A type of chiral luminescent polymer and its preparation method and application

Abstract

This invention discloses a class of chiral light-emitting polymers, their preparation methods, and applications. Their structural formulas are shown in Formula 1 or Formula 2. The chiral polymer light-emitting layer materials of the present invention are simple to synthesize, have high product yields, and can be prepared on a large scale. The organic films formed from these chiral polymer light-emitting layer materials exhibit high surface smoothness, redox resistance, high luminescence efficiency, and a high asymmetry factor, and can be used as the light-emitting layer of organic light-emitting diodes. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the field of organic electroluminescent materials and devices, and in particular relates to a chiral luminescent polymer and a preparation method and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs), as a next-generation display technology, offer advantages over traditional displays, such as low cost, low power consumption, flexibility, rich colors, and wide viewing angles. Their applications in solid-state lighting and flat-panel displays are growing rapidly. With in-depth research and development, their luminescent materials have evolved into three generations. The first generation of OLED materials consisted of traditional fluorescent molecules, the second generation consisted of phosphorescent OLED materials, and the third generation consisted of thermally activated delayed fluorescence (TADF) materials. These phosphorescent and TADF materials can effectively utilize 75% of triplet excitons, resulting in high external quantum efficiency.

[0003] Circularly polarized light, as a special type of polarized light in nature, plays an important role in biological navigation, signal transmission and perception. The phenomenon when a luminescent system emits different left-handed and right-handed circularly polarized light is called circularly polarized luminescence (CPL). Due to its unique chiral light emission and polarization mode, CPL has great potential application prospects in 3D display, asymmetric synthesis, information encryption and transmission. Using traditional physical methods, natural light needs to pass through optical devices such as linear polarizers and quarter-wave plates in order to achieve the emission of circularly polarized light. This synthesis method not only requires a large amount of expensive and complex optical equipment, but also causes a loss in light brightness.

[0004] Therefore, it is of great significance to provide a new thermally activated delayed fluorescent material with circularly polarized luminescence properties to construct a high-efficiency circularly polarized light-emitting organic diode (CP-OLED) device and realize the spontaneous emission of circularly polarized light. Summary of the Invention

[0005] The present invention aims to provide a class of chiral light-emitting polymers, their preparation methods, and applications. The polymers of the present invention are multi-resonant polymer materials. Organic light-emitting diodes (OLEDs) using organic thin film layers formed from them as light-emitting layers have the advantages of high efficiency, low driving voltage, long life, and low efficiency roll-off.

[0006] The polymer provided by the present invention has a structural formula as shown in Formula 1 or Formula 2:

[0007]

[0008] Formula 1 represents the R configuration, and Formula 2 represents the S configuration;

[0009] In formula 1 and formula 2, R1 each independently represents C1-C 10A straight chain or branched chain alkyl group, specifically a n-hexyl group;

[0010] In formula 1 and formula 2, x refers to any value between 0 and 0.5, excluding the endpoint 0;

[0011] Ar represents a group whose parent structure is any of the following structures:

[0012]

[0013] Wherein, * is the connection position, Y is O, S, -CH2-, -CH(R3)-, -C(R3)(R4)-, R3 and R4 are each independently selected from C1-C6 straight or branched alkyl;

[0014] n represents the degree of polymerization, n=10-300.

[0015] Specifically, Ar is selected from any one of the following groups:

[0016] The polymer represented by Formula 1 is any one of the compounds represented by Formulas RP1-RP13:

[0017]

[0018] The polymer represented by Formula 2 is any one of the compounds represented by Formulas SP1-SP13:

[0019]

[0020] The present invention also provides a method for preparing the polymer.

[0021] The preparation method of the polymer provided by the present invention (taking the polymer represented by Formula 1 as an example) comprises the following steps:

[0022] 1) Formula C R The compound shown reacts with 4,5-difluoro-2-bromobenzonitrile to obtain formula C R The compound shown in 1;

[0023]

[0024] 2) Formula C R The compound shown in 1 reacts with the borate ester of Ar to obtain the compound of formula D R The compound shown;

[0025]

[0026] Ar borate ester, formula D R In the above, Ar is defined as above;

[0027] 3) Formula A, B and D RThe compound is polymerized at a molar ratio of 0.5-x:0.5:x, and then end-capped with phenyl bromide and phenylboronic acid to obtain a polymer of formula 1; wherein x = 0-0.5 (excluding 0);

[0028]

[0029] In formula A and B, R1 is as defined above.

[0030] In step 1) of the above method, the reaction is carried out under alkaline conditions; the alkaline conditions can be specifically provided by potassium carbonate;

[0031] The potassium carbonate, 4,5-difluoro-2-bromobenzonitrile and the formula C R The molar ratio of the compounds may be 6 to 8:1:1; specifically, 6:1:1;

[0032] The reaction in step 1) is carried out in a solvent; specifically, the solvent is at least one of toluene, 1,4-dioxane, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide and N,N-dimethylformamide;

[0033] In step 1), the reaction temperature may be 60-100° C., specifically 70° C., and the reaction time may be 20-24 hours, specifically 24 hours;

[0034] The reaction is carried out under the protection of an inert gas, and the inert gas may specifically be nitrogen.

[0035] In step 2) of the above method, the reaction is carried out in the presence of Pd(PPh3)4 and potassium carbonate;

[0036] The Pd(PPh3)4, the potassium carbonate and the formula C R The molar ratio of the compound shown in 1 can be 0.1 to 0.01:6:1, specifically 0.01:6:1;

[0037] The formula C R The molar ratio of the compound 1 to the borate of Ar can be 1:1 to 4, specifically 1:1.4;

[0038] The reaction in step 2) is carried out in a solvent; specifically, the solvent is toluene;

[0039] In step 2), the reaction temperature may be 120° C., and the reaction time may be 20 to 24 hours, specifically 24 hours;

[0040] The reaction is carried out under the protection of an inert gas, and the inert gas may specifically be nitrogen.

[0041] In step 3) of the above method, the reaction is carried out in the presence of Pd(PPh3)4 and sodium carbonate;

[0042] The Pd(PPh3)4, the sodium carbonate and the formula D R The molar ratio of the compounds shown may be 0.2-0.01:5:0.01, specifically 0.03:3:0.006;

[0043] Formula A, B and Formula D R The molar ratio of the compounds shown may be 0.5-x:0.5:x, where x is any value between 0 and 0.5, specifically, x is 0.01;

[0044] The reaction in step 3) is carried out in a solvent; specifically, the solvent is toluene:ethanol:water, and the specific volume ratio can be 4:2:1;

[0045] The reaction temperature may be 70-120° C., specifically 80° C., and the reaction time may be 48-96 hours, specifically 96 hours;

[0046] The end-capping treatment refers to sequentially adding benzene bromide into the system for reaction, the reaction time can be 5 hours, and then adding phenylboronic acid for reaction, the reaction time can be 5 hours, and the system temperature is still 80°C;

[0047] The molar ratio of the compound represented by formula B to benzyl bromide can be 1:2;

[0048] The molar ratio of formula A to phenylboronic acid may be 1:2;

[0049] Step 3) is carried out under the protection of an inert gas, and the inert gas may specifically be nitrogen.

[0050] Formula D R The compounds shown also fall within the protection scope of the present invention.

[0051] The use of the above polymer as a thermally activated delayed fluorescent material in the preparation of an organic light emitting diode device also falls within the scope of protection of the present invention.

[0052] In the application, the polymer is used as a light-emitting material in an organic light-emitting diode device; that is, as a chiral light-emitting polymer material.

[0053] The present invention further provides an organic light emitting diode device, wherein the light emitting layer of the organic light emitting diode device is made of a polymer represented by Formula 1 or Formula 2, or contains a polymer represented by Formula 1 or Formula 2.

[0054] The present invention has the following advantages:

[0055] (1) The chiral polymer light-emitting layer material of the present invention has a simple synthesis method, a high product yield, and can be prepared on a large scale;

[0056] (2) The organic film formed by the chiral polymer light-emitting layer material of the present invention has high surface smoothness, anti-oxidation and reduction properties, high luminescence efficiency, and a high asymmetry factor and can be used as the light-emitting layer of an organic light-emitting diode. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a schematic structural diagram of the organic light emitting diode prepared in the present invention.

[0058] Figure 2 The synthetic route diagram of Example 1 of the present invention is shown in FIG.

[0059] Figure 3 This is the synthetic route diagram of Example 2 of the present invention.

[0060] Figure 4 The synthetic route diagram of Example 3 of the present invention is shown in FIG.

[0061] Figure 5 The synthetic route diagram of Example 4 of the present invention is shown in FIG.

[0062] Figure 6 The synthetic route diagram of Example 5 of the present invention.

[0063] Figure 7 The synthetic route diagram of Example 6 of the present invention is shown in FIG.

[0064] Figure 8 This is the synthetic route diagram of Example 7 of the present invention.

[0065] Figure 9 The synthetic route diagram of Example 8 of the present invention.

[0066] Figure 10 The synthetic route diagram of Example 9 of the present invention.

[0067] Figure 11 This is the synthetic route diagram of Example 10 of the present invention.

[0068] Figure 12 The synthetic route diagram of Example 11 of the present invention.

[0069] Figure 13 This is the synthetic route diagram of Example 12 of the present invention.

[0070] Figure 14 This is the synthetic route diagram of Example 13 of the present invention. DETAILED DESCRIPTION

[0071] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those skilled in the art and are not intended to limit the present invention in any way.

[0072] Unless otherwise specified, the experimental methods in the following examples are conventional methods and were performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials and reagents used in the following examples, unless otherwise specified, were all commercially available.

[0073] Example 1. Preparation of the compound represented by formula RP1

[0074] according to Figure 2 The compound represented by formula RP1 (x=0.01, R configuration) is prepared according to the flow chart shown.

[0075] The specific steps are as follows:

[0076] (1) Under nitrogen protection, compound C was added to a 500 mL double-necked round-bottom flask in sequence. R 5g (11.33mmol), 4,5-difluoro-2-bromobenzonitrile 2.46g (11.3mmol), potassium carbonate 324mg (67.98mmol), N,N-dimethylformamide 20ml. React at 70℃ for 24 hours. After the reaction system is cooled to room temperature (same at 25℃), 300ml of water and 300ml of dichloromethane are added thereto for extraction. The organic phase after extraction is dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase is distilled off to obtain a crude product. The crude product is purified by column chromatography with the elution solvent being petroleum ether: dichloromethane (4:1) to obtain 6.34g of yellow powder. The white powder is C R 1, with a yield of 91%.

[0077] C R The structural confirmation data of 1 are as follows: HRMS (MALDI TOF) m / z calcd for C 27 H 12 Br3NO2, [M] + 618.8418, found 618.8445)

[0078] (2) Under nitrogen protection, compound 11 g (2.40 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and reacted at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300 mL of water and 300 mL of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 900 mg of a yellow powder. The yellow powder was Ar1, and the yield was 75%.

[0079] The structural confirmation data of Ar1 are as follows: HRMS (MALDI TOF) m / z calcd for C 36 H 28 B2N2O2[M] + 542.2337, found 542.2356).

[0080] (3) Under nitrogen protection, compound Ar1300 mg (0.55 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 280mg of a yellow powder. The yellow powder is D R 1, the yield is 90%.

[0081] D R The structural confirmation data of 1 are as follows: HRMS (MALDI TOF) m / z calcd for C 57 H 28 BBr2N3O2[M] + 955.0641, found 955.0680.

[0082] (4) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R15 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.3 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 101 mg of yellow powder RP1 with a yield of 66%.

[0083] The structural confirmation data of RP1 are as follows: GPC (THF, polystyrene standard) analysis showed aMw=19804, Mn=9303and PDI=2.12.

[0084] Example 2: Preparation of the compound represented by formula RP2

[0085] according to Figure 3 The process flow chart shown in the figure is used to prepare the compound of formula RP2, wherein x = 0.01

[0086] The specific steps are as follows:

[0087] (1) Under nitrogen protection, compound 21 g (1.56 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and reacted at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300 mL of water and 300 mL of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 980 mg of a yellow powder. The yellow powder was Ar2, and the yield was 80%.

[0088] The structural confirmation data of Ar2 are as follows: HRMS (MALDI TOF) m / z calcd for C 52 H 60B2N2O2[M] + 766.4841, found 766.4886.

[0089] (2) Under nitrogen protection, compound Ar2 300 mg (0.39 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 280mg of a yellow powder. The yellow powder is D R 2, the yield is 90%.

[0090] D R The structural confirmation data of 2 are as follows: HRMS (MALDI TOF) m / z calcd for C 73 H 60 BBr2N3O2[M] + 1179.3145, found 1179.3110.

[0091] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 27 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The product was filtered to obtain 100 mg of yellow powder RP2 with a yield of 65%.

[0092] The structural confirmation data of RP2 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17804, Mn = 7303 and PDI = 2.43.

[0093] Example 3: Preparation of the compound represented by formula RP3

[0094] according to Figure 4 The flow chart shown is used to prepare the compound represented by formula RP3, wherein x=0.01.

[0095] The specific steps are as follows:

[0096] (1) Under nitrogen protection, compound 31 g (2.12 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and reacted at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300 mL of water and 300 mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 930 mg of a yellow powder. The yellow powder was Ar3, and the yield was 73%.

[0097] The structural confirmation data of Ar3 are as follows: HRMS (MALDI TOF) m / z calcd for C 40 H 36 B2N2O2[M] + 598.2963, found 598.2934.

[0098] (2) Under nitrogen protection, compound Ar3 300 mg (0.50 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 270mg of a yellow powder. The yellow powder is D R 3, with a yield of 63%.

[0099] D R The structural confirmation data of 3 are as follows: HRMS (MALDI TOF) m / z calcd for C 61 H 36 BBr2N3O2[M] + 1011.1267, found 1011.1257.

[0100] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 35mg (0.006mmol), 145mg (0.294mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176mg (0.5mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317mg (3mmol) of sodium carbonate, 435mg (0.03mmol) of Pd(PPh3), 4mL of toluene, 2mL of ethanol, and 1mL of water were refluxed at 80°C for 96 hours. Subsequently, 95mg (0.6mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73mg (0.6mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 122 mg of yellow powder RP3 with a yield of 69%.

[0101] The structural confirmation data of RP3 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 18905, Mn = 7523 and PDI = 2.51.

[0102] Example 4. Preparation of the compound represented by formula RP4

[0103] according to Figure 5 The flow chart shown is used to prepare the compound represented by formula RP4, wherein x=0.01.

[0104] The specific steps are as follows:

[0105] (1) Under nitrogen protection, compound 41g (2.23mmol), Ir[(COD)(OCH3)] 20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was incubated at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300mL of water and 300mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 890mg of a yellow powder. The yellow powder was Ar4 with a yield of 80%.

[0106] The structural confirmation data of Ar4 are as follows: HRMS (MALDI TOF) m / z calcd for C36H 28 B2N2O4[M] + 574.2235, found 574.2289.

[0107] (2) Under nitrogen protection, 300 mg (0.52 mmol) of compound Ar4, C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 287mg of a yellow powder. The yellow powder is D R 4, with a yield of 66%.

[0108] D R The structural confirmation data of 4 are as follows: HRMS (MALDI TOF) m / z calcd for C 57 H 28 BBr2N3O4[M] + 987.0540, found 987.0535.

[0109] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R45 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 97 mg of yellow powder RP4 with a yield of 63%.

[0110] The structural confirmation data of RP4 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17857, Mn = 7378 and PDI = 2.42.

[0111] Example 5. Preparation of the compound represented by formula RP5

[0112] according to Figure 6 The reaction scheme shown is for preparing the compound represented by formula RP5, wherein x=0.01.

[0113] The specific steps are as follows:

[0114] (1) Under nitrogen protection, compound 51g (2.08mmol), Ir[(COD)(OCH3)] 20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was stirred at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300mL of water and 300mL of dichloromethane were added to it for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with the elution solvent being petroleum ether:dichloromethane (4:1) to obtain 700mg of yellow powder. The yellow powder is Ar5, and the yield is 55%.

[0115] The structural confirmation data of Ar5 are as follows: HRMS (MALDI TOF) m / z calcd for C 36 H 28B2N2O2S2[M] + 606.1778, found 606.1768.

[0116] (2) Under nitrogen protection, 300 mg (0.49 mmol) of compound Ar, C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 289mg of a yellow powder. The yellow powder is D R 5, with a yield of 68%.

[0117] D R The structural confirmation data of 5 are as follows: HRMS (MALDI TOF) m / z calcd for C 57 H 28 BBr2N3O2S2[M] + 1019.0083, found 1019.0067.

[0118] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 55.3 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 123 mg of yellow powder RP5 with a yield of 70%.

[0119] The structural confirmation data of RP5 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17804, Mn = 7303 and PDI = 2.43.

[0120] Example 6. Preparation of the compound represented by formula RP6

[0121] according to Figure 7 The reaction scheme shown is for preparing the compound represented by formula RP6, wherein x=0.01.

[0122] The specific steps are as follows:

[0123] (1) Under nitrogen protection, compound 61g (2.00mmol), Ir[(COD)(OCH3)]20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence, and the mixture was kept at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with the elution solvent being petroleum ether: dichloromethane (4:1) to obtain 900mg of a yellow powder. The yellow powder is Ar6, and the yield is 71%.

[0124] The structural confirmation data of Ar6 are as follows: HRMS (MALDI TOF) m / z calcd for C 42 H 40 B2N2O2[M] + 626.3276, found 626.3278.

[0125] (2) Under nitrogen protection, compound Ar6 300 mg (0.48 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 356mg of a yellow powder. The yellow powder is D R 6, with a yield of 71%.

[0126] D R The structural confirmation data of 6 are as follows: HRMS (MALDI TOF) m / z calcd for C 63 H 40 BBr2N3O2[M] + 1039.1580, found 1039.1578.

[0127] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 66 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 130 mg of yellow powder RP6 with a yield of 80%.

[0128] The structural confirmation data of RP6 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17804, Mn = 7266 and PDI = 2.45.

[0129] Example 7. Preparation of the compound represented by formula RP7

[0130] according to Figure 8 The reaction scheme shown is for preparing the compound represented by formula RP7, wherein x=0.01.

[0131] The specific steps are as follows:

[0132] (1) Under nitrogen protection, compound 71g (1.16mmol), Ir[(COD)(OCH3)] 20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was incubated at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300mL of water and 300mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 980mg of a yellow powder. The yellow powder was Ar7 with a yield of 86%.

[0133] The structural confirmation data of Ar7 are as follows: HRMS (MALDI TOF) m / z calcd for C 68 H 62 B2N4O2[M] + 988.5059, found 988.5027.

[0134] (2) Under nitrogen protection, compound Ar7300 mg (0.30 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 310mg of a yellow powder. The yellow powder is D R 7, with a yield of 73%.

[0135] D R The structural confirmation data of 7 are as follows: HRMS (MALDI TOF) m / z calcd for C 89 H 62 BBr2N5O2[M] + 1401.3363, found 1401.3319.

[0136] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R78mg (0.006mmol), 145mg (0.294mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176mg (0.5mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317mg (3mmol) of sodium carbonate, 435mg (0.03mmol) of Pd(PPh3), 4mL of toluene, 2mL of ethanol, and 1mL of water were refluxed at 80°C for 96 hours. Subsequently, 95mg (0.6mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73mg (0.6mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 134 mg of yellow powder RP7 with a yield of 68%.

[0137] The structural confirmation data of RP7 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17804, Mn = 7303 and PDI = 2.43.

[0138] Example 8. Preparation of the compound represented by formula RP8

[0139] according to Figure 9 The reaction scheme shown is for preparing the compound represented by formula RP8, wherein x=0.01.

[0140] The specific steps are as follows:

[0141] (1) Under nitrogen protection, compound 81g (1.16mmol), Ir[(COD)(OCH3)]20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was kept at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with the elution solvent being petroleum ether: dichloromethane (4:1) to obtain 1002mg of a yellow powder. The yellow powder is Ar8 with a yield of 88%.

[0142] The structural confirmation data of Ar8 are as follows: HRMS (MALDI TOF) m / z calcd for C 68 H 58B2N4O2[M] + 984.4746, found 984.4778.

[0143] (2) Under nitrogen protection, 300 mg (0.30 mmol) of compound Ar8, C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 281mg of a yellow powder. The yellow powder is D R 8, with a yield of 66%.

[0144] D R The structural confirmation data of 8 are as follows: HRMS (MALDI TOF) m / z calcd for C 89 H 58 BBr2N5O2[M] + 1397.3050, found 1397.3065.

[0145] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 88.4 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 121 mg of yellow powder RP8 with a yield of 75%.

[0146] The structural confirmation data of RP8 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 16794, Mn = 8903 and PDI = 1.88.

[0147] Example 9, Preparation of the Compound of Formula RP9

[0148] according to Figure 10 The reaction scheme shown is for preparing the compound represented by formula RP9, wherein x=0.01.

[0149] The specific steps are as follows:

[0150] (1) Under nitrogen protection, compound 91 g (1.57 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and the mixture was stirred at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300 mL of water and 300 mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 700 mg of a yellow powder. The yellow powder was Ar9, and the yield was 58%.

[0151] The structural confirmation data of Ar9 are as follows: HRMS (MALDI TOF) m / z calcd for C 50 H 46 B2N2O2S[M] + 760.3466, found 760.3456.

[0152] (2) Under nitrogen protection, compound Ar9300 mg (0.39 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 279mg of a yellow powder. The yellow powder is D R 9, with a yield of 60%.

[0153] D R The structural confirmation data of 9 are as follows: HRMS (MALDI TOF) m / z calcd for C 71 H 46 BBr2N3O2S[M] + 1173.1771, found 1173.1786.

[0154] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 97g (0.006mmol), 145mg (0.294mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176mg (0.5mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317mg (3mmol) of sodium carbonate, 435mg (0.03mmol) of Pd(PPh3), 4mL of toluene, 2mL of ethanol, and 1mL of water were refluxed at 80°C for 96 hours. Subsequently, 95mg (0.6mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73mg (0.6mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 127 g of yellow powder RP9 with a yield of 82%.

[0155] The structural confirmation data of RP9 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17004, Mn = 7803 and PDI = 2.18.

[0156] Example 10: Preparation of the compound represented by formula RP10

[0157] according to Figure 11 The reaction scheme shown is for preparing the compound represented by formula RP10, wherein x=0.01.

[0158] The specific steps are as follows:

[0159] (1) Under nitrogen protection, compound 101 g (0.922 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and the mixture was incubated at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300 mL of water and 300 mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 970 mg of a yellow powder. The yellow powder was Ar10, and the yield was 86%.

[0160] The structural confirmation data of Ar10 are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H 64 B2N6O2[M] + 1210.5277, found 1210.5234.

[0161] (2) Under nitrogen protection, compound Ar10 300 mg (0.24 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 260mg of a yellow powder. The yellow powder is D R 10, with a yield of 66%.

[0162] D R The structural confirmation data of 10 are as follows: HRMS (MALDI TOF) m / z calcd for C 106 H 65 BBr2N6O2[M] + 1622.3629, found 1622.3678.

[0163] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R109.75 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 mL of water and 300 mL of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 111 g of yellow powder RP10 with a yield of 69%.

[0164] The structural confirmation data of RP10 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17904, Mn = 7076, and PDI = 2.53.

[0165] Example 11. Preparation of the compound represented by formula RP11

[0166] according to Figure 12 The reaction scheme shown is for preparing the compound represented by formula RP11, wherein x=0.01.

[0167] The specific steps are as follows:

[0168] (1) Under nitrogen protection, compound 111 g (1.56 mmol), Ir[(COD)(OCH3)] 20.1 g (0.16 mmol), dtbpy 0.11 g (0.031 mmol), bis-pinacol borate 0.475 g (1.87 mmol), and 20 mL of tetrahydrofuran were added to a 500 mL double-necked round-bottom flask in sequence and the mixture was incubated at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300 mL of water and 300 mL of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 5.18 g of a yellow powder. The yellow powder was Ar11, and the yield was 80%.

[0169] The structural confirmation data of Ar11 are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H56 B2N6O2[M] + 1202.4651, found 1202.4651.

[0170] (2) Under nitrogen protection, 1300 mg (0.39 mmol) of compound R1, C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 280mg of a yellow powder. The yellow powder is D R 11, with a yield of 90%.

[0171] D R The structural confirmation data of 11 are as follows: HRMS (MALDI TOF) m / z calcd for C 105 H 58 BN7O2[M] + 1459.4745, found 1459.4745.

[0172] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 117g (0.006mmol), 145mg (0.294mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176mg (0.5mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317mg (3mmol) of sodium carbonate, 435mg (0.03mmol) of Pd(PPh3), 4mL of toluene, 2mL of ethanol, and 1mL of water were refluxed at 80°C for 96 hours. Subsequently, 95mg (0.6mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73mg (0.6mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 101 g of yellow powder RP11 with a yield of 66%.

[0173] The structural confirmation data of RP11 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17804, Mn = 7303 and PDI = 2.43.

[0174] Example 12: Preparation of the compound represented by formula RP12

[0175] according to Figure 13 The reaction scheme shown in the figure is used to prepare the compound represented by formula RP12, wherein x = 0.01

[0176] The specific steps are as follows:

[0177] (1) Under nitrogen protection, compound 121g (1.25mmol), Ir[(COD)(OCH3)] 20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was kept at 70°C for 24 hours. After the reaction system was cooled to room temperature (same at 25°C), 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with the elution solvent being petroleum ether: dichloromethane (4:1) to obtain 518mg of a yellow powder. The yellow powder is Ar12, and the yield is 45%.

[0178] The structural confirmation data of Ar12 are as follows: HRMS (MALDI TOF) m / z calcd for C 62 H 66 B2N4O2[M] + 920.5372, found 920.5345.

[0179] (2) Under nitrogen protection, compound Ar12300 mg (0.32 mmol), C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 180mg of a yellow powder. The yellow powder is D R12, with a yield of 42%.

[0180] D R The structural confirmation data of 12 are as follows: HRMS (MALDI TOF) m / z calcd for C 83 H 66 BBr2N5O2[M] + 1333.3676, found 1333.3667.

[0181] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R 128 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboronic acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 ml of water and 300 ml of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 120 g of yellow powder RP12 with a yield of 85%.

[0182] The structural confirmation data of RP12 are as follows: GPC (THF, polystyrene standard) analysis showed a Mw = 17874, Mn = 7373 and PDI = 2.42.

[0183] Example 13: Preparation of the compound represented by formula RP13

[0184] according to Figure 14 The reaction scheme shown is for preparing the compound represented by formula RP13, wherein x=0.01.

[0185] The specific steps are as follows:

[0186] (1) Under nitrogen protection, compound 131g (1.22mmol), Ir[(COD)(OCH3)]20.1g (0.16mmol), dtbpy 0.11g (0.031mmol), bis-pinacol borate 0.475g (1.87mmol), and 20mL tetrahydrofuran were added to a 500mL double-necked round-bottom flask in sequence and the mixture was incubated at 70°C for 24 hours. After the reaction system was cooled to room temperature (same as at 25°C), 300mL of water and 300mL of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (4:1) as the eluting solvent to obtain 845mg of a yellow powder. The yellow powder was Ar13, and the yield was 84%.

[0187] The structural confirmation data of Ar13 are as follows: HRMS (MALDI TOF) m / z calcd for C 64 H 66 B2N4O2[M] + 944.5372, found 944.5334.

[0188] (2) Under nitrogen protection, 3300 mg (0.36 mmol) of compound Ar1, C R 1180mg (0.39mmol), Pd (PPh3) 445mg (0.039mmol), potassium carbonate 324mg (2.3mmol), and 20mL toluene were refluxed at 120°C for 24 hours. After the reaction system was cooled to room temperature, 300ml of water and 300ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase 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 232mg of a yellow powder. The yellow powder is D R 13, with a yield of 52%.

[0189] D R The structural confirmation data of 13 are as follows: HRMS (MALDI TOF) m / z calcd for C 85 H 68 BN5O2[M] + 1201.5466, found 1201.5478.

[0190] (3) Under nitrogen protection, compound D was added into a 500 mL double-necked round-bottom flask in sequence. R137.2 mg (0.006 mmol), 145 mg (0.294 mmol) of 2,7-dibromo-9,9-dipentylfluorene, 176 mg (0.5 mmol) of 2,7-diboronate-9,9-dipentylfluorene, 317 mg (3 mmol) of sodium carbonate, 435 mg (0.03 mmol) of Pd(PPh3), 4 mL of toluene, 2 mL of ethanol, and 1 mL of water were refluxed at 80°C for 96 hours. Subsequently, 95 mg (0.6 mmol) of bromobenzene was added to the system and the reaction continued for 5 hours. Then, 73 mg (0.6 mmol) of phenylboric acid was added to the system and the reaction continued for 5 hours. After the reaction system was cooled to room temperature, 300 mL of water and 300 mL of dichloromethane were added to extract it. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain the crude product. The crude product was dissolved in 2 mL of dichloromethane and added dropwise into 400 mL of methanol. The mixture was filtered to obtain 124 g of yellow powder RP13 with a yield of 83%.

[0191] The structural confirmation data of RP13 are as follows: GPC (THF, polystyrene standard) analysis showed Mw = 19804, Mn = 8499 and PDI = 2.33.

[0192] The above takes R configuration, x = 0.01 as an example. The S configuration is synthesized in exactly the same way. When x changes, the formula A, B, and D (D R / D S ) with an input ratio of 0.5-x:0.5:x.

[0193] Example 14: Preparation of device

[0194] The organic light emitting diode device made of the chiral polymer material prepared in Example 1 of the present invention was prepared and its performance was evaluated.

[0195] (1) The steps for fabricating an organic electroluminescent device using a chiral polymer material as a light-emitting layer are as follows:

[0196] 1) Pretreatment of glass substrate: Select a glass substrate with 3×3mm 2 A glass substrate with an indium tin oxide (ITO) film pattern as a transparent electrode is prepared; the glass substrate is cleaned with pure water, placed in ethanol for ultrasonic treatment, and then treated with a plasma cleaning machine to obtain a pretreated glass substrate.

[0197] 2) Vacuum evaporation: The hole injection layer and the light-emitting layer were spin-coated on the pre-treated glass substrate using a solution method. First, the hole injection layer PEDOT:PSS was spin-coated on the ITO glass substrate (3500 rpm, 60 s), followed by annealing at 120 ° C for 30 min and spin-coating the light-emitting layer (25 mg mL-1 , 3000rpm, 60s), then annealed at 140℃ for 10min. After cooling, the ITO glass substrate was transferred to the evaporation chamber and decompressed to 6×10 -4 Pa below; vacuum evaporation of electron transport layer and cathode, organic compound through resistance heating to The film formation rate is vacuum evaporated to form films in sequence (1: electron transport layer; 2: electron injection layer; 3: cathode). Among them, a glass substrate with an ITO transparent electrode is used as the anode; the chiral polymer material (P1) of the present invention with a film thickness of 80nm is used as the light-emitting layer; PEDOT:PSS with a film thickness of 40nm is used as the hole injection layer; Tmpypb with a film thickness of 40nm is used as the electron transport layer; lithium fluoride with a film thickness of 1nm is used as the electron injection layer; aluminum with a film thickness of 100nm is configured with a metal mask in a manner orthogonal to the ITO stripes to form the cathode to obtain an organic light-emitting diode. The film thickness is measured using a stylus film thickness meter. The schematic diagram of its structure is shown as follows. Figure 1 shown.

[0198] 3) Device packaging: The prepared organic electroluminescent device is sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of less than 0.1 ppm, and then the film-forming substrate is covered with a sealing cover with epoxy-type ultraviolet-curable resin glass and sealed by self-digging curing.

[0199] (II) Performance Evaluation of Organic Light-Emitting Diodes Based on Chiral Polymer Material P1: A direct current was applied to the fabricated organic circularly polarized light-emitting diodes, and the luminescence performance was evaluated using a Spectrascan PR670 luminance meter. The current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter. The luminescence properties of the organic light-emitting diodes were measured while varying the applied direct current voltage.

[0200] The fabricated organic electroluminescent device has CIE color coordinates of (0.21, 0.37), an external quantum efficiency of 17.5%, a current efficiency of 43.2 cd / A, a power efficiency of 43.1 lm / W, and an electroluminescent asymmetry factor of 0.12.

[0201] Table 1 Performance data of organic light emitting diode devices prepared from polymers prepared in Examples 1-13

[0202]

[0203] As can be seen from the data in Table 1, the chiral polymer material of the present invention has a wide range of applications and is suitable for the preparation of OLEDs. The organic film formed from the chiral polymer material of the present invention has high surface smoothness, redox resistance, and high luminous efficiency, and can be used as the light-emitting layer of an organic light-emitting diode. Organic light-emitting diodes using an organic thin film layer formed from a chiral polymer material as the light-emitting layer improve device efficiency, reduce device driving voltage, and achieve an ideal asymmetry factor.

[0204] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that further improvements can be made to the present invention. In short, according to the principles of the present invention, this application is intended to include any changes, uses or improvements to the present invention, including changes that depart from the disclosed scope in this application and are made using conventional techniques known in the art.

Claims

1. A polymer having a structural formula as shown in Formula 1 or Formula 2: Formula 1 represents the R configuration, and Formula 2 represents the S configuration; In formula 1 and formula 2, R1 each independently represents C1-C 10 A straight or branched chain alkyl group; In formula 1 and formula 2, x refers to any value between 0 and 0.5, excluding the endpoint 0; Ar represents a group whose parent structure is any of the following structures: in, * is the connection position, Y is O, S, -CH2-, -CH(R3)-, -C(R3)(R4)-, R3 and R4 are each independently selected from C1-C6 straight or branched alkyl; n represents the degree of polymerization, n=10-300.

2. The polymer according to claim 1, characterized in that Ar is selected from any one of the following groups: Among them, * is the connection position.

3. The polymer according to claim 1, characterized in that The polymer represented by Formula 1 is any one of the compounds represented by Formulas RP1-RP13:

4. The polymer according to claim 1, characterized in that The polymer represented by Formula 2 is any one of the compounds represented by Formulas SP1-SP13:

5. A method for preparing a polymer according to any one of claims 1 to 4, comprising the steps of: 1) Formula C R The compound shown reacts with 4,5-difluoro-2-bromobenzonitrile to obtain formula C R The compound shown in 1; 2) Formula C R The compound shown in 1 reacts with the borate ester of Ar to obtain the compound of formula D R The compound shown; Ar borate ester, formula D R In the above, Ar is defined as Ar in claim 1; 3) Formula A, B and D R The compound is polymerized at a molar ratio of 0.5-x:0.5:x, and then end-capped with phenyl bromide and phenylboronic acid to obtain the polymer shown in Formula 1; wherein, x = 0-0.5, excluding the endpoint 0; In formula A and B, the definition of R1 is the same as that of R1 in claim 1.

6. Formula D in claim 5 R The compound shown.

7. Use of the polymer according to any one of claims 1 to 4 as a thermally activated delayed fluorescent material.

8. The use according to claim 7, characterized in that The application is the application of the polymer in the preparation of organic light emitting diode devices.

9. An organic light emitting diode device, wherein a light emitting layer of the organic light emitting diode device is made of the polymer according to any one of claims 1 to 4, or contains the polymer according to any one of claims 1 to 4.

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