CN106543417B - Polymer containing five-membered sulfone-based fused heterocyclic unit and its application, five-membered sulfone-based fused heterocyclic monomer and its preparation method - Google Patents

Abstract

The invention discloses the polymer for containing five yuan of sulfuryl condensed hetero ring units and its applications and five yuan of sulfuryl condensed hetero ring monomers and preparation method thereof.Due to the presence of sulfuryl in polymer of the present invention containing five yuan of sulfuryl condensed hetero ring units, is conducive to improve electron affinity, promotes the injection and transmission of electronics, there is high fluorescence efficiency and chemical stability；Polymer can be improved in five yuan of moderate conjugate planes of sulfuryl condensed hetero ring unit hole and electronic transmission performance introduce alkyl chain in the active site of condensed ring and can be effectively improved the dissolubility of monomer in organic solvent without causing biggish spectral red shift.The present invention obtains polymer by Suzuki, Stille, Yamamoto polymerization reaction by five yuan of sulfuryl condensed hetero ring monomers.Polymer of the present invention containing five yuan of sulfuryl condensed hetero ring units has good dissolubility in organic solvent, is suitable for solution processing, is with a wide range of applications in organic photoelectric field.

Description

Polymers containing five-membered sulfone-based fused heterocyclic units and their applications and five-membered sulfone-based fused heterocyclic rings Monomer and its preparation method

technical field

The invention belongs to the field of organic optoelectronics, and specifically relates to a polymer containing five-membered sulfone-based condensed heterocyclic units, a preparation method and application thereof.

Background technique

Organic/polymer light-emitting diodes (O/PLEDs) are a class of light-emitting diodes based on small organic molecules and polymer materials. Advantages, it has broad application prospects in organic flat panel display and white lighting devices. Organic solar cell materials started in the 1990s. They are a new type of sustainable and renewable green energy tool, and are easy to prepare large-area flexible cells, so they have great application potential. Organic field-effect transistors are transistor devices that use organic semiconductor materials as the active layer, and have attracted widespread attention for their low cost, flexibility and bendability, and the ability to manufacture large-area devices. Therefore, the field of organic optoelectronics has attracted the attention of many research institutions in the world, and the development of new efficient and stable materials is the focus of attention in the field of organic optoelectronics.

The blue light polymer containing ternary sulfone group condensed ring (S,S-dioxy-dibenzothiophene) unit has a strong electron-withdrawing group (-SO ₂ -) that can increase the electron affinity and have a higher electron affinity. Mobility and fluorescence quantum efficiency, the sulfur atom reaches the highest valence bond state with oxidation resistance, and the alkyl substitution -S,S-dioxy-dibenzothiophene can greatly improve the solubility of monomers in organic solvents, The availability of high polymer content and ease of solution processing have attracted widespread attention [ZL200710031273.2; ZL200910193934.0].

The five-membered sulfone-based fused heterocyclic ring structure has a larger conjugation plane than the three-membered sulfone-based fused ring unit, which is conducive to improving the hole/electron transport of the material; the intramolecular D-A interaction also enhances the fluorescence of the unit. It has a high fluorescence quantum efficiency of the polymer film; the S atom in it has reached the highest chemical valence state, and the ability to resist oxidation is strong. At the same time, the five-membered sulfone-based fused heterocyclic ring structure has more reactive sites that can be modified, and the solubility can be improved by introducing an alkyl chain, which is easy to prepare solution-processable polymers; and halogen atoms can be introduced at different positions of the benzene ring, Polymerized monomers with different structures can be obtained, so that the conjugated length of the polymer can be effectively adjusted, the fluorescence emission of the polymer can be adjusted, and a polymer with a high content and an ideal spectrum can be obtained.

Compared with polymers containing seven-membered sulfone-based fused heterocyclic units, five-membered sulfone-based fused heterocyclic unit polymers have a smaller conjugation length, which effectively weakens the spectral red shift caused by increasing the content, and can A polymer with high content and good color coordinates is obtained, [CN 201510200637.X].

The present invention has developed a polymer containing five-membered sulfone-based condensed heterocyclic units and a preparation method thereof. This type of polymer has good solubility, is suitable for solution processing, and has a moderate conjugation length in luminescent materials. Fluorescence spectra and color coordinates. Due to the strong electron-withdrawing group sulfone group and the large conjugation plane, the electron mobility of the material is enhanced, and it will also be used as an electron acceptor material and a high-mobility organic semiconductor material in solar cells and organic field effect transistors. It has great application potential.

Contents of the invention

The invention provides a new method for synthesizing five-membered sulfone-based condensed heterocyclic monomers, which is introduced into conjugated polymers to synthesize polymers with five-membered sulfone-based condensed heterocyclic units in the main chain.

The invention provides a polymer material containing a five-membered sulfone-based condensed heterocyclic unit, and applies it to organic electroluminescence, organic solar cells and organic field effect transistors.

The five-membered sulfone-based condensed heterocyclic monomer of the present invention has the following chemical structural formula:

In the formula, X is Br or I atom; Y is N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R) , P(=O)R, S, S=O or SO ₂ ; R ₁ , R ₂ , R are independently represented as H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro , acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group with 1 to 30 carbon atoms, cycloalkyl group with 3 to 30 carbon atoms, aromatic hydrocarbon group with 6 to 60 carbon atoms or 3 to 30 carbon atoms 60 aromatic heterocyclic groups.

The preparation method of the five-membered sulfone-based condensed heterocyclic monomer comprises the following steps:

(1) Under nitrogen protection, dissolve halo-2-fluoro-iodobenzene in N,N-dimethylformamide, add potassium carbonate and ethanethiol, and react to obtain halo-2-iodo-ethylmercaptobenzene ;

(2) Using acetic acid as a solvent, under an ice bath, oxidizing the halo-2-iodo-ethylmercaptobenzene with hydrogen peroxide to obtain the halo-2-iodo-ethanesulfinylbenzene;

(3) Under the protection of an inert gas, the halogenated-2-iodo-ethanesulfinylbenzene is coupled with 0.9 to 1.1 times the molar equivalent of a pre-prepared aromatic heterocyclic boronic ester containing substituents to obtain an unclosed ring Halo-ethanesulfinylbenzene derivatives;

(4) Then, under the trifluoromethanesulfonic acid environment, after adding phosphorus pentoxide to react at room temperature, slowly add ice water, filter with suction, add the obtained solid into pyridine, reflux under nitrogen, neutralize with dilute hydrochloric acid solution after cooling Pyridine, to obtain the condensed heterocyclic compound after ring closure;

(5) Make solvent with dichloromethane, add m-chloroperoxybenzoic acid and oxidize at 0～5 ℃ for 10～24 hours, after the reaction finishes, neutralize excessive sodium hydroxide aqueous solution with cold 10～30% mass concentration m-chloroperoxybenzoic acid to obtain a monohalogenated condensed heterocyclic compound containing a sulfone group;

(6) Dissolve the monohalogenated condensed heterocyclic compound containing sulfone group in the mixed solution of trifluoroacetic acid-chloroform or N,N-dimethylformamide-chloroform, and add dropwise The chloroform solution of N-bromosuccinimide or the chloroform solution of liquid bromine with a concentration of 1-1.5 mol/L is reacted to obtain the monomer of the five-membered sulfone-based condensed heterocyclic unit.

Further, in step (1), the halo-2-fluoro-iodobenzene is bromo-2-fluoro-iodobenzene or iodo-2-fluoro-iodobenzene.

Further, in step (1), the molar ratios of potassium carbonate, ethanethiol and halo-2-fluoro-iodobenzene are 2-5:1 and 1-1.5:1, respectively.

Further, in step (1), the reaction is carried out at 90-100° C. for 10-12 hours.

Further, in step (2), the temperature of the ice bath is 0-5°C.

Further, in step (2), the hydrogen peroxide concentration is 30-50 wt%.

Further, in step (2), the oxidation time is 8-12 hours.

Further, in step (3), the inert gas includes argon or nitrogen.

Further, in step (3), the coupling reaction is carried out at 60° C. to 70° C. for 24 to 36 hours, and tetrakis(triphenylphosphine palladium) and tetra-n-butylammonium bromide are added as catalysts.

Furthermore, the molar ratios of tetrakis(triphenylphosphinepalladium) and tetra-n-butylammonium bromide to halo-2-fluoro-iodobenzene are 1:20-34 and 1:10-17, respectively.

Further, in step (4), the molar ratio of the phosphorus pentoxide to the halo-ethanesulfinylbenzene derivative is 10-20:1.

Further, in step (4), the reaction time is 24-36 hours.

Further, in step (4), the reflux is at 110-120° C. for 12-24 hours.

Further, in step (6), the molar ratios of N-bromosuccinimide and liquid bromine to the monohalogenated condensed heterocyclic compound containing sulfone groups are 1:1-1.3 and 1:1-1.2.

Further, in step (6), when the chloroform solution of N-bromosuccinimide or the chloroform solution of liquid bromine is added dropwise, the temperature is lower than 5°C.

Further, in step (6), the reaction is carried out at 60-70° C. for 5-8 hours.

Further, step (6) is omitted, and a five-membered sulfone-based fused heterocyclic monomer in which Y is a sulfone group is directly prepared from steps (1) to (5).

The polymer containing five-membered sulfone-based fused heterocyclic ring units based on the above-mentioned five-membered sulfone-based fused heterocyclic monomer has the following chemical structural formula:

In the formula: x, y are the mole fractions of the unit components, satisfying: 0<x≤1, x+y=1, n=1～300; R ₁ and R ₂ are independently expressed as H, D, F, CN , alkenyl, alkynyl, nitrile, amino, nitro, acyl, alkoxy, carbonyl, sulfone, alkyl with 1 to 30 carbon atoms, cycloalkyl with 3 to 30 carbon atoms, carbon atoms An aromatic hydrocarbon group with 6 to 60 carbon atoms or an aromatic heterocyclic group with 3 to 60 carbon atoms;

Ar is a compound or derivative of the following structure:

Among them, Z ₁ , Z ₂ , and R ₃ are independently represented as H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, carbon atom An alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, an aromatic hydrocarbon group with 6 to 60 carbon atoms, or an aromatic heterocyclic group with 3 to 60 carbon atoms.

The polymer containing five-membered sulfone-based condensed heterocyclic units is applied in organic electroluminescence, organic solar cells and organic field effect transistors.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The present invention provides a simple and effective synthetic route of a five-membered sulfone-based condensed heterocyclic monomer, the raw material is cheap, and is conducive to large-scale preparation and production;

(2) Alkylation modification can be carried out in the five-membered fused ring, which greatly improves the solubility of monomers and polymers, and obtains high-molecular weight, high-content five-membered sulfone-containing fused heterocyclic unit copolymers and homogeneous polymer, its solution processability is also significantly improved;

(3) The D-A interaction in the polymer molecule containing the five-membered sulfone-based fused heterocyclic unit also enhances the fluorescence of the unit and improves the fluorescence quantum efficiency of the material. The five-membered sulfone-based fused heterocyclic unit has moderate conjugation Plane, which is conducive to improving the hole and electron transport properties of the polymer, and can obtain polymers with higher efficiency and better spectrum;

(4) Monomers with different structures can be obtained through halogenation reactions at different positions, so that the conjugation length and conjugation planarity of the material can be effectively adjusted, and better fluorescence emission can be obtained.

Description of drawings

Fig. 1 is the ultraviolet-visible absorption spectrum of polymer P1, P2 and P3 film;

Fig. 2 is the photoluminescence spectrum of polymer P1, P2 and P3 film;

Fig. 3 is the voltage-current density-brightness curve of polymer P1, P2 and P3 film;

Figure 4 is the device EL spectrum curves of polymers P1, P2 and P3.

Detailed ways

The present invention will be further described below in conjunction with the examples, but the implementation of the present invention can be carried out within the scope of the aforementioned parameters, and is not limited to the following examples.

Example 1

Synthesis of 3,9-dibromo-S,S-dioxo-dibenzothienoindene (M-1)

(1) Preparation of 5-bromo-2-iodo-ethylmercaptobenzene (1): Under nitrogen protection, dissolve 4-bromo-2-fluoro-iodobenzene (30.1g, 100mmol) in 250mL N,N-di Add potassium carbonate (27.6g, 200mmol) and ethanethiol (7.2mL, 100mmol) to methylformamide, and react at 90°C for 12h; after the reaction, wash the organic phase with saturated aqueous sodium chloride, dry Dried over magnesium sulfate; evaporated the solvent, and purified the product by column chromatography using petroleum ether as the eluent to obtain a colorless liquid (30.9 g, 90%). ¹ H NMR (500 MHz, CDCl ₃ ) δ (ppm): 7.62 (d, 1H), 7.24 (d, 1H), 6.97 (dd, 1H), 2.95 (q, 2H), 1.40 (t, 3H).

(2) Preparation of 5-bromo-2-iodo-ethanesulfinylbenzene (2): Dissolve 5-bromo-2-iodo-ethylmercaptobenzene (14.81g, 43.2mmol) in 150mL acetic acid, 30 wt% hydrogen peroxide (4.4 mL, 43.2 mmol) was added under the bath, and reacted at room temperature for 12 hours. After stopping the reaction, extract, dry, evaporate the solvent, and purify by column chromatography using petroleum ether/tetrahydrofuran (6:1) as eluent to obtain a white solid (10.86g, 70%). ¹ H NMR (500MHz, CDCl ₃ )δ(ppm):7.92(d,1H),7.66(d,1H),7.34(dd,1H),3.16-3.07(m,1H),2.87-2.78(m, 1H), 1.30(t,3H).

(3) Preparation of 2-bromo-9,9-dioctylfluorene (3): Under nitrogen protection, dissolve 2-bromofluorene (24.5g, 100mmol) in 200mL dimethyl sulfoxide, and add 40mL Aqueous sodium hydroxide solution with a mass fraction of 50%; stir vigorously at room temperature to form a suspension; slowly add 1-bromo-n-octane (42.5g, 220mmol) dropwise, continue stirring overnight, then extract with dichloromethane; The organic phase was washed with aqueous sodium solution and dried over anhydrous magnesium sulfate; the solvent was evaporated, and the product was purified by column chromatography using petroleum ether as eluent to obtain a pale yellow liquid (42.2 g, 90%). ¹ H NMR (300MHz, CDCl ₃ )δ(ppm): 7.66–7.70(m,1H),7.58(d,1H),7.47(s,1H),7.45(s,1H),7.36–7.33(m, 3H), 1.98(t,4H), 1.30–1.06(m,20H), 0.88(t,6H), 0.63–0.59(m,4H).

(4) Preparation of 2-boronate-9,9-dioctylfluorene (4): Dissolve 2-bromo-9,9-dioctylfluorene (14.1 g, 30 mmol) in 150 mL of anhydrous tetrahydrofuran Medium; Add a 2.5M n-butyllithium n-hexane solution (21.6mL, 54mmol) dropwise at -78°C under the protection of argon, and react at -78°C for 1 hour; then quickly add 2-isopropoxy -4,4,5,5-Tetramethyl-1,3,2-ethylenedioxy borate (18mL, 45mmol), continue to keep warm for 40 minutes; gradually raise the reaction solution to room temperature and react overnight; the reaction ends Finally, the reaction solution was poured into water, extracted with dichloromethane, washed with saline, and dried over anhydrous magnesium sulfate; the solvent was evaporated, and purified by column chromatography using petroleum ether/dichloromethane (6:1) as eluent to obtain White solid (10.84 g, 70%). ¹ H NMR (300MHz, CDCl ₃ ) δ (ppm): 7.85-7.6 (m, 6H), 7.30 (m, 1H), 2.17 (t, 4H), 1.40 (s, 12H), 1.22-1.03 (m, 20H), 0.84(t,6H), 0.59(m,4H).

(5) Preparation of 2-(4-bromo-2-ethanesulfinylphenyl)-9,9-dioctylfluorene (5): 40 mL of 2M aqueous potassium carbonate solution, 2-(4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (8.36g, 16.2mmol) and 5-bromo-2- Iodine-ethanesulfinylbenzene (6.40g, 17.8mmol) was added to the reaction flask, and 150mL of toluene was added, nitrogen was blown, tetrakis(triphenylphosphine palladium) (0.94g, 0.81mmol) and tetra-n-butyl bromide were added Ammonium chloride (0.52g, 1.62mmol) was reacted at 60°C for 24 hours. The reaction was stopped and cooled to room temperature, and extracted 3 times with dichloromethane. After the organic layer was spin-dried, 200-300 mesh silica gel was used to pass through the chromatography column. The polarity of the eluent was petroleum ether/dichloromethane (6:1), and finally a light yellow viscous liquid (7.54g, 75% ). ¹ H NMR (500MHz, CDCl ₃ )δ(ppm):8.17(d,1H),7.76(d,1H),7.73(dd,1H),7.63(dd,1H),7.39-7.32(m,4H) ,7.29(dd,2H),2,51(td,1H),2.25(td,1H),2.05-1.87(m,4H),1.32-0.97(m,20H),0.95(t,3H),0.81 (dt,6H),0.69-0.50(m,4H).

(6) Preparation of 3-bromo-dibenzothienoindene (6): 2-(4-bromo-2-ethanesulfinylphenyl)-9,9-di-n-octylfluorene (6.3g, 10.1mmol) and phosphorus pentoxide (14.2g, 100mmol) were added to 20mL of trifluoromethanesulfonic acid, stirred at room temperature for 24 hours; The yellow solid powder was dried in the air; the light yellow solid powder was dissolved in 100 mL of pyridine, heated to 110°C under nitrogen and refluxed for 12 hours; the reaction was stopped and cooled to room temperature, and the pyridine was extracted and neutralized with hydrochloric acid. The column was chromatographed with petroleum ether to obtain a white solid (4.65 g, 80%). ¹ H NMR (500MHz, CDCl ₃ )δ(ppm):8.11(s,1H),8.05(d,1H),8.02(s,1H),7.98(d,1H),7.77(d,1H),7.57 (dd, 1H), 7.39-7.32 (m, 3H), 2.09-2.01 (m, 4H), 1.20-0.97 (m, 20H), 0.78 (dd, 6H), 0.63 (s, 4H).

(7) Preparation of 3-bromo-S, S-dioxo-dibenzothienoindene (7): 3-bromo-dibenzothienoindene (4.31g, 7.5mmol) and 3-chloroperoxy Benzoic acid (6.45g, 37.5mmol) was dissolved in 40mL of dichloromethane and reacted for 10 hours at 5°C in an ice bath; after the reaction, the reaction solution was poured into cold 10% mass concentration of sodium hydroxide aqueous solution and stirred for 30 Minutes; the organic layer was washed with water (150mL×3), concentrated and passed through a chromatography column, the eluent polarity was petroleum ether/dichloromethane (6:1), and a white powder solid (4.10g, 90%) was obtained. ¹ H NMR (500MHz, CDCl ₃ )δ(ppm):8.09(s,1H),7.95(d,1H),7.79-7.71(m,3H),7.67(s,1H),7.42-7.39(m, 2H), 7.38-7.35(m, 1H), 2.09-1.96(m, 4H), 1.23-0.97(m, 20H), 0.79(t, 6H), 0.57(dd, 4H).

(8) Preparation of 3,9-dibromo-S, S-dioxo-dibenzothienoindene (M-1): 3-bromo-S, S-dioxo-dibenzothienoindene ( 1.5g, 2.5mmol) was dissolved in a mixed solution of 16mL trifluoroacetic acid and 5mL chloroform, and then N-bromosuccinimide (0.55g, 3.1mmol) was dispersed in 3mL chloroform, avoid Add dropwise to the reaction solution under light conditions, heat up to 60°C, and react for 5 hours under dark conditions; pour the reaction solution into water and extract with dichloromethane, and use eluent petroleum ether/dichloromethane (6:1 ) through a chromatography column, and the product was recrystallized from ethanol/tetrahydrofuran to obtain a white flaky solid (1.37 g, 80%). ¹ H NMR (500MHz, CDCl ₃ )δ(ppm): 8.06(s,1H),7.96(d,1H),7.78(dd,1H),7.73(d,1H),7.65(s,1H),7.61 (d,1H),7.54(dd,1H),7.50(d,1H),2.04-1.96(m,4H),1.24-0.99(m,20H),0.80(t,6H),0.63-0.51(m , 4H). MS (APCI): m/z (%): 686.1 [M ⁺ ].

Example 2

Synthesis of 2,9-dibromo-S,S-dioxo-dibenzothienoindene (M-2)

(1) Preparation of 4-bromo-2-iodo-ethylmercaptobenzene (8): Under nitrogen protection, 5-bromo-2-fluoro-iodobenzene (24.08g, 80mmol) was dissolved in 250mL N,N-di Add potassium carbonate (38.64g, 280mmol) and ethanethiol (7.0mL, 98mmol) to methylformamide, and react at 100°C for 10h; after the reaction, wash the organic phase with saturated aqueous sodium chloride solution, dry Dried over magnesium sulfate; the solvent was evaporated, and the product was purified by column chromatography using petroleum ether as the eluent to obtain a colorless liquid (21.96 g, 80%). MS (APCI): m/z (%): 344.1 [M ⁺ ].

(2) Preparation of 4-bromo-2-iodo-ethanesulfinylbenzene (9): Dissolve 4-bromo-2-iodo-ethylmercaptobenzene (11.85g, 34.6mmol) in 150mL acetic acid, Add hydrogen peroxide (3.52mL, 34.6mmol) with a concentration of 30wt% under bath conditions, and react at room temperature for 10 hours; after stopping the reaction, extract, dry, evaporate the solvent, and use petroleum ether/tetrahydrofuran (6:1) as the eluent column Purification by chromatography gave a white solid (8.69g, 70%). MS (APCI): m/z (%): 359.1 [M ⁺ ].

(3) Preparation of 2-(5-bromo-2-ethanesulfinylphenyl)-9,9-di-n-octylfluorene (10): 32 mL of 2M potassium carbonate aqueous solution, 2-(4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (6.69g, 13.0mmol) and 4-bromo-2- Iodine-ethanesulfinylbenzene (5.12g, 14.2mmol) was added to the reaction flask, and 100mL of toluene was added, nitrogen was blown, tetrakis(triphenylphosphine palladium) (0.75g, 0.65mmol) and tetra-n-butyl bromide were added Ammonium chloride (0.42g, 1.30mmol) was reacted at 60°C for 24 hours; the reaction was stopped and cooled to room temperature, and extracted 3 times with dichloromethane; the organic layer was spin-dried and passed through a chromatographic column with 200-300 mesh silica gel, The polarity of the eluent was petroleum ether/dichloromethane (6:1), and finally a light yellow viscous liquid (5.63g, 70%) was obtained. MS (APCI): m/z (%): 622.8 [M ⁺ ].

(4) Preparation of 2-bromo-dibenzothienoindene (11): 2-(5-bromo-2-ethanesulfinylphenyl)-9,9-di-n-octylfluorene (5.04g, 8.1mmol) and phosphorus pentoxide (11.36g, 80mmol) were added to 20mL trifluoromethanesulfonic acid, stirred at room temperature for 24 hours; Yellow solid powder and air-dried; Dissolve light yellow solid powder in 100mL pyridine, heat to 110°C under nitrogen and reflux for 12 hours; stop the reaction and cool to room temperature, extract and neutralize the pyridine with hydrochloric acid; layer with petroleum ether Column analysis gave a white solid (3.72g, 80%). MS (APCI): m/z (%): 576.7 [M ⁺ ].

(5) Preparation of 2-bromo-S,S-dioxo-dibenzothienoindene (12): 2-bromo-dibenzothienoindene (3.45g, 6.0mmol) and 3-chloroperoxy Benzoic acid (5.16g, 30mmol) was dissolved in 40mL of dichloromethane and reacted in an ice bath at 5°C for 10 hours; after the reaction, the reaction solution was poured into cold 10% mass concentration of sodium hydroxide aqueous solution and stirred for 30 minutes ; The organic layer was washed with water (150mL×3), concentrated and passed through a chromatography column with petroleum ether/dichloromethane (6:1) as the polarity eluent to obtain a white powder solid (3.28g, 90%). MS (APCI): m/z (%): 607.8 [M ⁺ ].

(6) Preparation of 2,9-dibromo-S, S-dioxo-dibenzothienoindene (M-2): 2-bromo-S, S-dioxo-dibenzothienoindene ( 1.5g, 2.5mmol) was dissolved in a mixed solution of 16mL trifluoroacetic acid and 5mL chloroform, and then N-bromosuccinimide (0.58g, 3.3mmol) was dispersed in 2.5mL chloroform, Add it dropwise to the reaction solution under light-shielding conditions, heat up to 70° C., and react for 5 hours under light-shielding conditions; pour the reaction solution into water and extract with dichloromethane, and use eluent petroleum ether/dichloromethane (6: 1) After passing through the chromatography column, the product was recrystallized from ethanol/tetrahydrofuran to obtain a white flaky solid (1.37 g, 80%). MS (APCI): m/z (%): 686.1 [M ⁺ ].

Example 3

Synthesis of 3,8-dibromo-S,S-dioxo-dibenzothienoindole (M-3)

(1) Preparation of 2-bromo-N-(2-decyltetradecyl)carbazole (13): 2-bromocarbazole (9.84g, 40mmol) and sodium hydroxide (16g, 400mmol) were dissolved in In 150mL dimethyl sulfoxide, heated to 60°C under nitrogen, slowly added 2-decyltetradecyl bromide (16.68g, 40mmol), reacted for 8 hours; stopped the reaction and cooled to room temperature, poured the reaction solution into water It was extracted with dichloromethane and purified by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a colorless liquid (16.30 g, 70%). MS (APCI): m/z (%): 583.6 [M ⁺ ].

(2) Preparation of 2-boronate-N-(2-decyltetradecyl)carbazole (14): 2-bromo-N-(2-decyltetradecyl)carbazole (10.82 g, 18.6mmol) was dissolved in 150mL of anhydrous tetrahydrofuran; under the protection of argon, add dropwise a 2.5M n-hexane solution of n-butyl lithium (13.4mL, 33.5mmol) at -78°C, and react at -78°C 1 hour; then quickly add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethylenedioxy borate (11.2mL, 27.9mmol), and continue the incubation reaction for 40 minute; the reaction solution was gradually raised to room temperature and reacted for 12 hours; after the reaction, the reaction solution was poured into water, extracted with dichloromethane, washed with saline, and dried over anhydrous magnesium sulfate. The solvent was evaporated and purified by column chromatography using petroleum ether/dichloromethane (6:1) as eluent to obtain a colorless oily liquid (7.02g, 60%). MS (APCI): m/z (%): 630.7 [M ⁺ ].

(3) Preparation of 2-(4-bromo-2-ethanesulfinylphenyl)-N-(2-decyltetradecyl)carbazole (15): 25 mL of 2M potassium carbonate aqueous solution, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(2-decyltetradecyl)carbazole (6.30g, 10mmol) and 5-bromo-2-iodo-ethanesulfinylbenzene (3.23g, 9mmol) were added to the reaction flask, and 100mL of toluene was added, nitrogen was blown, and tetrakis(triphenylphosphine palladium) (0.32g, 0.27 mmol) and tetra-n-butylammonium bromide (0.18g, 0.54mmol), reacted for 36 hours at 70°C; stopped the reaction and cooled to room temperature, and extracted 3 times with methylene chloride; after the organic layer was spin-dried, use 200～ 300-mesh silica gel was passed through a chromatographic column, and the polarity of the eluent was petroleum ether/dichloromethane (6:1), and finally a light yellow viscous liquid (4.63g, 70%) was obtained. ¹ H NMR (500MHz, CDCl ₃ )δ(ppm): 8.19(d,1H),8.16-8.09(m,2H),7.69(dd,1H),7.51(t,1H),7.42(d,1H) ,7.38(s,1H),7.33-7.26(m,2H),7.17(d,1H),4.16(d,2H),2.52-2.42(m,1H),2.25-2.15(m,1H),2.14 -2.06(m,1H),1.46-1.06(m,40H),0.90(dt,6H).

(4) Preparation of 3-bromo-dibenzothienoindole (16): 2-(4-bromo-2-ethanesulfinylphenyl)-N-(2-decyltetradecyl) Carbazole (4.41g, 6mmol) and phosphorus pentoxide (17.04g, 120mmol) were added to 20mL of trifluoromethanesulfonic acid, and stirred at room temperature for 36 hours; after the reaction, the reaction solution was added dropwise to ice water, and the mixture The light yellow solid powder was obtained by suction filtration and dried in the air; the light yellow solid powder was dissolved in 100mL of pyridine, heated to 120°C under nitrogen and refluxed for 24 hours; the reaction was stopped and cooled to room temperature, and the pyridine was extracted and neutralized with hydrochloric acid; The column chromatography was carried out with petroleum ether to obtain a pale yellow solid (3.31 g, 80%). ¹ H NMR (500MHz, CDCl ₃ )δ(ppm):8.47(s,1H),8.14(d,1H),8.05(d,1H),8.01(s,1H),7.98(d,1H),7.55 (dd,1H),7.53-7.46(m,1H),7.40(d,1H),7.27-7.23(m,1H),4.23(d,2H),2.25-2.16(m,1H),1.45-1.10 (m,40H),0.91-0.84(m,6H).

(5) Preparation of 3-bromo-S, S-dioxo-dibenzothienoindole (17): 3-bromo-dibenzothienoindole (2.76g, 4mmol) and 3-chloroperoxide Oxybenzoic acid (3.44g, 20mmol) was dissolved in 40mL of dichloromethane and reacted in an ice bath at 0°C for 24 hours; after the reaction, the reaction solution was poured into cold 30% mass concentration of sodium hydroxide aqueous solution and stirred for 30 Minutes; the organic layer was washed with water (150mL×3), concentrated and passed through a chromatography column with petroleum ether/dichloromethane (6:1) as the polarity eluent to obtain a pale yellow solid (2.60g, 90%). ¹ H NMR (500MHz, CDCl ₃ ) δ (ppm): 8.46 (s, 1H), 8.08 (d, 1H), 7.92 (d, 1H), 7.70 (dd, 1H), 7.66 (d, 1H), 7.55 (d,1H),7.54-7.50(m,1H),7.38(d,1H),7.34-7.29(m,1H),4.17(d,2H),2.15-2.04(m,1H),1.44-1.13 (m,40H),0.91-0.84(m,6H).

(6) Preparation of 3,8-dibromo-S,S-dioxo-dibenzothienoindole (M-3): 3-bromo-S,S-dioxo-diphenyl Thienoindole (1.80g, 2.5mmol) was dissolved in a mixed solution of 10mL chloroform and 8mL N,N-dimethylformamide, and N-bromosuccinimide (0.49g, 2.75mmol ) was dissolved in 2mL N,N-dimethylformamide, and added dropwise to the reaction solution under the condition of avoiding light; after reacting at 0°C for 1 hour, the temperature was raised to room temperature and continued to stir for 12 hours; the reaction solution was poured into water and washed with dichloro Extracted with methane, passed through the chromatographic column with eluent petroleum ether/dichloromethane (6:1), and recrystallized the product with n-hexane/tetrahydrofuran to obtain a white powder solid (1.6 g, 80%). ¹ H NMR (500MHz, CDCl ₃ ) δ (ppm): 8.33 (s, 1H), 8.09 (d, 1H), 7.91 (d, 1H), 7.66 (dd, 1H), 7.59 (d, 1H), 7.57 (dd,1H),7.49(s,1H),7.22(d,1H),4.15(d,2H),2.10-1.98(m,1H),1.45-1.08(m,40H),0.91-0.84(m ,6H).MS(APCI):m/z(%):800.6[M ⁺ ].

Example 4

Synthesis of 3,8-dibromo-S,S-dioxo-dibenzothienooxindene (M-4)

(1) Preparation of 3-boronate-dibenzofuran (18): Under nitrogen protection, 3-bromo-dibenzofuran (19.77g, 80mmol) was dissolved in 250mL 1,4-dioxane , adding biboronate (24.38g, 96mmol), potassium acetate (15.68g, 0.16mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (2.93g, 4mmol); warming up to 85°C and reacting for 12 hours, after the reaction, the reaction solution was poured into water, extracted with dichloromethane, washed with brine; the solvent was evaporated, and purified by column chromatography to obtain a white solid (16.70g, 71%). MS (APCI): m/z (%): 295.1 [M ⁺ ].

(2) Preparation of 3-(4-bromo-2-ethanesulfinylphenyl)-dibenzofuran (19): 75 mL of 2M potassium carbonate aqueous solution, 3-(4,4,5,5 -Tetramethyl-1,3,2-dioxaborolan-2-yl)-dibenzofuran (8.82g, 30mmol) and 5-bromo-2-iodo-ethanesulfinylbenzene (10.77g, 30mmol) was added into the reaction flask, and 120mL of toluene was added, and nitrogen gas was added, tetrakis(triphenylphosphine palladium) (1.39g, 1.2mmol) and tetra-n-butylammonium bromide (0.77g, 2.4mmol) were added, at 65 The reaction was carried out at ℃ for 30 hours; the reaction was stopped and cooled to room temperature, and extracted 3 times with dichloromethane. The organic layer was spin-dried and passed through a chromatographic column with 200-300 mesh silica gel to finally obtain a massive solid (8.39 g, 70%). MS (APCI): m/z (%): 400.2 [M ⁺ ].

(3) Preparation of 3-bromo-dibenzothienooxindene (20): 3-(4-bromo-2-ethanesulfinylphenyl)-dibenzofuran (7.98g, 20mmol) and five Diphosphorus oxide (42.6g, 300mmol) was added to 50mL of trifluoromethanesulfonic acid, stirred at room temperature for 30 hours; after the reaction was completed, the reaction solution was added dropwise to ice water, and the solid powder obtained by suction filtration of the mixed solution was dried in the air Dissolve the solid powder in 100mL of pyridine, heat to reflux at 115°C under nitrogen for 16 hours; stop the reaction and cool to room temperature, extract and neutralize the pyridine with hydrochloric acid; obtain a powdered solid (4.94g, 70%) after purification. MS (APCI): m/z (%): 354.2 [M ⁺ ].

(4) Preparation of 3-bromo-S, S-dioxo-dibenzothienoindene (21): 3-bromo-dibenzothienoindene (3.53g, 10mmol) and 3-chloroperoxide Oxybenzoic acid (8.6g, 50mmol) was dissolved in 40mL of dichloromethane and reacted in an ice bath at 0°C for 16 hours; after the reaction, the reaction solution was poured into cold 20% mass concentration of sodium hydroxide aqueous solution and stirred for 30 Minutes; the organic layer was washed with water (150mL×3), concentrated and passed through a chromatography column, the eluent polarity was petroleum ether/ethyl acetate (6:1), and a powder solid (3.47g, 90%) was obtained. MS (APCI): m/z (%): 386.2 [M ⁺ ].

(5) Preparation of 3,8-dibromo-S,S-dioxo-dibenzothienoindene (M-4): 3-bromo-S,S-dioxo-dibenzothienoindene Indene (2.32g, 6mmol) was dissolved in 50mL of chloroform solution, liquid bromine (0.31mL, 6mmol) was dispersed in 5mL of chloroform, and added dropwise to the reaction solution under dark conditions. More than 5°C; the reaction was completed at 0°C for 7 hours, the liquid bromine was quenched with sodium bisulfite, extracted with dichloromethane and purified by chromatography, and recrystallized from chlorobenzene to obtain a powder solid (1.69g, 61%). MS (APCI): m/z (%): 465.1 [M ⁺ ].

Example 5

Synthesis of 3,9-dibromo-S,S-dioxo-dibenzothieno(11-methylene)indene (M-5)

(1) Preparation of 2-bromo-9-(two-methylmercapto-methylene)fluorene (22): 2-bromofluorene (19.61g, 80mmol) was dissolved in dimethyl sulfoxide solution and separated at room temperature Potassium tert-butoxide (18.88g, 168.3mmol) was added in batches, and then carbon disulfide (6.78g, 89.2mmol) was added. After reacting for 30 minutes, methyl iodide (23.88g, 168.3mmol) was slowly added dropwise to the reaction solution and stirred for 12 hours. After the reaction, the reaction solution was poured into water, extracted with dichloromethane, washed with brine; the solvent was evaporated, and purified by column chromatography to obtain a yellow solid (10.06g, 36%). MS (APCI): m/z (%): 350.2 [M ⁺ ].

(2) Preparation of 2-bromo-9-(1-octyl-nonamethylene)fluorene (23): 2-bromo-9-(two-methylmercapto-methylene)fluorene ( 8.75g, 25mmol) and 0.1M Li ₂ CuCl ₄ tetrahydrofuran solution (6.9mL, 0.69mmol) were added to 100mL tetrahydrofuran solution, and then slowly added dropwise 2M octylmagnesium bromide ether solution (29.4mL, 58,7mmol ), after reacting for 4 hours, the reaction solution was quenched with 10% aqueous sodium hydroxide solution, extracted with dichloromethane and purified by column chromatography to obtain a light yellow oily liquid (6.62g, 55%). MS (APCI): m/z (%): 482.5 [M ⁺ ].

(3) 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(1-octyl-nonamethylene)fluorene ( 24) Preparation: Under nitrogen protection, dissolve 2-bromo-9-(1-octyl-nonamethylene)fluorene (14.48g, 30mmol) in 200mL of 1,4-dioxane, and add biboron in sequence Ester (9.75g, 36mmol), potassium acetate (6.27g, 64mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (1.17g, 1.6mmol); 85°C and reacted for 12 hours. After the reaction, the reaction solution was poured into water, extracted with dichloromethane, and washed with brine. The solvent was evaporated and purified by column chromatography to obtain a light yellow oily liquid (10.94 g, 69%). MS (APCI): m/z (%): 529.6 [M ⁺ ].

(4) Preparation of 2-(4-bromo-2-ethanesulfinylphenyl)-9-(1-octyl-nonylidene)fluorene (25): 25 mL of 2M potassium carbonate aqueous solution, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(1-octyl-nonylidene)fluorene (5.29g, 10mmol) and 5-bromo-2-iodo-ethanesulfinylbenzene (3.59g, 10mmol) were added to the reaction flask, and 80mL of toluene was added, nitrogen was blown, and tetrakis(triphenylphosphine palladium) (0.58g, 0.5 mmol) and tetra-n-butylammonium bromide (0.32g, 1mmol), reacted at 60°C for 24 hours; stopped the reaction and cooled to room temperature, and extracted 3 times with dichloromethane; spin-dried the organic layer with 100-200 The mesh silica gel was passed through the chromatography column to finally obtain a light yellow liquid (5.13 g, 81%). MS (APCI): m/z (%): 634.7 [M ⁺ ].

(5) Preparation of 3-bromo-dibenzothieno(11-methylene)indene (26): 2-(4-bromo-2-ethanesulfinylphenyl)-9-(1-octyl Base-nonylidene)fluorene (5.07g, 8mmol) and phosphorus pentoxide (11.36g, 80mmol) were added in 20mL trifluoromethanesulfonic acid, stirred at room temperature for 24 hours; after the reaction was completed, the reaction solution was added dropwise into ice water, and the mixture was suction-filtered to obtain a light yellow solid powder, which was dried in the air. The light yellow solid powder was dissolved in 60mL of pyridine, heated to 110°C under nitrogen and refluxed for 12 hours; the reaction was stopped and cooled to room temperature, the pyridine was extracted and neutralized with hydrochloric acid; an oily liquid (3.76g, 79%) was obtained after purification. MS (APCI): m/z (%): 588.7 [M ⁺ ].

(6) Preparation of 3-bromo-S, S-dioxo-dibenzothieno(11-methylene)indene (27): 3-bromo-dibenzothieno(11-methylene) Indene (2.94g, 5mmol) and 3-chloroperoxybenzoic acid (4.3g, 25mmol) were dissolved in 30mL of dichloromethane and reacted for 10 hours under ice bath conditions at 5°C; after the reaction, the reaction solution was poured into a cold Stir in 10% aqueous sodium hydroxide solution for 30 minutes; the organic layer was washed with water (150 mL×3), concentrated and purified by column chromatography to obtain a powder solid (2.79 g, 90%). MS (APCI): m/z (%): 620.6 [M ⁺ ].

(7) Preparation of 3,9-dibromo-S,S-dioxo-dibenzothieno(11-methylene)indene (M-5): 3-bromo-S,S-dioxo- Dibenzothieno(11-methylene)indene (1.86g, 3mmol) was dissolved in a mixed solution of 16mL trifluoroacetic acid and 5mL chloroform, and then N-bromosuccinimide (0.66g, 4.03mmol) was dispersed in 4mL of chloroform, added dropwise to the reaction solution under dark conditions, and after heating up to 65°C, reacted for 8 hours under dark conditions; the reaction solution was poured into water and extracted with dichloromethane and passed Purified by column chromatography to obtain a powdery solid (1.36 g, 65%). MS (APCI): m/z (%): 699.65 [M ⁺ ].

Example 6

Synthesis of 3,9-dibromo-bis(S,S-dioxo-dibenzothiophene)(M-6)

(1) Preparation of 1,4-dioctylbenzene (28): under nitrogen protection, 1,4-dibromobenzene (10.62g, 45mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, and 1,3-bis( Diphenylphosphinopropane) nickel dichloride (0.73g, 1.35mmol), then 60mL concentration is that 2M octylmagnesium bromide ethyl ether solution is slowly added dropwise in the reaction solution, stops the reaction after reacting for 12 hours, pours the reaction solution It was extracted with dichloromethane in water, and purified by column chromatography using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain a colorless oily liquid (8.86 g, 65%). MS (APCI): m/z (%): 303.5 [M ⁺ ].

(2) Preparation of 1,4-dibromo-2,5-dioctylbenzene (29): Dissolve 1,4-dioctylbenzene (7.58g, 25mmol) in 100mL chloroform solution under ice bath , liquid bromine (10g, 62.5mmol) was diluted with chloroform and slowly added dropwise to the reaction solution, and stirred in the dark for 12 hours; the reaction was stopped, the reaction solution was poured into water and extracted with dichloromethane, and purified by column chromatography , using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent to obtain colorless crystals (7.48 g, 65%). MS (APCI): m/z (%): 461.3 [M ⁺ ].

(3) Preparation of 1,4-diboronate-2,5-dioctylbenzene (30): Dissolve 1,4-dibromo-2,5-dioctylbenzene (6.9g, 15mmol) in In 100mL of anhydrous tetrahydrofuran; under the protection of argon, add dropwise a n-hexane solution (11.3mL, 22.5mmol) with a concentration of 2.5M n-butyl lithium at -78°C, and react at -78°C for 1 hour; then quickly add 2 -Isopropoxy-4,4,5,5-tetramethyl-1,3,2-ethanedioxy borate (11mL, 27mmol), continue to keep warm for 40 minutes; gradually raise the reaction solution to room temperature React for 12 hours; after the reaction, pour the reaction solution into water, extract with dichloromethane, wash with brine, and dry over anhydrous magnesium sulfate. The solvent was evaporated and purified by column chromatography using petroleum ether/dichloromethane (3:1) as eluent to obtain a white solid (4.99g, 60%). MS (APCI): m/z (%): 555.4 [M ⁺ ].

(4) Preparation of 4,4'-dibromo-2,2"-(bisethylsulfinylphenyl)-2',5'-dioctylbenzene (31): 25mL of 2M potassium carbonate Aqueous solution, 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,5-dioctylbenzene (4.43g, 8mmol ) and 5-bromo-2-iodo-ethanesulfinylbenzene (6.32g, 17.6mmol) were added to the reaction flask, and 100mL of toluene was added, nitrogen was blown, tetrakis (triphenylphosphine palladium) (0.92g, 0.8 mmol) and tetra-n-butylammonium bromide (0.52g, 1.6mmol), reacted for 24 hours at 60°C; stopped the reaction and cooled to room temperature, and extracted 3 times with methylene chloride; after the organic layer was spin-dried, use 200～ 300 mesh silica gel was passed through the chromatographic column, and the polarity of the eluent was petroleum ether/tetrahydrofuran (6:1), and finally obtained a light yellow solid (3.06g, 50%). MS (APCI): m/z (%): 765.8 [M ⁺ ].

(5) Preparation of 3,9-dibromo-bis(dibenzothiophene) (32): 4,4'-dibromo-2,2"-(bisethylsulfinylphenyl)-2', 5'-Dioctylbenzene (2.30g, 3mmol) and phosphorus pentoxide (8.52g, 60mmol) were added in 15mL of trifluoromethanesulfonic acid, stirred at room temperature for 24 hours; after the reaction, the reaction solution was added dropwise to In ice water, filter the mixture with suction to obtain a light yellow solid powder and dry it in the air; dissolve the light yellow solid powder in 50 mL of pyridine, heat to 120°C under nitrogen and reflux for 16 hours; stop the reaction and cool to room temperature, extract and wash with hydrochloric acid and the pyridine therein. The column chromatography was carried out with petroleum ether to obtain a light yellow solid (1.21g, 60%). MS (APCI): m/z (%): 673.6 [M ⁺ ].

(6) Preparation of 3,9-dibromo-bis(S,S-dioxo-dibenzothiophene) (M-6): 3,9-dibromo-bis(dibenzothiophene) (1.01g , 1.5mmol) and 3-chloroperoxybenzoic acid (2.58g, 15mmol) were dissolved in 20mL of dichloromethane and reacted for 10 hours under ice bath conditions at 5°C; after the reaction, the reaction solution was poured into a cold 10% mass The solution was stirred for 30 minutes in a concentrated sodium hydroxide aqueous solution; the organic layer was washed with water (150mL×3), concentrated and passed through a chromatographic column, and the polarity of the eluent was petroleum ether/tetrahydrofuran (3:1) to obtain a light yellow solid (0.99 g, 90%). MS

(APCI): m/z (%): 737.6 [M ⁺ ].

Example 7

Preparation of Poly(9,9-Di-n-octylfluorene-co-3,9-S,S-dioxo-dibenzothienoindene)(P1-P5)

Polymer P1: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3mmol), 2,7-dibromo-9,9-di-n-octylfluorene (147.9mg, 0.27mmol) and 3,9-dibromo-S,S-dioxo-dibenzothienoindene (20.6 mg, 0.03mmol) was added to 8mL toluene, 1mg palladium acetate, 2mg tricyclohexylphosphine and 0.8mL tetraethylammonium hydroxide were added at the same time, the temperature was stabilized at 80°C for 36 hours, and then 25mg phenylboronic acid was added to block and in React at 80°C for 12 hours, then add 0.2mL bromobenzene for the second capping and react at 80°C for 12 hours, then stop the reaction and cool to room temperature, precipitate into methanol, filter and Soxhlet extraction (successively with methanol , acetone and n-hexane), and then the polymer was dissolved in toluene and passed through the chromatographic column, precipitated into methanol and filtered again to obtain a fibrous polymer (P1) (150 mg, 60%). ¹ HNMR (500MHz, CDCl ₃ )δ(ppm): 8.19(br,ArH),7.98(br,ArH),7.95-7.80(br,ArH),7.78-7.45(br,ArH),7.40-7.30(br ,ArH),2.13(br,CH ₂ ),1.36-1.02(br,CH ₂ ),0.90-0.77(br,CH ₃ ).

Polymer P2: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (131.5mg, 0.24mmol) and 3,9-dibromo-S,S-dioxy-dibenzothienoindene (41.2mg , 0.06mmol), the preparation process is the same as P1; yield: 70%. ¹ H NMR (500MHz, CDCl ₃ )δ(ppm): 8.18(br,ArH),7.98(br,ArH),7.93-7.80(br,ArH),7.78-7.45(br,ArH),7.40-7.30( br,ArH),2.13(br,CH ₂ ),1.36-0.96(br,CH ₂ ),0.90-0.77(br,CH ₃ ).

Polymer P3: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (115.1mg, 0.21mmol) and 3,9-dibromo-S,S-dioxy-dibenzothienoindene (61.8mg , 0.09mmol), the preparation process is the same as P1; yield: 60%. ¹ H NMR (500MHz, CDCl ₃ )δ(ppm): 8.18(br,ArH),7.98(br,ArH),7.92-7.80(br,ArH),7.78-7.45(br,ArH),7.40-7.30( br,ArH),2.13(br,CH ₂ ),1.34-1.01(br,CH ₂ ),0.90-0.75(br,CH ₃ ).

Polymer P4: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (98.6mg, 0.18mmol) and 3,9-dibromo-S,S-dioxy-dibenzothienoindene (82.4mg , 0.12mmol), the preparation process is the same as P1; yield: 75%. ¹ H NMR (500MHz, CDCl ₃ ) δ (ppm): 8.18 (br, ArH), 7.98 (br, ArH), 7.92-7.80 (br, ArH), 7.79-7.45 (br, ArH), 7.40-7.30 ( br,ArH),2.13(br,CH ₂ ),1.32-1.01(br,CH ₂ ),0.91-0.76(br,CH ₃ ).

Polymer P5: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3 mmol) and 3,9-dibromo-S,S-dioxo-dibenzothienoindene (206.1mg, 0.3mmol), the preparation process was the same as P1; to obtain fibrous polymer (P5) (200mg, 72%) ; M _n : 147.9 kDa, PDI: 2.33.

Example 8

Preparation of Poly(3,9-S,S-Dioxy-Dibenzothienoindene)(P6)

In a nitrogen glove box, 3,9-dibromo-S,S-dioxo-dibenzothienoindene (412.2 mg, 0.6 mmol) was added to 30 mL of tetrahydrofuran, and 1 g of bis(1,5-cyclooctyl Diene)nickel, 0.5g of 1,5-cyclooctadiene and 0.8g of bipyridine, the temperature was stabilized at 80°C for 4 days, then 0.5mL of bromobenzene was added and reacted at 80°C for 20 hours, and then the reaction Stop cooling to room temperature, precipitate into methanol, filter and Soxhlet extraction (successively use methanol, acetone and n-hexane), then dissolve the polymer in chloroform and pass through the chromatography column, precipitate again into methanol and filter to obtain a powder solid , Yield: 40%. M _n : 3.8 kDa, PDI: 2.12.

Example 9

Preparation of poly(N-9'-heptadecylcarbazole-co-3,9-S,S-dioxo-dibenzothienoindene)(P7-P10)

Polymer P7: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-N-9'-heptadecylcarbazole (197.1 mg, 0.3mmol), 2,7-dibromo-N-9'-heptadecylcarbazole (152.0mg, 0.27mmol) and 3,9-dibromo-S,S-dioxo-dibenzothiophene Indene (20.6mg, 0.03mmol) was added to 8mL of toluene, 1mg of palladium acetate, 2mg of tricyclohexylphosphine and 0.8mL of tetraethylammonium hydroxide were added at the same time, the temperature was stabilized at 80°C for 36 hours, and then 25mg of phenylboronic acid was added Capped and reacted at 80°C for 12 hours, then added 0.2mL bromobenzene for the second capping and reacted at 80°C for 12 hours, then stopped the reaction and cooled to room temperature, precipitated into methanol, filtered and extracted by Soxhlet (methanol, acetone and n-hexane were used successively), and then the polymer was dissolved in toluene to pass through the chromatographic column, precipitated into methanol and filtered again to obtain a fibrous polymer (P7), with a yield of 67%. M _n : 47.7kDa, PDI: 1.80.

Polymer P8: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-N-9'-heptadecylcarbazole (197.1 mg , 0.3mmol), 2,7-dibromo-N-9'-heptadecylcarbazole (135.1mg, 0.24mmol) and 3,9-dibromo-S,S-dioxo-dibenzothieno Indene (41.2mg, 0.06mmol), the same preparation process as P7; yield: 65%. M _n : 62.9kDa, PDI: 1.87.

Polymer P9: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-N-9'-heptadecylcarbazole (197.1 mg , 0.3mmol), 2,7-dibromo-N-9'-heptadecylcarbazole (118.2mg, 0.21mmol) and 3,9-dibromo-S,S-dioxo-dibenzothieno Indene (61.8mg, 0.09mmol), the same preparation process as P7; yield: 70%. M _n : 316.1kDa, PDI: 2.40.

Polymer P10: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-N-9'-heptadecylcarbazole (197.1 mg , 0.3mmol), 2,7-dibromo-N-9'-heptadecylcarbazole (101.3mg, 0.18mmol) and 3,9-dibromo-S,S-dioxo-dibenzothieno Indene (82.4mg, 0.12mmol), the same preparation process as P7; yield: 69%. M _n : 147.7kDa, PDI: 2.18.

Polymer P11: 2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-N-9'-heptadecylcarbazole (197.1 mg ,0.3mmol), 3,9-dibromo-S,S-dioxy-dibenzothienoindene (206.1mg, 0.3mmol), to obtain fibrous polymer (P11), the preparation process is the same as P7; yield: 66%. M _n : 58.8 kDa, PDI: 1.91.

Example 10

Preparation of Poly(9,9-Di-n-octylfluorene-co-3,8-S,S-dioxo-dibenzothienoindole)(P12)

2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3mmol), 2,7-dibromo-9,9-di-n-octylfluorene (131.5mg, 0.24mmol) and 3,8-dibromo-S,S-dioxy-dibenzothienoindole (48.0mg, 0.06 mmol) was added to 8 mL of toluene, 1 mg of palladium acetate, 2 mg of tricyclohexylphosphine and 0.8 mL of tetraethylammonium hydroxide were added at the same time, the temperature was stabilized at 80 ° C for 36 hours, and then 25 mg of phenylboronic acid was added to end-cap and heated at 80 ° C Reacted for 12 hours, then added 0.2 mL bromobenzene for the second capping and reacted at 80 ° C for 12 hours, then stopped the reaction and cooled to room temperature, precipitated into methanol, and filtered Soxhlet extraction (successively with methanol, acetone and n-hexane), then the polymer was dissolved in toluene and passed through the chromatographic column, precipitated again into methanol and filtered to obtain a fibrous polymer (P12), yield: 62%. M _n : 46.8 kDa, PDI: 1.89.

Example 11

Preparation of Poly[9,9-Di-n-octylfluorene-co-3,9-bis(S,S-dioxo-dibenzothiophene)](P13)

2,7-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-9,9-di-n-octylfluorene (192.6mg, 0.3mmol), 2,7-dibromo-9,9-di-n-octylfluorene (131.5mg, 0.24mmol) and 3,8-dibromo-S,S-dioxy-dibenzothienoindole (44.2mg, 0.06 mmol) was added to 8 mL of toluene, 1 mg of palladium acetate, 2 mg of tricyclohexylphosphine and 0.8 mL of tetraethylammonium hydroxide were added at the same time, the temperature was stabilized at 80 ° C for 36 hours, and then 25 mg of phenylboronic acid was added to end-cap and heated at 80 ° C Reacted for 12 hours, then added 0.2 mL bromobenzene for the second capping and reacted at 80 ° C for 12 hours, then stopped the reaction and cooled to room temperature, precipitated into methanol, and filtered Soxhlet extraction (successively with methanol, acetone and n-hexane), then the polymer was dissolved in toluene and passed through the chromatographic column, precipitated again into methanol and filtered to obtain a fibrous polymer (P13), yield: 64%. M _n : 67.3 kDa, PDI: 1.99.

Example 12

Preparation of Poly(3,8-S,S-Dioxy-Dibenzothienoindole)(P14)

In a nitrogen glove box, 3,9-dibromo-S,S-dioxo-dibenzothienoindene (412.2 mg, 0.6 mmol) was added to 30 mL of tetrahydrofuran, and 1.0 g of bis(1,5-cyclo Octadiene) Nickel, 0.5g of 1,5-cyclooctadiene and 0.8g of bipyridine, the temperature was stabilized at 80°C for 4 days, then 0.5mL of bromobenzene was added and reacted at 80°C for 20 hours, then the The reaction is stopped and cooled to room temperature, precipitated into methanol, filtered and extracted by Soxhlet (methanol, acetone and n-hexane successively), and then the polymer is dissolved in chloroform and passed through the chromatography column, precipitated into methanol and filtered again to obtain fiber Polymer (P14), Yield: 33%. M _n : 3.0 kDa, PDI: 2.7.

Example 13

Preparation of poly[2,5-dioctyloxybenzene-alt-3,9-bis(S,S-dioxo-dibenzothiophene)](P15)

1,4-bis(4,4,5,5-tetramethyl-1,3-dioxo-2-boryl)-2,5-di-n-octyloxybenzene (175.8mg, 0.3mmol) and 3,9-dibromo-bis(S,S-dioxo-dibenzothiophene) (220.9 mg, 0.3 mmol) were added to 10 mL of toluene, and 1 mg of palladium acetate, 2 mg of tricyclohexylphosphine and 0.8 mL of tetra Ethyl ammonium hydroxide, the temperature was stabilized at 80°C for 36 hours, then 25 mg of phenylboronic acid was added to block and react at 80°C for 12 hours, then 0.2 mL of bromobenzene was added for the second time to block and react at 80°C for 12 hours , then stop the reaction and cool to room temperature, precipitate into methanol, filter and Soxhlet extraction (successively use methanol, acetone and n-hexane), then dissolve the polymer with toluene and pass through the chromatography column, precipitate again into methanol and filter , to obtain fibrous polymer (P15), yield: 53%. M _n : 19.1 kDa, PDI: 2.21.

Example 14

Fabrication of Polymer Electroluminescent Devices

On the pre-made indium tin oxide (ITO) glass, the square resistance is 15Ω, firstly use acetone, detergent, deionized water and isopropanol to ultrasonically clean, and plasma treatment for 10 minutes; There is polyethoxythiophene (PEDOT:PSS) film of polystyrene sulfonic acid, the thickness is 150nm; PEDOT:PSS film is dried at 80 ℃ in vacuum oven for 8 hours; Then the polymer xylene solution (1wt.% ) was spin-coated on the surface of the PEDOT:PSS film with a thickness of 80nm; finally, a 1.5nm-thick CsF layer and a 120nm-thick metal Al layer were sequentially vapor-deposited on the light-emitting layer.

The structure of the obtained electroluminescent device is: ITO/PEDOT:PSS/polymer/CsF/Al.

The ultraviolet-visible absorption spectra of polymer P1, P2, and P3 films are shown in Figure 1. From Figure 1, it can be seen that the absorption peaks of polymers P1, P2, and P3 are around 395 nm, where the absorption is the molecular backbone π-π Excellent jump absorption.

The thin film photoluminescence spectra of polymers P1, P2 and P3 are shown in Figure 2. From Figure 2, it can be seen that the emission of polymers P1, P2 and P3 has no obvious red shift and widen.

The voltage-current density-brightness curves of polymer P1, P2 and P3 films are shown in Figure 3. From Figure 3, it can be seen that polymers P1, P2 and P3 have lower turn-on voltage and higher brightness, indicating that the material composition The film property is good, the energy level is relatively matched, and it has good fluorescence characteristics.

The device EL spectrum curves of polymers P1, P2, and P3 are shown in Figure 4. It can be seen from Figure 4 that the emission of polymers P1, P2, and P3 has no obvious red shift and widen.

The properties of the electroluminescent devices prepared by polymers are shown in Table 1.

Table 1 Luminescence properties of polymer devices

It can be seen from Table 1 that the polymer containing pentamed sulfone-based fused heterocyclic units has lower turn-on voltage, higher current efficiency and brightness, and more ideal color coordinates, indicating that the material has better film-forming properties. And relatively matching energy levels, it has good fluorescence characteristics.

Claims (7)

1. the preparation method of five yuan of sulfuryl condensed hetero ring monomers, which comprises the steps of:

(1) under nitrogen protection, the fluoro- iodobenzene of halogenated -2- is dissolved in n,N-Dimethylformamide, potassium carbonate and ethyl mercaptan is added, Reaction obtains the iodo- second sulfydryl benzene of halogenated -2-；

(2) solvent is made with acetic acid, under ice bath, with the iodo- second sulfydryl benzene of the halogenated -2- of hydrogen peroxide oxidation, it is sub- obtains the iodo- second of halogenated -2- Sulphonyl benzene；

(3) under inert gas protection, the iodo- second iodosobenzene of halogenated -2- and 0.9~1.1 times of molar equivalent are well prepared in advance Structure isHeteroaromatic boron ester containing substituent group carries out coupling reaction, obtains non-cyclization Halogenated-second iodosobenzene derivative, Y be N (R), C (R)₂、Si(R)₂, O, C=N (R), C=C (R)₂, P (R), P (=O) R, S, S=O or SO₂；R₁、R₂, R be independently expressed as H, D, F, CN, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alcoxyl Base, carbonyl, sulfuryl, the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon atom number are 6~60 aromatic series The aromatic heterocycle that alkyl or carbon atom number are 3~60；

(4) it then under trifluoromethanesulfonic acid environment, after phosphorus pentoxide reaction is added at room temperature, is slowly added in ice water, filters, Obtained solid is added in pyridine, refluxed under nitrogen, it is cooling after in dilute hydrochloric acid solution and pyridine, the condensed hetero ring after obtaining cyclization Compound；

(5) solvent is made with methylene chloride, metachloroperbenzoic acid is added and aoxidizes 10~24 hours at 0~5 DEG C, after reaction, With in the sodium hydrate aqueous solution of 10~30% cold mass concentrations and excessive metachloroperbenzoic acid, the list containing sulfuryl is obtained Halogenated fused heterocyclic compound；

(6) the monohaloalkyl fused heterocyclic compound containing sulfuryl is dissolved in trifluoroacetic acid-chloroform or N,N-dimethylformamide-three In the mixed solution of chloromethanes, under the conditions of being protected from light, the trichlorine that concentration is the N- bromo-succinimide of 1~1.5mol/L is added dropwise The chloroform soln of dichloromethane or bromine, reaction, obtains the monomer of five yuan of sulfuryls condensed hetero ring unit.

2. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that in step (1), institute Stating the fluoro- iodobenzene of halogenated -2- is the fluoro- iodobenzene of bromo -2- or the fluoro- iodobenzene of iodo -2-；The potassium carbonate and ethyl mercaptan and halogenated -2- The molar ratio of fluoro- iodobenzene is respectively 2~5:1 and 1~1.5:1；The reaction is reacted 10~12 hours at 90~100 DEG C； The reaction is reacted 10~12 hours at 90~100 DEG C.

3. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that in step (2), institute Stating ice bath temperature is 0~5 DEG C；The hydrogen peroxide concentration is 30~50wt%；The time of the oxidation is 8~12h.

4. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that in step (3), institute Stating coupling reaction is 24~36h of reaction at 60~70 DEG C, and four (triphenylphosphine palladiums) are added in reaction and tetra-n-butyl ammonium bromide is made Catalyst；The molar ratio of four (triphenylphosphine palladiums) and tetra-n-butyl ammonium bromide and the fluoro- iodobenzene of halogenated -2- be respectively 1:20~ 34 and 1:10~17；The inert gas includes argon gas or nitrogen.

5. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that in step (4), institute The molar ratio for stating phosphorus pentoxide and halogenated-second iodosobenzene derivative is 10~20:1；The time of the reaction is 24~36 Hour；The reflux is flowed back 12~24 hours at 110~120 DEG C.

6. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that in step (6), institute State N- bromo-succinimide and bromine and the monohaloalkyl fused heterocyclic compound containing sulfuryl molar ratio be respectively 1:1~1.3 and 1:1~1.2；Be added dropwise N- bromo-succinimide chloroform soln or bromine chloroform soln when, temperature is below 5 ℃；The reaction is reacted 5~8 hours at 60~70 DEG C.

7. the preparation method of five yuan of sulfuryls condensed hetero ring monomer according to claim 1, which is characterized in that it omits step (6), Five yuan of sulfuryl condensed hetero ring monomers that Y is sulfuryl are directly prepared by step (1)~(5).