added to the flask using a syringe and stirred for 1 hour. Then, 1.76 g (9.45 mmol) of isopropyl alcohol pinacol borate was added to the flask and the reaction system was transferred to room temperature and stirred for 24 hours. After the reaction was completed, water and ethyl acetate were added to extract the flask. The combined organic phase was washed with a saturated sodium chloride solution (150 mL × 2). The washed organic phase was dried with anhydrous sodium sulfate, filtered, and then the organic solvent was distilled to obtain a crude product. The crude product was purified by column chromatography, and the elution solvent was petroleum ether: ethyl acetate (24:1). 1.46 g of a white solid, namely C1, was obtained with a yield of 55%.

[0052] The structural confirmation data of C1 are as follows: HR-MS (APCI): m / z calcd for.C 56 H 55 B2N2O4[M+H] + 840.4315, found 840.4334.

[0053] (3) 504 mg (0.60 mmol) of compound C1, 175 mg (0.60 mmol) of Ar01, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added to a 25 mL pressure-resistant sealed tube. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 169 mg of an orange-red solid, which was R-BITPAP01, and the yield was 39%.

[0054] The purification process of R-BITPAP01 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing (gel permeation chromatography was used to test the average molecular weight of the sample. The sample was prepared as a THF solution of about 10 mg / mL, and the mobile phase was THF, the same below) showed that its number-average molecular weight Mn = 11456; the weight-average molecular weight M w w = 24454; the dispersity index PDI = 2.13.

[0055] Example 2. Preparation of the compound represented by the formula R-BITPAP02

[0056] R-BITPAP02 was synthesized based on C1

[0057]

[0058] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C1, 210 mg (0.60 mmol) of Ar02, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 164 mg of a dark red solid, which was R-BITPAP02, and the yield was 35%.

[0059] The purification process of R-BITPAP02 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number average molecular weight Mn = 10998; weight average molecular weight M w w = 24656; polydispersity index PDI = 2.24.

[0060] Example 3. Preparation of the compound represented by formula R-BITPAP03

[0061] R-BITPAP03 is synthesized based on compound C1

[0062]

[0063] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C1, 205 mg (0.60 mmol) of Ar03, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 167 mg of an orange-red solid, which was R-BITPAP03, with a yield of 36%.

[0064] The purification process of R-BITPAP03 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 13364; the weight-average molecular weight M w w = 26512; the dispersity index PDI = 1.98.

[0065] Example 4. Preparation of the compound represented by formula R-BITPAP04

[0066] R-BITPAP04 is synthesized based on compound C1

[0067]

[0068] (1) In a 100 mL single-neck flask, 3.64 g (10.0 mmol) of 2,7-dibromo-9,10-phenanthrenequinone, 1.13 g (10.5 mmol) of diaminomaleonitrile, and 40 mL of glacial acetic acid were added, and the reaction was carried out at 110 °C for 24 hours. After the reaction system was cooled to room temperature, the solvent was removed by vacuum filtration. The filter cake was washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent was petroleum ether:dichloromethane:ethyl acetate (10:5:0.5), and 3.84 g of an orange-red solid was obtained, which was Ar04, with a yield of 88%.

[0069] The structure confirmation data of Ar04 are as follows: HR-MS (APCI): m / z calcd for.C 18 H7Br2N4[M+H] + 436.9015, found 436.9019.

[0070] (2) Add 504 mg (0.60 mmol) of compound C1, 262 mg (0.60 mmol) of Ar04, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate into a 25 mL pressure-resistant sealed tube in sequence. Then repeat the evacuation and gas replacement three times. Add 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 under an argon atmosphere and tightly seal the tube. Then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours. Then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform to the system for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol, and filtered under reduced pressure. Then the filter cake is dried in vacuo to obtain 218 mg of a bright red solid, which is R-BITPAP04, and the yield is 42%.

[0071] The purification process of R-BITPAP04 itself can prove the occurrence of the polymerization reaction without the need for structure proof. GPC test shows that its number-average molecular weight Mn = 11325; weight-average molecular weight M w w = 25447; polydispersity index PDI = 2.25.

[0072] Example 5. Preparation of the compound represented by formula R-BITPAP05

[0073] R-BITPAP05 is synthesized based on compound C1

[0074]

[0075] (1) 2,7-Dibromo-9,10-phenanthrenequinone (3.64 g, 10.0 mmol), 4,5-diamino-phthalonitrile (1.66 g, 10.5 mmol) and 40 mL of glacial acetic acid were added to a 100 mL single-necked flask, and the reaction was carried out at 110 °C for 24 h. After the reaction system was cooled to room temperature, the solvent was removed by suction filtration under reduced pressure. The filter cake was washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The eluting solvent was petroleum ether:dichloromethane:ethyl acetate (10:5:0.5), and 4.33 g of orange-yellow solid, namely Ar05, was obtained with a yield of 89%.

[0076] The structure confirmation data of Ar05 are as follows: HR-MS (APCI): m / z calcd for.C 22 H9Br2N4[M + H] + 486.9187, found 486.9170.

[0077] (2) Compound C1 (504 mg, 0.60 mmol), Ar05 (293 mg, 0.60 mmol), tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol) and sodium carbonate (636 mg, 6.00 mmol) were successively added to a 25 mL pressure-resistant sealed tube, and then evacuated and refilled with gas three times. 9 mL of a mixed solvent of dioxane:water with a volume ratio of 2:1 was added under an argon atmosphere, and the sealed tube was tightly sealed, and then the reaction was carried out at 95 °C for 72 h. A dioxane solution containing phenylboronic acid (36.6 mg, 0.30 mmol) was added to the reaction system, and the reaction was continued for 5 h; then bromobenzene (46.8 mg, 0.30 mmol) was added to the reaction system, and the reaction was continued for 5 h. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phases were washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 h. The obtained dichloromethane extract was concentrated, precipitated in methanol and filtered under reduced pressure, and then the filter cake was dried in vacuo to obtain 220 mg of orange-red solid, namely R-BITPAP05, with a yield of 40%.

[0078] The purification process of R-BITPAP05 itself can prove the occurrence of the polymerization reaction without the need for structure proof. GPC test shows that its number-average molecular weight Mn = 10087; weight-average molecular weight M w w = 23455; polydispersity index PDI = 2.33.

[0079] Example 6. Preparation of the compound represented by formula R-BITPAP06

[0080] R-BITPAP06 is synthesized based on compound C1

[0081]

[0082] (1) Add 3.64 g (10.0 mmol) of 2,7-dibromo-9,10-phenanthrenequinone, 1.68 g (10.5 mmol) of 5,6-diaminopyrazine-2,3-dicarbonitrile and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by suction filtration under reduced pressure. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The eluting solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.85 g of bright red solid, which is Ar06, and the yield is 79%.

[0083] The structure confirmation data of Ar06 is as follows: HR-MS (APCI): m / z calcd for.C 20 H7Br2N6[M+H] + 488.9133, found 488.9141.

[0084] (2) Add 504 mg (0.60 mmol) of compound C1, 293 mg (0.60 mmol) of Ar06, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate into a 25 mL pressure-resistant sealed tube in sequence, then evacuate and replace the gas three times, add 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 under an argon atmosphere and seal the tube tightly, and then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours; then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform to the system for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol, and filtered under reduced pressure, and then the filter cake is dried in vacuo to obtain 215 mg of dark red solid, which is R-BITPAP06, and the yield is 39%.

[0085] The purification process of R-BITPAP06 itself can prove the occurrence of the polymerization reaction without the need for structural proof. The GPC test shows that its number-average molecular weight Mn = 9967; the weight-average molecular weight M w = 21447; the dispersity index PDI = 2.37.

[0086] Example 7. Preparation of the compound represented by the formula R-BITPAP07

[0087] R-BITPAP07 is synthesized based on Compound C1

[0088]

[0089] (1) Add 3.66 g (10.0 mmol) of 3,8-dibromo-1,10-phenanthroline-5,6-dione, 1.13 g (10.5 mmol) of diaminomaleonitrile, and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by vacuum filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.59 g of orange-red solid, which is Ar07, and the yield is 82%.

[0090] The structural confirmation data of Ar07 are as follows: HR-MS (APCI): m / z calcd for.C 16 H5Br2N6[M+H] + 438.8889, found 438.8898.

[0091] (2) 504 mg (0.60 mmol) of compound C1, 263 mg (0.60 mmol) of Ar07, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added to a 25 mL pressure-resistant sealed tube. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 182 mg of a dark red solid, which was R-BITPAP07, and the yield was 35%.

[0092] The purification process of R-BITPAP07 itself can prove the occurrence of the polymerization reaction without the need for structural proof. The GPC test shows that its number-average molecular weight Mn = 11011; the weight-average molecular weight M w w = 23666; the dispersity index PDI = 2.15.

[0093] Example 8. Preparation of the compound represented by the formula R-BITPAP08

[0094] Synthesis of R-BITPAP08 based on compound C1

[0095]

[0096] (1) 3.66 g (10.0 mmol) of 3,8-dibromo-1,10-phenanthroline-5,6-dione, 1.66 g (10.5 mmol) of 4,5-diaminophthalonitrile, and 40 mL of glacial acetic acid were added to a 100 mL single-necked flask, and the reaction was carried out at 110 °C for 24 hours. After the reaction system was cooled to room temperature, the solvent was removed by vacuum filtration. The filter cake was washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent was petroleum ether:dichloromethane:ethyl acetate (10:5:0.5), and 3.95 g of an orange solid, which was Ar08, was obtained, and the yield was 81%.

[0097] The structural confirmation data of Ar08 are as follows: HR-MS (APCI): m / z calcd for.C 20 H7Br2N6[M+H] + 488.9118, found 488.9106.

[0098] (2) 504 mg (0.60 mmol) of compound C1, 293 mg (0.60 mmol) of Ar08, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added to a 25 mL pressure-resistant sealed tube. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours; then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 165 mg of a red solid, which was R-BITPAP08, and the yield was 30%.

[0099] The purification process of R-BITPAP08 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing showed that its number-average molecular weight Mn = 10976; weight-average molecular weight M w w = 23475; polydispersity index PDI = 2.14.

[0100] Example 9. Preparation of the compound shown by formula R-BITPAP09

[0101] R-BITPAP09 is synthesized based on compound C1

[0102]

[0103] (1) Add 3.66 g (10.0 mmol) of 3,8-dibromo-1,10-phenanthroline-5,6-dione, 1.68 g (10.5 mmol) of 5,6-diaminopyrazine-2,3-dicarbonitrile and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by vacuum filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The eluting solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.53 g of a red solid, which is Ar09, with a yield of 72%.

[0104] The structure confirmation data of Ar09 are as follows: HR-MS (APCI): m / z calcd for.C 18 H5Br2N8[M+H] + 490.9002, found 490.8999.

[0105] (2) Add 504 mg (0.60 mmol) of compound C1, 294 mg (0.60 mmol) of Ar09, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium and 636 mg (6.00 mmol) of sodium carbonate into a 25 mL pressure-resistant sealed tube in sequence, then evacuate and refill with gas three times, add 9 mL of a mixed solvent of dioxane and water with a volume ratio of 2:1 under an argon atmosphere and seal the tube tightly, and then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours; then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform to the system for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol and filtered under reduced pressure, and then the filter cake is dried under vacuum to obtain 182 mg of a red-brown solid, which is R-BITPAP09, with a yield of 33%.

[0106] The purification process of R-BITPAP09 itself can prove the occurrence of the polymerization reaction without the need for structure proof. GPC test shows that its number-average molecular weight Mn = 12246; weight-average molecular weight M w w = 24498; polydispersity index PDI = 2.00.

[0107] Example 10. Preparation of the compound represented by Formula R-BITPAP10

[0108] R-BITPAP10 is synthesized based on compound C1

[0109]

[0110] (1) Add 3.64 g (10.0 mmol) of 3,6-dibromo-9,10-phenanthrenequinone, 1.13 g (10.5 mmol) of diaminomaleonitrile, and 40 mL of glacial acetic acid to a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by vacuum filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.75 g of orange-red solid, which is Ar10, with a yield of 86%.

[0111] The structure confirmation data of Ar10 is as follows: HR-MS (APCI): m / z calcd for.C 18 H7Br2N4[M+H] + 436.9015, found 436.9008.

[0112] (2) Add 504 mg (0.60 mmol) of compound C1, 262 mg (0.60 mmol) of Ar10, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate to a 25 mL pressure-resistant sealed tube in sequence, then evacuate and refill with gas three times, add 9 mL of a mixed solvent of dioxane:water with a volume ratio of 2:1 under an argon atmosphere and tightly seal the sealed tube, and then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours; then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform to the system for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol, and filtered under reduced pressure, and then the filter cake is dried in vacuo to obtain 208 mg of red solid, which is R-BITPAP10, with a yield of 40%.

[0113] The purification process of R-BITPAP10 itself can prove the occurrence of the polymerization reaction without the need for structural proof. The GPC test shows that its number-average molecular weight Mn = 14375; the weight-average molecular weight M w w = 31165; the dispersity index PDI = 2.17.

[0114] Example 11. Preparation of the compound represented by formula R-BITPAP11

[0115] R-BITPAP11 is synthesized based on compound C1

[0116]

[0117] (1) Add 3.64 g (10.0 mmol) of 3,6-dibromo-9,10-phenanthrenequinone, 1.66 g (10.5 mmol) of 4,5-diaminophthalonitrile and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by reduced-pressure filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.89 g of orange-yellow solid, which is Ar11, and the yield is 80%.

[0118] The structure confirmation data of Ar11 are as follows: HR-MS (APCI): m / z calcd for.C 22 19H9Br2N4[M+H] + 486.9187, found 486.9197.

[0119] (2) 504 mg (0.60 mmol) of compound C1, 293 mg (0.60 mmol) of Ar11, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added to a 25 mL pressure-resistant sealed tube. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phases were washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 231 mg of an orange-red solid, which was R-BITPAP11, with a yield of 42%.

[0120] The purification process of R-BITPAP11 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 15776; weight-average molecular weight M w w = 32367; polydispersity index PDI = 2.05.

[0121] Example 12. Preparation of the compound represented by formula R-BITPAP12

[0122] Synthesis of R-BITPAP12 based on compound C1

[0123]

[0124] (1) 3.64 g (10.0 mmol) of 3,6-dibromo-9,10-phenanthrenequinone, 1.68 g (10.5 mmol) of 5,6-diaminopyrazine-2,3-dicarbonitrile, and 40 mL of glacial acetic acid were added to a 100 mL single-necked flask, and the reaction was carried out at 110 °C for 24 hours. After the reaction system was cooled to room temperature, the solvent was removed by vacuum filtration. The filter cake was washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent was petroleum ether:dichloromethane:ethyl acetate (10:5:0.5), and 3.46 g of a red solid, which was Ar12, was obtained with a yield of 71%.

[0125] The structural confirmation data of Ar12 are as follows: HR-MS (APCI): m / z calcd for.C 20 H7Br2N6[M+H] + 488.9133, found 488.9126.

[0126] (2) Add 504 mg (0.60 mmol) of compound C1, 293 mg (0.60 mmol) of Ar12, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate into a 25 mL pressure-resistant sealed tube in sequence. Then evacuate and refill with gas three times. Add 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 under an argon atmosphere and tightly seal the tube. Then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours. Then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol, and filtered under reduced pressure. Then the filter cake is dried in vacuo to obtain 176 mg of a dark red solid, which is R-BITPAP12, and the yield is 32%.

[0127] The purification process of R-BITPAP12 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 13945; weight-average molecular weight M w w = 29736; polydispersity index PDI = 2.13.

[0128] Example 13. Preparation of the compound shown by formula R-BITPAP13

[0129] R-BITPAP13 is synthesized based on compound C1

[0130]

[0131] (1) 2,9-dibromo-1,10-phenanthroline-5,6-dione (3.66 g, 10.0 mmol), diaminomaleonitrile (1.13 g, 10.5 mmol) and 40 mL of glacial acetic acid were added to a 100 mL single-necked flask, and the reaction was carried out at 110 °C for 24 h. After the reaction system was cooled to room temperature, the solvent was removed by vacuum filtration. The filter cake was washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent was petroleum ether:dichloromethane:ethyl acetate (10:5:0.5), and 3.85 g of orange-red solid was obtained, which was Ar13, with a yield of 88%.

[0132] The structure confirmation data of Ar13 are as follows: HR-MS (APCI): m / z calcd for.C 16 H5Br2N6[M+H] + 438.8889, found 438.8899.

[0133] (2) Compound C1 (504 mg, 0.60 mmol), Ar13 (263 mg, 0.60 mmol), tetrakis(triphenylphosphine)palladium (104 mg, 0.09 mmol) and sodium carbonate (636 mg, 6.00 mmol) were successively added to a 25 mL pressure-resistant sealed tube, and then evacuated and replaced with gas three times. Under an argon atmosphere, 9 mL of a mixed solvent of dioxane:water with a volume ratio of 2:1 was added and the sealed tube was tightly sealed, and then the reaction was carried out at 95 °C for 72 h. A dioxane solution containing phenylboronic acid (36.6 mg, 0.30 mmol) was added to the reaction system, and the reaction was continued for 5 h; then bromobenzene (46.8 mg, 0.30 mmol) was added to the reaction system, and the reaction was continued for 5 h. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phases were washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 h. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then the filter cake was dried under vacuum to obtain 161 mg of red solid, which was R-BITPAP13, with a yield of 31%.

[0134] The purification process of R-BITPAP13 itself can prove the occurrence of the polymerization reaction without the need for structure proof. GPC test shows that its number-average molecular weight Mn = 14775; weight-average molecular weight M w w = 29981; polydispersity index PDI = 2.03.

[0135] Example 14, Preparation of the Compound Shown by Formula R-BITPAP14

[0136] R-BITPAP14 is synthesized based on Compound C1

[0137]

[0138] (1) Add 3.66 g (10.0 mmol) of 2,9-dibromo-1,10-phenanthroline-5,6-dione, 1.66 g (10.5 mmol) of 4,5-diaminoophthalonitrile and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by vacuum filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The eluting solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.75 g of orange-yellow solid, which is Ar14, and the yield is 77%.

[0139] The structure confirmation data of Ar14 is as follows: HR-MS (APCI): m / z calcd for.C 20 H7Br2N6[M+H] + 488.9118, found 488.9125.

[0140] (2) Add 504 mg (0.60 mmol) of Compound C1, 293 mg (0.60 mmol) of Ar14, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate into a 25 mL pressure-resistant sealed tube in sequence, then evacuate and refill with gas three times. Add 9 mL of a mixed solvent of dioxane and water with a volume ratio of 2:1 under an argon atmosphere and tightly seal the sealed tube, and then react at 95 °C for 72 hours. Add 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid to the reaction system and continue to react for 5 hours; then add 46.8 mg (0.30 mmol) of bromobenzene to the reaction system and react for another 5 hours. After the reaction system is cooled to room temperature, add water and chloroform to the system for extraction. The combined organic phase is washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase is concentrated by rotary evaporation to remove part of the solvent, it is precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product is successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent is about 18 - 24 hours. The obtained dichloromethane extract is concentrated, precipitated in methanol, and filtered under reduced pressure, and then the filter cake is dried in vacuo to obtain 182 mg of orange-red solid, which is R-BITPAP14, and the yield is 33%.

[0141] The purification process of R-BITPAP14 itself can prove the occurrence of the polymerization reaction without structural proof. The GPC test shows that its number-average molecular weight Mn = 15772; the weight-average molecular weight M w = 34376; the dispersity index PDI = 2.18.

[0142] Example 15. Preparation of the compound represented by formula R-BITPAP15

[0143] R-BITPAP15 is synthesized based on compound C1

[0144]

[0145] (1) Add 3.66 g (10.0 mmol) of 2,9-dibromo-1,10-phenanthroline-5,6-dione, 1.68 g (10.5 mmol) of 5,6-diaminopyrazine-2,3-dicarbonitrile and 40 mL of glacial acetic acid into a 100 mL single-necked flask, and react at 110 °C for 24 hours. After the reaction system is cooled to room temperature, the solvent is removed by vacuum filtration. The filter cake is washed with a small amount of ethanol and n-hexane, and then purified by column chromatography. The elution solvent is petroleum ether:dichloromethane:ethyl acetate (10:5:0.5) to obtain 3.82 g of bright red solid, which is Ar15, and the yield is 78%.

[0146] The structure confirmation data of Ar15 are as follows: HR-MS (APCI): m / z calcd for.C 18 H5Br2N8[M + H] + 490.9002, found 490.9008.

[0147] (2) 504 mg (0.60 mmol) of compound C1, 294 mg (0.60 mmol) of Ar15, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added to a 25 mL pressure-resistant sealed tube. Then, the evacuation and filling with argon were repeated three times. 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added under an argon atmosphere, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phases were washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 199 mg of a dark red solid, which was R-BITPAP15 with a yield of 36%.

[0148] The purification process of R-BITPAP15 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 14386; weight-average molecular weight M w w = 29698; polydispersity index PDI = 2.06.

[0149] Example 16. Preparation of the compound represented by formula S-BITPAP01

[0150]

[0151]

[0152] (1) Under argon protection, 25.00 g (11.5 mmol) of compound A, 19.52 g (69.0 mmol) of p-bromoiodobenzene, 595 mg (0.58 mmol) of tris(dibenzylideneacetone)dipalladium-chloroform adduct, 500 mg (1.73 mmol) of tri-tert-butylphosphine tetrafluoroborate, 8.83 g (92.0 mmol) of sodium tert-butoxide and 120 mL of dried toluene were added to a 250 mL double-necked round-bottom flask in sequence, and the mixture was reacted at 110° C. for 24 hours. After the reaction system was cooled to room temperature, a large amount of water and dichloromethane were added thereto for extraction, and the combined organic phase was washed with a saturated sodium chloride solution (150 mL×2), dried over anhydrous sodium sulfate, filtered, and then the organic solvent was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (4:1) as the eluting solvent to obtain 7.24 g of a white solid, B2, with a yield of 85%.

[0153] The structural confirmation data of B2 are as follows: HR-MS (APCI): m / z calcd for.C 44 H 31 Br2N2[M+H] + 745.0825, found 745.0831.

[0154] (2) Under argon protection, 2.34 g (3.15 mmol) of compound B2 and 35 mL of deoxygenated and dried tetrahydrofuran were added to a 100 mL double-necked round-bottom flask in sequence. After cooling to -78°C, 3.28 mL of 2.4 M n-butyl lithium in n-hexane solution was slowly added to the flask using a syringe and stirred for 1 hour. Then, 1.76 g (9.45 mmol) of isopropyl alcohol pinacol borate was added to the flask and the reaction system was transferred to room temperature and stirred for 24 hours. After the reaction was completed, water and ethyl acetate were added to extract the compound. The combined organic phase was washed with a saturated sodium chloride solution (150 mL × 2). The washed organic phase was dried with anhydrous sodium sulfate, filtered, and then the organic solvent was distilled to obtain a crude product. The crude product was purified by column chromatography, and the elution solvent was petroleum ether: ethyl acetate (24:1). 1.41 g of a white solid, namely C2, was obtained with a yield of 53%.

[0155] The structural confirmation data of C2 are as follows: HR-MS (APCI): m / z calcd for.C 56 H 55 B2N2O4[M+H] + 840.4315, found 840.4312.

[0156] (3) 25 mL pressure-resistant sealed tube was successively added with 504 mg (0.60 mmol) of compound C2, 175 mg (0.60 mmol) of Ar01, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate. Then, the evacuation and gas replacement were repeated three times. Under the argon atmosphere, 9 mL of a mixed solvent with a volume ratio of dioxane to water of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours; then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 178 mg of an orange-red solid, which was S-BITPAP01, and the yield was 41%.

[0157] The purification process of S-BITPAP01 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 11998; weight-average molecular weight M w w = 25735; polydispersity index PDI = 2.14.

[0158] Example 17. Preparation of the compound represented by formula S-BITPAP02

[0159] S-BITPAP02 is synthesized based on C2

[0160]

[0161] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 210 mg (0.60 mmol) of Ar02, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 163 mg of a dark red solid, which was S-BITPAP02, and the yield was 35%.

[0162] The purification process of S-BITPAP02 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 12465; weight-average molecular weight M w w = 27785; dispersity index PDI = 2.23.

[0163] Example 18. Preparation of the compound represented by formula S-BITPAP03

[0164] S-BITPAP03 is synthesized based on compound C2

[0165]

[0166] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 205 mg (0.60 mmol) of Ar03, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 144 mg of an orange-red solid, which was S-BITPAP03, and the yield was 31%.

[0167] The purification process of S-BITPAP03 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 11376; weight-average molecular weight M w w = 26078; polydispersity index PDI = 2.29.

[0168] Example 19. Preparation of the compound represented by formula S-BITPAP04

[0169] S-BITPAP04 is synthesized based on compound C2 and Ar04

[0170]

[0171] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 262 mg (0.60 mmol) of Ar04, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 176 mg of a bright red solid, which was S-BITPAP04, with a yield of 34%.

[0172] The purification process of S-BITPAP04 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 9890; the weight-average molecular weight M w w = 21368; the dispersity index PDI = 2.16.

[0173] Example 20, Preparation of the Compound Represented by Formula S-BITPAP05

[0174] S-BITPAP05 is synthesized based on compound C2 and Ar05

[0175]

[0176] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar05, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were successively added. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was carried out for another 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was vacuum dried to obtain 203 mg of an orange-red solid, which was S-BITPAP05, and the yield was 37%.

[0177] The purification process of S-BITPAP05 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 11370; the weight-average molecular weight M w w = 24421; the dispersity index PDI = 2.15.

[0178] Example 21. Preparation of the compound represented by formula S-BITPAP06

[0179] S-BITPAP06 is synthesized based on compound C2 and Ar06

[0180]

[0181] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar06, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 193 mg of a dark red solid, which was S-BITPAP06, with a yield of 35%.

[0182] The purification process of S-BITPAP06 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 11867; weight-average molecular weight M w w = 23665; polydispersity index PDI = 1.99.

[0183] Example 22: Preparation of the compound represented by formula S-BITPAP07

[0184] S-BITPAP07 is synthesized based on compound C2 and Ar07

[0185]

[0186] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 263 mg (0.60 mmol) of Ar07, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. A dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phases were washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, precipitation was carried out in methanol, and then filtration under reduced pressure was carried out to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 198 mg of a dark red solid, which was S-BITPAP07, and the yield was 38%.

[0187] The purification process of S-BITPAP07 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 12490; weight-average molecular weight M w w = 26251; dispersity index PDI = 2.10.

[0188] Example 23. Preparation of the compound shown by formula S-BITPAP08

[0189] S-BITPAP08 is synthesized based on compound C2 and Ar08

[0190]

[0191] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar08, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 177 mg of a red solid, which was S-BITPAP08, with a yield of 32%.

[0192] The purification process of S-BITPAP08 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 9794; weight-average molecular weight M w w = 22576; dispersity index PDI = 2.31.

[0193] Example 24. Preparation of the compound represented by formula S-BITPAP09

[0194] S-BITPAP09 is synthesized based on compound C2 and Ar09

[0195]

[0196] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 294 mg (0.60 mmol) of Ar09, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was subjected to Soxhlet extraction successively using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 191 mg of a red-brown solid, which was S-BITPAP09, with a yield of 35%.

[0197] The purification process of S-BITPAP09 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC test shows that its number-average molecular weight Mn = 10579; weight-average molecular weight M w w = 23667; polydispersity index PDI = 2.24.

[0198] Example 25. Preparation of the compound represented by formula S-BITPAP10

[0199] S-BITPAP10 is synthesized based on compound C2 and Ar10

[0200]

[0201] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 262 mg (0.60 mmol) of Ar10, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 199 mg of a red solid, which was S-BITPAP10, with a yield of 38%.

[0202] The purification process of S-BITPAP10 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 13876; weight-average molecular weight M w w = 28898; dispersity index PDI = 2.08.

[0203] Example 26. Preparation of the compound represented by formula S-BITPAP11

[0204] S-BITPAP11 is synthesized based on compound C2 and Ar11

[0205]

[0206] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar11, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. A dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 197 mg of an orange-red solid, which was S-BITPAP11, with a yield of 36%.

[0207] The purification process of S-BITPAP11 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 16009; the weight-average molecular weight M w w = 35565; the dispersity index PDI = 2.22.

[0208] Example 27. Preparation of the compound represented by formula S-BITPAP12

[0209] S-BITPAP12 is synthesized based on compound C2 and Ar12

[0210]

[0211] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar12, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added in sequence. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. To the reaction system, 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added, and the reaction continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 193 mg of a dark red solid, which was S-BITPAP12, with a yield of 35%.

[0212] The purification process of S-BITPAP12 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 14421; weight-average molecular weight M w w = 30098; polydispersity index PDI = 2.09.

[0213] Example 28. Preparation of the compound shown by formula S-BITPAP13

[0214] S-BITPAP13 is synthesized based on compound C2 and Ar13

[0215]

[0216] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 263 mg (0.60 mmol) of Ar13, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove some solvents, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was subjected to Soxhlet extraction successively with acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried in vacuo to obtain 177 mg of a red solid, which was S-BITPAP13, and the yield was 34%.

[0217] The purification process of S-BITPAP13 itself can prove the occurrence of the polymerization reaction without the need for structure proof. GPC test shows that its number-average molecular weight Mn = 14228; weight-average molecular weight M w w = 30678; polydispersity index PDI = 2.16.

[0218] Example 29. Preparation of the compound represented by formula S-BITPAP14

[0219] S-BITPAP14 is synthesized based on compound C2 and Ar14

[0220]

[0221] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 293 mg (0.60 mmol) of Ar14, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and filling with gas were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. A dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, and the extraction time for each solvent was about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 182 mg of an orange-red solid, which was S-BITPAP14, and the yield was 33%.

[0222] The purification process of S-BITPAP14 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 13899; weight-average molecular weight M w w = 30019; dispersity index PDI = 2.16.

[0223] Example 30. Preparation of the compound shown by formula S-BITPAP15

[0224] S-BITPAP15 is synthesized based on compound C2 and Ar15

[0225]

[0226] To a 25 mL pressure-resistant sealed tube, 504 mg (0.60 mmol) of compound C2, 294 mg (0.60 mmol) of Ar15, 104 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium, and 636 mg (6.00 mmol) of sodium carbonate were added successively. Then, the evacuation and gas replacement were repeated three times. Under an argon atmosphere, 9 mL of a mixed solvent with a dioxane:water volume ratio of 2:1 was added, and the sealed tube was tightly sealed. Then, the reaction was carried out at 95 °C for 72 hours. 1.5 mL of a dioxane solution containing 36.6 mg (0.30 mmol) of phenylboronic acid was added to the reaction system, and the reaction was continued for 5 hours. Then, 46.8 mg (0.30 mmol) of bromobenzene was added to the reaction system, and the reaction was continued for 5 hours. After the reaction system was cooled to room temperature, water and chloroform were added to the system for extraction. The combined organic phase was washed successively with 50 mL of 1 M hydrochloric acid, 1 M sodium bicarbonate solution, and saturated sodium chloride solution. After the washed organic phase was concentrated by rotary evaporation to remove part of the solvent, it was precipitated in methanol and then filtered under reduced pressure to obtain the crude product. The crude product was successively subjected to Soxhlet extraction using acetone, n-hexane, and dichloromethane as solvents, with each solvent extraction time being about 18 - 24 hours. The obtained dichloromethane extract was concentrated, precipitated in methanol, and filtered under reduced pressure. Then, the filter cake was dried under vacuum to obtain 171 mg of a dark red solid, which was S-BITPAP15, with a yield of 31%.

[0227] The purification process of S-BITPAP15 itself can prove the occurrence of the polymerization reaction without the need for structural proof. GPC testing shows that its number-average molecular weight Mn = 15998; weight-average molecular weight M w w = 34219; polydispersity index PDI = 2.14.

[0228] Example 31. Preparation of Organic Light-Emitting Diode Devices

[0229] The general preparation process and main performance research of an organic light-emitting diode prepared with the luminescent materials involved in the present invention, such as those in Formula 1 and Formula 2, as the light-emitting layer.

[0230] (I) The manufacturing steps of an organic electroluminescent device with any one of the compounds R-BITPAP01 - R-BITPAP15 or S-BITPAP01 - S-BITPAP15 as the light-emitting layer are as follows (taking R-BITPAP01 as an example):

[0231] (1) Pretreatment of the glass substrate: Select a glass substrate with a 3×3 mm 2 indium tin oxide (ITO) film pattern as the transparent electrode; wash the glass substrate with pure water, put it into ethanol for ultrasonic treatment, and then treat it with a plasma cleaner to obtain the pretreated glass substrate.

[0232] (2) Solution processing: On the pre-treated glass substrate, device preparation for the light-emitting layer and each layer between the light-emitting layer and the anode is carried out by solution processing. First, place the pre-treated glass substrate in an air atmosphere, directly and evenly apply commercially available PEDOT:PSS on the front side of the substrate, then use a spin coater to process it at a speed of 2500 revolutions per minute for 60 seconds and place the spin-coated substrate on a heating stage and heat it at 120 °C for 30 minutes. The obtained thin film is used as the hole transport layer; after the substrate is slowly cooled to room temperature, transfer it to a nitrogen atmosphere, and evenly apply the pre-prepared mixed solution of R-BITPAP01:TADF sensitizer:mCP = 1:9:90 (dissolved in deoxygenated and dried chlorobenzene, with a total concentration of 10 - 20 mg / mL; when R-BITPAP04 - R-BITPAP15 and S-BITPAP04 - S-BITPAP15 are used as the light-emitting materials, TADF sensitizer does not need to be added, and according to different wavelengths, mCP / TPBi:POT2T / CBP:POT2T is selected as the host material) on the front side of the substrate, then use a spin coater to process it at a speed of 2500 revolutions per minute for 60 seconds and place the spin-coated substrate on a heating stage in a nitrogen atmosphere and heat it at 150 °C for 10 minutes, then adjust the temperature to 120 °C and heat it for another 30 minutes. The obtained thin film is used as the light-emitting layer.

[0233] (3) Vacuum evaporation: On the glass substrate after solution processing, device preparation for each layer after the light-emitting layer is carried out by vacuum evaporation. First, put the glass substrate after solution processing into the vacuum evaporation chamber and reduce the pressure to below 6×10 -4 Pa; then use resistance heating to evaporate the corresponding organic materials layer by layer onto the pre-treated glass substrate in sequence; in order: electron transport layer, electron injection layer, cathode (for some compounds, a hole blocking layer will be added during device preparation: the hole blocking layer is located between the light-emitting layer and the electron transport layer). Among them, the glass substrate with an ITO transparent electrode is used as the anode; TPBi with a film thickness of 35 nm is used as the electron transport layer; (when the light-emitting layer uses CBP:POT2T as the mixed host, this layer is changed to TmPYPb); lithium fluoride with a film thickness of 1 nm is used as the electron injection layer; aluminum with a film thickness of 100 nm is configured with a metal mask orthogonal to the ITO stripes to form the cathode, and an organic light-emitting diode is obtained. The film thickness is measured with a stylus film thickness gauge. The schematic diagram of the device structure is as Figure 1 shown.

[0234] (4) Device encapsulation: Seal the fabricated organic electroluminescent device in a nitrogen atmosphere glove box with a water and oxygen concentration below 0.1 ppm, then use a sealing cover made of epoxy-type ultraviolet curable resin glass to cover the above-mentioned film-forming substrate and seal it by self-digging and curing.

[0235] (2) Performance evaluation of the organic electroluminescent device prepared according to the above process with any one of the compounds R-BITPAP01 to R-BITPAP15 or S-BITPAP01 to S-BITPAP15 as the light-emitting layer: A direct current is applied to the fabricated organic circularly polarized light-emitting diode, and a Spectrascan PR670 luminance meter is used to evaluate the luminescence performance; a computer-controlled Keithley 2400 digital source meter is used to measure the current-voltage characteristics. The luminescence properties of the organic light-emitting diode are measured under varying applied direct current voltages. Table 2 records the external quantum efficiency (EQE) and electroluminescent asymmetry factor (g EL ).

[0236] Table 2 Data sheet of the performance of all fabricated organic light-emitting diode devices related to Example 31

[0237] Compound EQE (%) <![CDATA[g EL > Compound EQE (%) <![CDATA[g EL > R-BITPAP01 17.8 <![CDATA[+1.4×10 -3 > S-BITPAP01 17.4 <![CDATA[-1.5×10 -3 > R-BITPAP02 4.2 <![CDATA[+1.9×10 -3 > S-BITPAP02 4.4 <![CDATA[-1.8×10 -3 > R-BITPAP03 9.1 <![CDATA[+1.6×10 -3 > S-BITPAP03 9.0 <![CDATA[-1.6×10 -3 > R-BITPAP04 7.0 <![CDATA[+1.9×10 -3 > S-BITPAP04 7.1 <![CDATA[-2.0×10 -3 > R-BITPAP05 10.5 <![CDATA[+1.1×10 -3 > S-BITPAP05 10.4 <![CDATA[-1.1×10 -3 > R-BITPAP06 8.1 <![CDATA[+2.2×10 -3 > S-BITPAP06 8.3 <![CDATA[-2.4×10 -3 > R-BITPAP07 8.2 <![CDATA[+1.2×10 -3 > S-BITPAP07 8.0 <![CDATA[-1.1×10 -3 > R-BITPAP08 11.4 <![CDATA[+0.9×10 -3 > S-BITPAP08 11.7 <![CDATA[-0.9×10 -3 > R-BITPAP09 5.4 <![CDATA[+1.4×10 -3 > S-BITPAP09 5.5 <![CDATA[-1.4×10 -3 > R-BITPAP10 6.2 <![CDATA[+1.6×10 -3 > S-BITPAP10 5.8 <![CDATA[-1.7×10 -3 > R-BITPAP11 9.5 <![CDATA[+1.0×10 -3 > S-BITPAP11 9.6 <![CDATA[-1.1×10 -3 > R-BITPAP12 4.1 <![CDATA[+1.5×10 -3 > S-BITPAP12 4.0 <![CDATA[-1.5×10 -3 > R-BITPAP13 6.9 <![CDATA[+1.9×10 -3 > S-BITPAP13 6.7 <![CDATA[-2.0×10 -3 > R-BITPAP14 10.2 <![CDATA[+1.4×10 -3 > S-BITPAP14 10.0 <![CDATA[-1.3×10 -3 > R-BITPAP15 3.9 <![CDATA[+1.8×10 -3 > S-BITPAP15 3.8 <![CDATA[-1.8×10 -3 >

[0238] As can be seen from the data in Table 1, the OLED devices prepared with the fluorescent material based on the novel axially chiral double donor fragment of the present invention as the light-emitting layer guest material can all operate stably and have relatively good external quantum efficiency, and the corresponding OLED devices can all exhibit obvious CPEL properties.

Claims

1. A polymer represented by Formula 1 or Formula 2; In each formula, n represents the degree of polymerization of the polymer, which is 10 to 18; The number average molecular weight of the polymer is 9000-21000, and the weight average molecular weight is 16000-43000; Ar represents an aza-fused ring and its derivatives having two connection sites, and its specific structure is a didehydrogenated atomic group of any structure in the following formula:

2. The polymer according to claim 1, wherein: The polymer is any one of the formulas R-BITPAP01 to R-BITPAP15 and S-BITPAP01 to S-BITPAP15:

3. The method for preparing the polymer according to claim 1 or 2, comprising the steps of: S1, the compound represented by formula A1 or the compound represented by formula A2 reacts with p-bromoiodobenzene to obtain the compound represented by formula B1 or the compound represented by formula B2; S2, reacting the compound represented by formula B1 or the compound represented by formula B2 with isopropyl pinacol borate to obtain the compound represented by formula C1 or the compound represented by C2; S3, the compound represented by formula C1 or the compound represented by formula C2 reacts with the corresponding double-site chromophore Ar to obtain the compound represented by formula 1 or the compound represented by formula 2; The dual-site chromophore Ar group is a didehydrogenated atom group represented by any of the following structures:

4. The preparation method according to claim 3, wherein: In step S1, the reaction is carried out in the presence of tris(dibenzylideneacetone)dipalladium-chloroform adduct, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide; The molar ratio of the tris(dibenzylideneacetone)dipalladium-chloroform adduct, the tri-tert-butylphosphine tetrafluoroborate, the sodium tert-butoxide and the compound represented by formula A1 or the compound represented by formula A2 is 0.05-0.10:0.15-0.30:6-8:1; The molar ratio of the compound represented by formula A1 or the compound represented by formula A2 to the p-bromoiodobenzene is 1:6-8; The reaction is carried out in dried toluene; The reaction temperature is 100-120° C., and the reaction time is 12-36 hours.

5. The preparation method according to claim 3 or 4, characterized in that: In step S2, the reaction is carried out in the presence of n-butyllithium; The molar ratio of n-butyl lithium to the compound represented by formula B1 or the compound represented by formula B2 is 2.1 to 2.5:1; The molar ratio of the compound represented by formula B1 or the compound represented by formula B2 to the isopropyl pinacol borate is 1:3 to 3.5; The reaction is carried out in deoxygenated and dried tetrahydrofuran; The reaction temperature is -78°C to -50°C, and the reaction time is 12 to 36 hours.

6. The preparation method according to claim 3 or 4, characterized in that: In step S3, the reaction is carried out in the presence of tetrakis(triphenylphosphine)palladium, sodium carbonate, phenylboric acid and bromobenzene; The molar ratio of the tetrakis(triphenylphosphine)palladium, the sodium carbonate, the phenylboric acid, the bromobenzene and the compound represented by formula C1 or the compound represented by formula C2 is 0.10-0.30:6.0-15.0:0.25-1:0.25-1:1; The molar ratio of the compound represented by formula C1 or the compound represented by formula C2 to the double-site chromophore Ar is 1:0.95-1.05; The reaction is carried out in a mixed solvent of dioxane and water; The reaction temperature is 90-100° C., and the reaction time is 48-96 hours.

7. Use of the polymer according to claim 1 or 2 in the preparation of an organic light-emitting diode device.

8. The application according to claim 7, wherein: The polymer is used as a light-emitting material of the organic light-emitting diode device.

9. An organic light emitting diode device, characterized in that: The light-emitting material used in the light-emitting layer of the organic light-emitting diode device comprises the polymer according to claim 1 or 2.

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