CN106543417A - Polymer containing five yuan of sulfuryl condensed hetero ring units and its application are with five yuan of sulfuryl condensed hetero ring monomers and preparation method thereof - Google Patents

Polymer containing five yuan of sulfuryl condensed hetero ring units and its application are with five yuan of sulfuryl condensed hetero ring monomers and preparation method thereof Download PDF

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CN106543417A
CN106543417A CN201610932980.8A CN201610932980A CN106543417A CN 106543417 A CN106543417 A CN 106543417A CN 201610932980 A CN201610932980 A CN 201610932980A CN 106543417 A CN106543417 A CN 106543417A
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sulfuryl
yuan
hetero ring
condensed hetero
bromo
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杨伟
张俞浩
应磊
郭婷
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses the polymer containing five yuan of sulfuryl condensed hetero ring units and its application are with 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, be conducive to improving electron affinity, promote the injection and transmission of electronics, with high fluorescence efficiency and chemical stability；Five yuan of moderate conjugate planes of sulfuryl condensed hetero ring unit can improve the hole of polymer and electronic transmission performance without causing larger spectral red shift, while the avtive spot in condensed ring introduces alkyl chain and can be effectively improved monomer dissolubility in organic solvent.The present invention obtains polymer by Suzuki, Stille, Yamamoto polyreaction 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

Polymer containing five yuan of sulfuryl condensed hetero ring units and its application and five yuan of sulfuryl condensed hetero rings Monomer and preparation method thereof
Technical field
The invention belongs to organic photoelectric field, and in particular to the polymer containing five yuan of sulfuryl condensed hetero ring units and its preparation side Method and application.
Background technology
Organic/polymer LED (O/PLED) is a class sending out based on organic molecule and polymeric material Optical diode, with light weight, actively it is luminous, visual angle is wide, energy consumption is low, it is easy make the advantages such as flexible and large size panel, organic Have broad application prospects in flat pannel display and white-light illuminating device.Organic solar battery material is started in last century 90 years In generation, be the green energy resource instrument of the new sustainable regeneration of a class, and easily prepares large area flexible battery, has huge application Potentiality.Organic field effect tube is the transistor device using organic semiconducting materials as active layer, with its low cost, flexibility It is flexible and receive significant attention the characteristics of broad area device can be prepared.Therefore, the world has been attracted in organic photoelectric field The concern of upper numerous research institution, and develop Jiao received much concern during new and effective stable material is even more organic photoelectric field Point.
The blue light frequency-doubling of the condensed ring of sulfuryl containing ternary (S, S- dioxo-dibenzothiophene) unit is due to strong electron-withdrawing group Group (- SO2-) electron affinity can be improved, there are higher electron mobility and fluorescence quantum efficiency, sulphur atom reaches highest price Bonded state has non-oxidizability, and alkyl replacement-S, and S- dioxo-dibenzothiophenes can greatly improve monomer in organic solvent In dissolubility, can obtain high-load polymer and be easy to solution processing, therefore suffer from extensive concern [ZL 200710031273.2；ZL200910193934.0].
And five yuan of sulfuryl condensed hetero ring structures have bigger conjugate planes compared to ternary sulfuryl condensed ring unit, be conducive to carrying Hole/the electric transmission of high material；Intramolecular D-A interacts and also enhances the fluorescence of unit, has higher polymerization The fluorescence quantum efficiency of thing thin film；S atom therein has reached highest chemical valence state, and antioxidative ability is stronger.Meanwhile, five First sulfuryl condensed hetero ring structure has more modifiable reflecting points, can improve dissolubility by introducing alkyl chain, it is easy to prepare The polymer of solution processable；And halogen atom can be introduced in the diverse location of phenyl ring, the polymerized monomer of different structure is obtained, from And the conjugate length of polymer can be effectively adjusted, the fluorescent emission of polymer is adjusted, high-load is obtained and spectrum is comparatively ideal Polymer.
And compared to the polymer containing seven yuan of sulfuryl condensed hetero ring units, five yuan of sulfuryl condensed hetero ring unit polymer are with less Conjugate length, effectively reduce and increase the spectral red shift for causing with content, high-load is obtained and chromaticity coordinates is preferable Polymer, [CN 201510200637.X].
The present invention develops polymer containing five yuan of sulfuryl condensed hetero ring units and preparation method thereof, and such polymer has very well Dissolubility, be suitable for solution processing, moderate conjugate length has preferable fluorescence spectrum and color to sit in being used in luminescent material Mark.Due to rolling into a ball sulfuryl and larger conjugate planes with strong electron-withdrawing group, the electron mobility of material is strengthened, and which is used as electricity Sub- acceptor material and high mobility organic semi-conducting material will be also had in terms of solaode and organic field effect tube Very big application potential.
The content of the invention
The present invention provides the new synthetic method of five yuan of sulfuryl condensed hetero ring monomers, and is introduced in conjugated polymer, closes Into polymer of the main chain containing five yuan of sulfuryl condensed hetero ring units.
The invention provides the polymeric material containing five yuan of sulfuryl condensed hetero ring units, and it is applied to organic electroluminescence In light, organic solar batteries and organic field effect tube.
Five yuan of sulfuryls condensed hetero ring monomer of the present invention, with following chemical structural formula：
In formula, X is Br or I atoms；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 SO2；R1、R2, R be independently expressed as H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alcoxyl Base, carbonyl, sulfuryl, the alkyl of carbon number 1～30, the cycloalkyl of carbon number 3～30, carbon number are 6～60 aromatic series Alkyl or carbon number are 3～60 aromatic heterocycle.
The preparation method of five yuan of sulfuryls condensed hetero ring monomer, comprises the steps：
(1), under nitrogen protection, halo -2- fluoro- iodobenzene is dissolved in DMF, potassium carbonate and second sulfur is added Alcohol, reaction obtain the iodo- second sulfydryl benzene of halo -2-；
(2) solvent is made with acetic acid, under ice bath, with hydrogen peroxide by halo -2- iodo- second sulfydryl benzene oxidatoin, obtains halo -2- Iodo- second iodosobenzene；
(3) under inert gas shielding, the iodo- second iodosobenzenes of halo -2- are previously prepared with 0.9～1.1 times of molar equivalent The good heteroaromatic boron ester containing substituent group carries out coupling reaction, obtains the halo-second iodosobenzene derivant of non-cyclization；
(4) and then under trifluoromethanesulfonic acid environment, after phosphorus pentoxide reaction is added under room temperature, it is slowly added in frozen water, Sucking filtration, during the solid that obtains adds pyridine, refluxed under nitrogen, with dilute hydrochloric acid solution and pyridine after cooling, after obtaining cyclization Fused heterocyclic compound；
(5) solvent is made with dichloromethane, adds metachloroperbenzoic acid to aoxidize 10～24 hours at 0～5 DEG C, reaction terminates Afterwards, with the metachloroperbenzoic acid in the sodium hydrate aqueous solution of 10～30% cold mass concentrations with excess, obtain containing sulfuryl Monohaloalkyl fused heterocyclic compound；
(6) the monohaloalkyl fused heterocyclic compound containing sulfuryl is dissolved in into trifluoroacetic acid-chloroform or N, N- dimethyl formyl In the mixed solution of amine-chloroform, under the conditions of lucifuge, Deca concentration is the N- bromo-succinimides of 1～1.5mol/L Chloroform soln or bromine chloroform soln, reaction, obtain the monomer of five yuan of sulfuryls condensed hetero ring unit.
Further, in step (1), the fluoro- iodobenzene of the halo -2- is the fluoro- iodobenzenes of bromo -2- or the fluoro- iodine of iodo -2- Benzene.
Further, in step (1), the potassium carbonate and ethyl mercaptan are respectively 2 with the mol ratio of the fluoro- iodobenzenes of halo -2- ～5：1 and 1～1.5：1.
Further, in step (1), the reaction is reacted 10～12 hours at 90～100 DEG C.
Further, in step (2), the ice bath temperature is 0～5 DEG C.
Further, in step (2), the hydrogen peroxide concentration is 30～50wt%.
Further, in step (2), the oxidization time is 8～12h.
Further, in step (3), the noble gases include argon or nitrogen.
Further, in step (3), the coupling reaction is 24～36h of reaction at 60 DEG C～70 DEG C, reacts and adds four (triphenylphosphine palladium) and tetra-n-butyl ammonium bromide make catalyst.
Further, the mol ratio of four (triphenylphosphine palladiums) and tetra-n-butyl ammonium bromide and the fluoro- iodobenzenes of halo -2- Respectively 1:20～34 and 1:10～17.
Further, in step (4), the phosphorus pentoxide is 10 with the mol ratio of halo-second iodosobenzene derivant ～20：1.
Further, in step (4), the time of the reaction is 24～36 hours.
Further, in step (4), the backflow is flowed back 12～24 hours at 110～120 DEG C.
Further, in step (6), N- bromo-succinimides and bromine and the monohaloalkyl fused heterocyclic compound containing sulfuryl Mol ratio be 1:1～1.3 and 1:1～1.2.
Further, in step (6), the chloroform of the chloroform soln or bromine of Deca N- bromo-succinimide During solution, temperature is below 5 DEG C.
Further, in step (6), the reaction is reacted 5～8 hours at 60～70 DEG C.
Further, step (6) is omitted, and five yuan of sulfuryls that Y is sulfuryl is directly prepared by step (1)～(5) thick miscellaneous Ring monomer.
Based on the polymer containing five yuan of sulfuryl condensed hetero ring units of above-mentioned five yuan of sulfuryls condensed hetero ring monomer, with following chemistry Structural formula：
In formula：The molar fraction of x, y for unit component, meets:0<X≤1, x+y=1, n=1～300；R1、R2It is only respectively It is vertical to be expressed as H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxyl, carbonyl, sulfuryl, carbon number 1～30 Alkyl, the cycloalkyl of carbon number 3～30, the aromatic hydrocarbyl that carbon number is 6～60 or virtue that carbon number is 3～60 Fragrant race's heterocyclic radical；
Ar is the compound or derivant of following structure：
Wherein, Z1、Z2、R3H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alcoxyl are expressed as independently Base, carbonyl, sulfuryl, the alkyl of carbon number 1～30, the cycloalkyl of carbon number 3～30, the fragrance that carbon number is 6～60 Race's alkyl or carbon number are 3～60 aromatic heterocycle.
The polymer for containing five yuan of sulfuryl condensed hetero ring units is in organic electroluminescent, organic solar batteries and organic field Apply in effect transistor.
Compared with prior art, the invention has the advantages that with benefit effect：
(1) the invention provides a kind of synthetic route of simple and effective five yuan of sulfuryls condensed hetero ring monomer, cost of material is low It is honest and clean, be conducive to scale to prepare production；
(2) modification can be alkylated in five yuan of condensed ring, significantly improves the dissolubility of monomer and polymer, obtain High molecular, five yuan of unit copolymers of condensed hetero ring containing sulfuryl of high-load and homopolymer, its solution processability also significantly can be carried It is high；
(3) D-A in the polymer molecule containing five yuan of sulfuryl condensed hetero ring units interacts and also enhances the fluorescence of unit Property, the fluorescence quantum efficiency of material is improve, five yuan of sulfuryl condensed hetero ring units have moderate conjugate planes, are conducive to improving poly- The hole of compound and electronic transmission performance, are obtained that efficiency is higher and the preferable polymer of spectrum；
(4) monomer of different structure is obtained by the halogenating reaction of diverse location, such that it is able to effectively adjust material Conjugate length and conjugate planes, obtain preferable fluorescent emission.
Description of the drawings
Fig. 1 is polymer P 1, the uv-visible absorption spectra of P2 and P3 thin film；
Fig. 2 is polymer P 1, the photoluminescence spectra of P2 and P3 thin film；
Fig. 3 is polymer P 1, the voltage-current density-brightness curve of P2 and P3 thin film；
Fig. 4 is the device EL curves of spectrum of polymer P 1, P2 and P3.
Specific embodiment
The present invention is further elaborated with reference to embodiments, but the enforcement of the present invention can be in the range of aforementioned parameters Hold and implement, however it is not limited to following examples.
Embodiment 1
The synthesis of bis- bromo- S of 3,9-, S- dioxo-dibenzothiophenes indenes (M-1)
(1) preparation of the iodo- second sulfydryl benzene (1) of the bromo- 2- of 5-：Under nitrogen protection, by 4- bromo- 2- fluoro- iodobenzene (30.1g, 100mmol) it is dissolved in 250mL DMFs, and adds potassium carbonate (27.6g, 200mmol) and ethyl mercaptan (7.2mL, 100mmol), reacts 12h at 90 DEG C；After reaction terminates, organic faciess are washed with saturated sodium-chloride water solution, it is anhydrous Magnesium sulfate is dried；Boil off solvent, product petroleum ether makees the purification of eluant column chromatography, obtain colourless liquid (30.9g, 90%).1H NMR(500MHz,CDCl3)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 the iodo- second iodosobenzenes (2) of the bromo- 2- of 5-：By 5- bromo- 2- iodo- second sulfydryl benzene (14.81g, 43.2mmol) it is dissolved in 150mL acetic acid, concentration is added under 0 DEG C of ice bath for the hydrogen peroxide (4.4mL, 43.2mmol) of 30wt%, room Temperature reaction 12 hours.After stopped reaction, extract, be dried, boil off solvent, with petroleum ether/tetrahydrofuran (6:1) make eluant post layer Analysis purification, obtain white solid (10.86g, 70%).1H NMR(500MHz,CDCl3)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 the bromo- 9,9- di-n-octyls fluorenes (3) of 2-：Under nitrogen protection, will be 2- bromine fluorenes (24.5g, 100mmol) molten In 200mL dimethyl sulfoxide, and add the sodium hydrate aqueous solution that 40mL mass fractions are 50%；Shape is stirred vigorously under room temperature Into suspension；1- bromine normal octanes (42.5g, 220mmol) is slowly added dropwise, after continuing to be stirred overnight, is extracted with dichloromethane；With full Organic faciess are washed with sodium-chloride water solution, anhydrous magnesium sulfate is dried；Solvent is boiled off, product petroleum ether is made eluant column chromatography and carried It is pure, obtain weak yellow liquid (42.2g, 90%).1H NMR(300MHz,CDCl3)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- borates -9,9- di-n-octyl fluorenes (4):By 2- bromo- 9,9- di-n-octyl fluorenes (14.1g, 30mmol) it is dissolved in 150mL anhydrous tetrahydro furans；Argon protection under when -78 DEG C Deca concentration be 2.5M n-BuLis just Hexane solution (21.6mL, 54mmol), reacts 1 hour at -78 DEG C；2- isopropoxies -4,4,5,5- four is rapidly joined subsequently Methyl isophthalic acid, 3,2- ethylenedioxy borates (18mL, 45mmol) continue insulation reaction 40 minutes；Reactant liquor is gradually increased to into room Temperature reaction is overnight；Reactant liquor is poured into water after terminating by reaction, is done with dichloromethane extraction, brine It, anhydrous magnesium sulfate It is dry；Solvent is boiled off, with petroleum ether/dichloromethane (6:1) make eluant column chromatography purification, obtain white solid (10.84g, 70%) 。1H NMR(300MHz,CDCl3)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- (the bromo- 2- second sulfenyl phenyl of 4-) -9,9- di-n-octyl fluorenes (5)：By the carbon that 40mL concentration is 2M Sour aqueous solutions of potassium, 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -9,9- di-n-octyl fluorenes (8.36g, 16.2mmol) it is added in reaction bulb with the iodo- second iodosobenzenes (6.40g, 17.8mmol) of the bromo- 2- of 5-, and adds 150mL first Benzene, leads to nitrogen, adds four (triphenylphosphine palladium) (0.94g, 0.81mmol) and tetra-n-butyl ammonium bromide (0.52g, 1.62mmol), React 24 hours at 60 DEG C.Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane.Use after organic layer is spin-dried for 200～300 mesh silica gel cross chromatographic column, and the polarity of eluant is petroleum ether/dichloromethane (6:1), finally give faint yellow sticky Shape liquid (7.54g, 75%).1H NMR(500MHz,CDCl3)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 the bromo- dibenzothiophenes of 3- indenes (6)：Will be 2- (the bromo- 2- second sulfenyl phenyl of 4-) -9,9- two just pungent Base fluorenes (6.3g, 10.1mmol) and phosphorus pentoxide (14.2g, 100mmol) are added in 20mL trifluoromethayl sulfonic acids, room temperature bar Stir 24 hours under part；Reaction after terminating is added drop-wise to reactant liquor in frozen water, and mixed liquor sucking filtration is obtained flaxen solid powder Simultaneously dry at end；Faint yellow solid powder is dissolved in 100mL pyridines, heated under nitrogen flows back 12 hours to 110 DEG C；Stopped reaction And room temperature is cooled to, extract and be neutralized with hydrochloric acid pyridine therein.Chromatographic column is crossed with petroleum ether, obtain white solid (4.65g, 80%).1H NMR(500MHz,CDCl3)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 the bromo- S of 3-, S- dioxo-dibenzothiophenes indenes (7)：By 3- bromo- dibenzothiophenes indenes (4.31g, In 7.5mmol) being dissolved in 40mL dichloromethane with 3- chloroperoxybenzoic acids (6.45g, 37.5mmol) and under 5 DEG C of condition of ice bath Reaction 10 hours；30 points are stirred in reacting the sodium hydrate aqueous solution for after terminating pour reactant liquor into 10% cold mass concentration Clock；Organic layer washes (150mL × 3) with water, concentrates and cross chromatographic column, and eluant polarity is petroleum ether/dichloromethane (6:1), obtain To white powder solid (4.10g, 90%).1H NMR(500MHz,CDCl3)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 bis- bromo- S of 3,9-, S- dioxo-dibenzothiophenes indenes (M-1)：By 3- bromo- S, S- dioxies-dibenzo Thieno indenes (1.5g, 2.5mmol) is dissolved in the mixed solution of 16mL trifluoroacetic acids and 5mL chloroform, then by N- bromo fourths After imidodicarbonic diamide (0.55g, 3.1mmol) is dispersed in 3mL chloroform, it is added drop-wise under the conditions of lucifuge in reactant liquor, heats up To after 60 DEG C, react 5 hours under the conditions of lucifuge；By reactant liquor be poured into water and with dichloromethane extract, with eluent petroleum ether/ Dichloromethane (6:1) cross chromatographic column, product ethanol/tetrahydrofuran be recrystallized to give white flaky solid (1.37g, 80%).1H NMR(500MHz,CDCl3)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+]。
Embodiment 2
The synthesis of bis- bromo- S of 2,9-, S- dioxo-dibenzothiophenes indenes (M-2)
(1) preparation of the iodo- second sulfydryl benzene (8) of the bromo- 2- of 4-：Under nitrogen protection, by 5- bromo- 2- fluoro- iodobenzene (24.08g, 80mmol) it is dissolved in 250mL DMFs, and adds potassium carbonate (38.64g, 280mmol) and ethyl mercaptan (7.0mL, 98mmol), reacts 10h at 100 DEG C；After reaction terminates, organic faciess are washed with saturated sodium-chloride water solution, it is anhydrous Magnesium sulfate is dried；Boil off solvent, product petroleum ether makees the purification of eluant column chromatography, obtain colourless liquid (21.96g, 80%).MS (APCI):M/z (%):344.1[M+]。
(2) preparation of the iodo- second iodosobenzenes (9) of the bromo- 2- of 4-：By 4- bromo- 2- iodo- second sulfydryl benzene (11.85g, 34.6mmol) be dissolved in 150mL acetic acid, under 0 DEG C of condition of ice bath add concentration for 30wt% hydrogen peroxide (3.52mL, 34.6mmol), room temperature reaction 10 hours；After stopped reaction, extract, be dried, boil off solvent, with petroleum ether/tetrahydrofuran (6:1) Make eluant column chromatography purification, obtain white solid (8.69g, 70%).MS(APCI):M/z (%):359.1[M+]。
(3) preparation of 2- (the bromo- 2- second sulfenyl phenyl of 5-) -9,9- di-n-octyl fluorenes (10)：By 32mL concentration for 2M's Wet chemical, 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -9,9- di-n-octyl fluorenes (6.69g, 13.0mmol) it is added in reaction bulb with the iodo- second iodosobenzenes (5.12g, 14.2mmol) of the bromo- 2- of 4-, and adds 100mL first Benzene, leads to nitrogen, adds four (triphenylphosphine palladium) (0.75g, 0.65mmol) and tetra-n-butyl ammonium bromide (0.42g, 1.30mmol), React 24 hours at 60 DEG C；Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane；Use after organic layer is spin-dried for 200～300 mesh silica gel cross chromatographic column, and the polarity of eluant is petroleum ether/dichloromethane (6:1), finally give faint yellow sticky Shape liquid (5.63g, 70%).MS(APCI):M/z (%):622.8[M+]。
(4) preparation of the bromo- dibenzothiophenes of 2- indenes (11)：Will be 2- (the bromo- 2- second sulfenyl phenyl of 5-) -9,9- two just pungent Base fluorenes (5.04g, 8.1mmol) and phosphorus pentoxide (11.36g, 80mmol) are added in 20mL trifluoromethayl sulfonic acids, room temperature bar Stir 24 hours under part；Reaction after terminating is added drop-wise to reactant liquor in frozen water, and mixed liquor sucking filtration is obtained flaxen solid powder Simultaneously dry at end；Faint yellow solid powder is dissolved in 100mL pyridines, heated under nitrogen flows back 12 hours to 110 DEG C；Stopped reaction And room temperature is cooled to, extract and be neutralized with hydrochloric acid pyridine therein；Chromatographic column is crossed with petroleum ether, obtain white solid (3.72g, 80%).MS(APCI):M/z (%):576.7[M+]。
(5) preparation of the bromo- S of 2-, S- dioxo-dibenzothiophenes indenes (12)：By 2- bromo- dibenzothiophenes indenes During (3.45g, 6.0mmol) and 3- chloroperoxybenzoic acids (5.16g, 30mmol) are dissolved in 40mL dichloromethane and in 5 DEG C of ice baths Under the conditions of react 10 hours；Stir in reacting the sodium hydrate aqueous solution for after terminating pour reactant liquor into 10% cold mass concentration 30 minutes；Organic layer washes (150mL × 3) with water, concentrates and cross chromatographic column, and eluant polarity is petroleum ether/dichloromethane (6: 1), obtain white powder solid (3.28g, 90%).MS(APCI):M/z (%):607.8[M+]。
(6) preparation of bis- bromo- S of 2,9-, S- dioxo-dibenzothiophenes indenes (M-2)：By 2- bromo- S, S- dioxies-dibenzo Thieno indenes (1.5g, 2.5mmol) is dissolved in the mixed solution of 16mL trifluoroacetic acids and 5mL chloroform, then by N- bromo fourths After imidodicarbonic diamide (0.58g, 3.3mmol) is dispersed in 2.5mL chloroform, it is added drop-wise under the conditions of lucifuge in reactant liquor, rises Temperature is reacted 5 hours under the conditions of lucifuge to after 70 DEG C；Reactant liquor is poured into water and is extracted with dichloromethane, eluant pet is used Ether/dichloromethane (6:1) cross chromatographic column, product ethanol/tetrahydrofuran be recrystallized to give white flaky solid (1.37g, 80%).MS(APCI):M/z (%):686.1[M+]。
Embodiment 3
Bis- bromo- S of 3,8-, the synthesis of S- dioxo-dibenzothiophene diindyls (M-3)
(1) preparation of the bromo- N- of 2- (2- decyl myristyls) carbazole (13)：By 2- bromine carbazoles (9.84g, 40mmol) and hydrogen Sodium oxide (16g, 400mmol) is dissolved in 150mL dimethyl sulfoxide, and heated under nitrogen is slowly added to 2- decyls 14 to 60 DEG C Alkyl bromide (16.68g, 40mmol), reacts 8 hours；Stopped reaction and room temperature is cooled to, reactant liquor is poured into water and uses dichloro Methane is extracted, and with column chromatography purification, with 200～300 mesh silica gel as fixing phase, petroleum ether is eluant, obtains colourless liquid (16.30g, 70%).MS(APCI):M/z (%):583.6[M+]。
(2) preparation of 2- borates-N- (2- decyl myristyls) carbazole (14)：By 2- bromo- N- (the 2- decyl tetradecanes Base) carbazole (10.82g, 18.6mmol) is dissolved in 150mL anhydrous tetrahydro furans；Under argon protection, when -78 DEG C, Deca concentration is The hexane solution (13.4mL, 33.5mmol) of 2.5M n-BuLis, reacts 1 hour at -78 DEG C；2- is rapidly joined subsequently different 40 points of insulation reaction is continued in propoxyl group -4,4,5,5- tetramethyl -1,3,2- ethylenedioxy borates (11.2mL, 27.9mmol) Clock；Reactant liquor is gradually increased to into room temperature reaction 12 hours；Reaction terminate after reactant liquor is poured into water, with dichloromethane extraction, Brine It, anhydrous magnesium sulfate are dried.Solvent is boiled off, with petroleum ether/dichloromethane (6:1) make the purification of eluant column chromatography, Colourless oil liquid (7.02g, 60%).MS(APCI):M/z (%):630.7[M+]。
(3) preparation of 2- (the bromo- 2- second sulfenyl phenyl of 4-)-N- (2- decyl myristyls) carbazole (15)：25mL is dense Spend the wet chemical for 2M, 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases)-N- (the 2- decyl tetradecanes Base) carbazole (6.30g, 10mmol) and the iodo- second iodosobenzenes (3.23g, 9mmol) of the bromo- 2- of 5- are added in reaction bulb, and add 100mL toluene, logical nitrogen, addition four (triphenylphosphine palladium) (0.32g, 0.27mmol) and tetra-n-butyl ammonium bromide (0.18g, 0.54mmol), react 36 hours at 70 DEG C；Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane；By organic layer Chromatographic column is crossed with 200～300 mesh silica gel after being spin-dried for, the polarity of eluant is petroleum ether/dichloromethane (6:1), finally give Faint yellow glutinous thick liquid (4.63g, 70%).1H NMR(500MHz,CDCl3)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 the bromo- dibenzothiophenes diindyls (16) of 3-：By 2- (the bromo- 2- second sulfenyl phenyl of 4-)-N- (the 2- last of the ten Heavenly stems Base myristyl) carbazole (4.41g, 6mmol) and phosphorus pentoxide (17.04g, 120mmol) be added to 20mL fluoroform sulphurs In acid, stir 36 hours under room temperature condition；Reaction after terminating is added drop-wise to reactant liquor in frozen water, and mixed liquor sucking filtration is obtained yellowish The pressed powder of color simultaneously dries；Faint yellow solid powder is dissolved in 100mL pyridines, heated under nitrogen is little to 120 DEG C of backflows 24 When；Stopped reaction is simultaneously cooled to room temperature, extracts and be neutralized with hydrochloric acid pyridine therein；Chromatographic column is crossed with petroleum ether, obtains yellowish Color solid (3.31g, 80%).1H NMR(500MHz,CDCl3)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 the bromo- S of 3-, S- dioxo-dibenzothiophene diindyl (17)：By 3- bromo- dibenzothiophenes diindyl During (2.76g, 4mmol) and 3- chloroperoxybenzoic acids (3.44g, 20mmol) are dissolved in 40mL dichloromethane and in 0 DEG C of ice bath bar React 24 hours under part；30 are stirred in reacting the sodium hydrate aqueous solution for after terminating pour reactant liquor into 30% cold mass concentration Minute；Organic layer washes (150mL × 3) with water, concentrates and cross chromatographic column, and eluant polarity is petroleum ether/dichloromethane (6:1), Obtain faint yellow solid (2.60g, 90%).1H NMR(500MHz,CDCl3)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) bis- bromo- S of 3,8-, the preparation of S- dioxo-dibenzothiophene diindyls (M-3)：Under ice bath, by 3- bromo- S, S- bis- Oxygen-dibenzothiophenes diindyl (1.80g, 2.5mmol) is dissolved in 10mL chloroform and 8mLN, the mixing of dinethylformamide In solution, then N- bromo-succinimides (0.49g, 2.75mmol) are dissolved in into 2mLN, in dinethylformamide after, keep away It is added drop-wise in reactant liquor under optical condition；After 0 DEG C is reacted 1 hour, it is warming up to room temperature and continues stirring 12 hours；Pour reactant liquor into water In and with dichloromethane extract, with eluent petroleum ether/dichloromethane (6:1) chromatographic column, product normal hexane/tetrahydrofuran are crossed Be recrystallized to give white powder solid (1.6g, 80%).1H NMR(500MHz,CDCl3)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+].
Embodiment 4
The synthesis of bis- bromo- S of 3,8-, S- dioxo-dibenzothiophenes benzofuran (M-4)
(1) preparation of 3- borates-dibenzofurans (18):Nitrogen protection under, by 3- bromo- dibenzofurans (19.77g, 80mmol) it is dissolved in 250mL Isosorbide-5-Nitraes-dioxane, sequentially adds connection borate (24.38g, 96mmol), potassium acetate (15.68g, 0.16mmol), [1,1'- double (diphenylphosphino) ferrocene] palladium chloride (2.93g, 4mmol)；It is warming up to 85 DEG C And react 12 hours, reactant liquor is poured into water after terminating by reaction, with dichloromethane extraction, brine It；Solvent is boiled off, is used Column chromatography purification, obtain white solid (16.70g, 71%).MS(APCI):M/z (%):295.1[M+]。
(2) preparation of 3- (the bromo- 2- second sulfenyl phenyl of 4-)-dibenzofurans (19)：By the carbonic acid that 75mL concentration is 2M Aqueous solutions of potassium, 3- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases)-dibenzofurans (8.82g, 30mmol) and The iodo- second iodosobenzenes (10.77g, 30mmol) of the bromo- 2- of 5- are added in reaction bulb, and add 120mL toluene, lead to nitrogen, are added Four (triphenylphosphine palladium) (1.39g, 1.2mmol) and tetra-n-butyl ammonium bromide (0.77g, 2.4mmol), at 65 DEG C, reaction 30 is little When；Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane.With 200～300 mesh silica gel mistakes after organic layer is spin-dried for Chromatographic column, finally give blocks of solid (8.39g, 70%).MS(APCI):M/z (%):400.2[M+]。
(3) preparation of the bromo- dibenzothiophenes of 3- benzofuran (20)：By 3- (the bromo- 2- second sulfenyl phenyl of 4-)-dibenzo furan Mutter (7.98g, 20mmol) and phosphorus pentoxide (42.6g, 300mmol) is added in 50mL trifluoromethayl sulfonic acids, room temperature condition Lower stirring 30 hours；Reaction after terminating is added drop-wise to reactant liquor in frozen water, and the pressed powder that mixed liquor sucking filtration is obtained simultaneously dries； Pressed powder is dissolved in 100mL pyridines, heated under nitrogen flows back 16 hours to 115 DEG C；Stopped reaction is simultaneously cooled to room temperature, extraction Take and be neutralized with hydrochloric acid pyridine therein；Obtain after purification powder solid (4.94g, 70%).MS(APCI):M/z (%): 354.2[M+]。
(4) preparation of the bromo- S of 3-, S- dioxo-dibenzothiophenes benzofuran (21)：By 3- bromo- dibenzothiophenes benzofuran During (3.53g, 10mmol) and 3- chloroperoxybenzoic acids (8.6g, 50mmol) are dissolved in 40mL dichloromethane and in 0 DEG C of ice bath bar React 16 hours under part；30 are stirred in reacting the sodium hydrate aqueous solution for after terminating pour reactant liquor into 20% cold mass concentration Minute；Organic layer washes (150mL × 3) with water, concentrates and cross chromatographic column, and eluant polarity is petrol ether/ethyl acetate (6:1), Obtain powder solid (3.47g, 90%).MS(APCI):M/z (%):386.2[M+]。
(5) preparation of bis- bromo- S of 3,8-, S- dioxo-dibenzothiophenes benzofuran (M-4)：By 3- bromo- S, S- dioxies-hexichol Simultaneously benzofuran (2.32g, 6mmol) is dissolved in 50mL chloroform solns bithiophene, and bromine (0.31mL, 6mmol) is dispersed in 5mL After in chloroform, it is added drop-wise under the conditions of lucifuge in reactant liquor, during Deca, in bottle, temperature is less than 5 DEG C；At 0 DEG C react 7 hours it is complete Finish, bromine is quenched with sodium sulfite, is extracted with dichloromethane and powder solid is obtained by using column chromatography, chlorobenzene recrystallization (1.69g, 61%).MS(APCI):M/z (%):465.1[M+]。
Embodiment 5
Bis- bromo- S of 3,9-, the synthesis of S- dioxo-dibenzothiophenes simultaneously (11- methylene) indenes (M-5)
(1) preparation of the bromo- 9- of 2- (two-first sulfydryl-methylene) fluorenes (22):2- bromine fluorenes (19.61g, 80mmol) is dissolved in In dimethyl sulphoxide solution, potassium tert-butoxide (18.88g, 168.3mmol) is dividedly in some parts at room temperature, Carbon bisulfide is subsequently adding (6.78g, 89.2mmol), after reacting 30 minutes, is slowly added dropwise iodomethane (23.88g, 168.3mmol) in reactant liquor and stirs Mix 12 hours, reactant liquor is poured into water after terminating by reaction, with dichloromethane extraction, brine It；Solvent is boiled off, post layer is used Analysis method purification obtain yellow solid (10.06g, 36%).MS(APCI):M/z (%):350.2[M+]。
(2) preparation of the bromo- 9- of 2- (1- octyl groups-nonyl methylene) fluorenes (23)：Under ice bath, by 2- bromo- 9- (two-first sulfydryls-Asia Methyl) fluorenes (8.75g, 25mmol) and concentration is 0.1M Li2CuCl4Tetrahydrofuran solution (6.9mL, 0.69mmol) add In 100mL tetrahydrofuran solutions, the diethyl ether solution (29.4mL, 58,7mmol) of 2M octyl group magnesium bromides, reaction 4 are then slowly added dropwise After hour, reactant liquor is quenched with 10% sodium hydrate aqueous solution, then is extracted with dichloromethane and pass through column chromatography and purify to obtain Pale yellow oily liquid (6.62g, 55%).MS(APCI):M/z (%):482.5[M+]。
(3) 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -9- (1- octyl groups-nonyl methylene) fluorenes (24) Preparation：Under nitrogen protection, 2- bromo- 9- (1- octyl groups-nonyl methylene) fluorenes (14.48g, 30mmol) is dissolved in into 200mL1,4- bis- In six ring of oxygen, connection borate (9.75g, 36mmol), potassium acetate (6.27g, 64mmol), [1,1'- double (diphenyl are sequentially added Phosphino-) ferrocene] palladium chloride (1.17g, 1.6mmol)；It is warming up to 85 DEG C and reacts 12 hours, reacts reactant liquor after terminating It is poured into water, with dichloromethane extraction, brine It.Solvent is boiled off, with column chromatography purification, pale yellow oily liquid is obtained (10.94g, 69%).MS(APCI):M/z (%):529.6[M+]。
(4) preparation of 2- (the bromo- 2- second sulfenyl phenyl of 4-) -9- (1- octyl groups-nonyl methylene) fluorenes (25)：By 25mL concentration For the wet chemical of 2M, 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -9- (1- octyl groups-nonyl methylene Base) fluorenes (5.29g, 10mmol) and the iodo- second iodosobenzenes (3.59g, 10mmol) of the bromo- 2- of 5- are added in reaction bulb, and add 80mL toluene, logical nitrogen, addition four (triphenylphosphine palladium) (0.58g, 0.5mmol) and tetra-n-butyl ammonium bromide (0.32g, 1mmol), react 24 hours at 60 DEG C；Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane；Organic layer is spin-dried for Chromatographic column is crossed with 100～200 mesh silica gel afterwards, finally give weak yellow liquid (5.13g, 81%).MS(APCI):M/z (%): 634.7[M+]。
(5) preparation of the bromo- dibenzothiophenes of 3- simultaneously (11- methylene) indenes (26)：By 2- (the bromo- 2- second iodosobenzenes of 4- Base) -9- (1- octyl groups-nonyl methylene) fluorenes (5.07g, 8mmol) and phosphorus pentoxide (11.36g, 80mmol) be added to 20mL tri- In fluoromethane sulfonic acid, stir 24 hours under room temperature condition；Reaction after terminating is added drop-wise to reactant liquor in frozen water, by mixed liquor sucking filtration Obtain flaxen pressed powder and dry.Faint yellow solid powder is dissolved in 60mL pyridines, heated under nitrogen is returned to 110 DEG C Stream 12 hours；Stopped reaction is simultaneously cooled to room temperature, extracts and be neutralized with hydrochloric acid pyridine therein；Oily liquids are obtained after purification (3.76g, 79%).MS(APCI):M/z (%):588.7[M+]。
(6) the bromo- S of 3-, the preparation of S- dioxo-dibenzothiophenes simultaneously (11- methylene) indenes (27)：By 3- bromo- dibenzo thiophene Simultaneously (11- methylene) indenes (2.94g, 5mmol) and 3- chloroperoxybenzoic acids (4.3g, 25mmol) are dissolved in 30mL dichloromethane for fen In and under 5 DEG C of condition of ice bath react 10 hours；Reactant liquor is poured into after terminating the hydroxide of 10% cold mass concentration for reaction Stir 30 minutes in sodium water solution；Organic layer washes (150mL × 3) with water, concentrates and crosses column chromatography, obtain powder solid (2.79g, 90%).MS(APCI):M/z (%):620.6[M+]。
(7) bis- bromo- S of 3,9-, the preparation of S- dioxo-dibenzothiophenes simultaneously (11- methylene) indenes (M-5)：By 3- bromo- S, S- Simultaneously (11- methylene) indenes (1.86g, 3mmol) is dissolved in the mixed of 16mL trifluoroacetic acids and 5mL chloroform to dioxo-dibenzothiophene Close in solution, then after N- bromo-succinimides (0.66g, 4.03mmol) are dispersed in 4mL chloroform, lucifuge condition Under be added drop-wise in reactant liquor, after being warming up to 65 DEG C, under the conditions of lucifuge react 8 hours；Reactant liquor is poured into water and dichloromethane is used Alkane extracts and passes through column chromatography purification, obtain powder solid (1.36g, 65%).MS(APCI):M/z (%):699.65[M+]。
Embodiment 6
Bromo- double (S, the S- dioxo-dibenzothiophene) synthesis (M-6) of 3,9- bis-
(1) preparation of 1,4- dioctyls benzene (28):Under nitrogen protection, Isosorbide-5-Nitrae-dibromobenzene (10.62g, 45mmol) is dissolved in In 150mL anhydrous tetrahydro furans, double (diphenylphosphine propane) Nickel Chlorides (0.73g, 1.35mmol) of 1,3- are added, then will 60mL concentration is slowly added dropwise in reactant liquor for the octyl group magnesium bromide diethyl ether solution of 2M, stopped reaction after reacting 12 hours, will be anti- Answer liquid to be poured into water to be extracted with dichloromethane, with column chromatography purification, with 200～300 mesh silica gel as fixing phase, petroleum ether is to wash De- agent, obtain colourless oil liquid (8.86g, 65%).MS(APCI):M/z (%):303.5[M+]。
(2) preparation of bis- bromo- 2,5- dioctyls benzene (29) of 1,4-:Under ice bath, by Isosorbide-5-Nitrae-dioctyl benzene (7.58g, 25mmol) it is dissolved in 100mL chloroform solns, bromine (10g, 62.5mmol) is slowly added dropwise after being diluted with chloroform into anti- In answering liquid, lucifuge is stirred 12 hours；Stopped reaction, reactant liquor is poured into water and is extracted with dichloromethane, with column chromatography purification, With 200～300 mesh silica gel as fixing phase, petroleum ether is eluant, obtain clear crystal (7.48g, 65%).MS(APCI):m/z (%):461.3[M+]。
(3) preparation of 1,4- diborates -2,5- dioctyl benzene (30)：By bis- bromo- 2,5- dioctyls benzene of 1,4- (6.9g, 15mmol) it is dissolved in 100mL anhydrous tetrahydro furans；Argon protection under when -78 DEG C Deca concentration be 2.5M n-BuLis just Hexane solution (11.3mL, 22.5mmol), reacts 1 hour at -78 DEG C；2- isopropoxy -4,4,5,5- are rapidly joined subsequently Insulation reaction is continued 40 minutes in tetramethyl -1,3,2- ethylenedioxy borates (11mL, 27mmol)；Reactant liquor is gradually increased to Room temperature reaction 12 hours；Reactant liquor is poured into water after terminating by reaction, with dichloromethane extraction, brine It, anhydrous slufuric acid Magnesium is dried.Solvent is boiled off, with petroleum ether/dichloromethane (3:1) make eluant column chromatography purification, obtain white solid (4.99g, 60%).MS(APCI):M/z (%):555.4[M+]。
(4) 4,4 '-two bromo- 2,2 "-(double second sulfenyl phenyl) -2 ', the preparation of 5 '-dioctyl benzene (31)：25mL is dense Spend the wet chemical for 2M, Isosorbide-5-Nitrae-two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -2,5- dioctyls Benzene (4.43g, 8mmol) and the iodo- second iodosobenzenes (6.32g, 17.6mmol) of the bromo- 2- of 5- are added in reaction bulb, and are added 100mL toluene, logical nitrogen, addition four (triphenylphosphine palladium) (0.92g, 0.8mmol) and tetra-n-butyl ammonium bromide (0.52g, 1.6mmol), react 24 hours at 60 DEG C；Stopped reaction is simultaneously cooled to room temperature, is extracted 3 times with dichloromethane；Organic layer is revolved Chromatographic column is crossed with 200～300 mesh silica gel after dry, the polarity of eluant is petroleum ether/tetrahydrofuran (6:1), finally give light Yellow solid (3.06g, 50%).MS(APCI):M/z (%):765.8[M+]。
(5) preparation of 3,9- bis- bromo- double (dibenzothiophenes) (32)：By 4,4 '-two bromo- 2,2 "-(double second iodosobenzenes Base) -2 ', 5 '-dioctyl benzene (2.30g, 3mmol) and phosphorus pentoxide (8.52g, 60mmol) are added to 15mL fluoroform sulphurs In acid, stir 24 hours under room temperature condition；Reaction after terminating is added drop-wise to reactant liquor in frozen water, and mixed liquor sucking filtration is obtained yellowish The pressed powder of color simultaneously dries；Faint yellow solid powder is dissolved in 50mL pyridines, heated under nitrogen is little to 120 DEG C of backflows 16 When；Stopped reaction is simultaneously cooled to room temperature, extracts and be neutralized with hydrochloric acid pyridine therein.Chromatographic column is crossed with petroleum ether, obtains yellowish Color solid (1.21g, 60%).MS(APCI):M/z (%):673.6[M+]。
(6) bromo- double (S, S- dioxo-dibenzothiophene) preparations (M-6) of 3,9- bis-：By 3,9- bis- bromo- double (dibenzo thiophenes Fen) (1.01g, 1.5mmol) and 3- chloroperoxybenzoic acids (2.58g, 15mmol) be dissolved in 20mL dichloromethane in and in 5 DEG C of ice React 10 hours under the conditions of bath；Stir in reacting the sodium hydrate aqueous solution for after terminating pour reactant liquor into 10% cold mass concentration Mix 30 minutes；Organic layer washes (150mL × 3) with water, concentrates and cross chromatographic column, and eluant polarity is petroleum ether/tetrahydrofuran (3: 1), obtain faint yellow solid (0.99g, 90%).MS
(APCI):M/z (%):737.6[M+]。
Embodiment 7
Poly- (9,9- di-n-octyl fluorenes-co-3,9-S, S- dioxo-dibenzothiophenes indenes) preparation (P1-P5)
Polymer P 1：By 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (147.9mg, 0.27mmol) and bis- bromo- S of 3,9-, S- bis- Simultaneously indenes (20.6mg, 0.03mmol) is added in 8mL toluene oxygen-dibenzothiophenes, while adding 1mg palladium, tri- hexamethylenes of 2mg Base phosphine and 0.8mL tetraethyl ammonium hydroxides, temperature stabilization are reacted at 80 DEG C 36 hours, add afterwards 25mg phenylboric acids end-blocking and React 12 hours at 80 DEG C, add 0.2mL bromobenzenes and block for second and react at 80 DEG C 12 hours, afterwards reaction is stopped Room temperature is cooled to, in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane) afterwards will polymerization for precipitating Thing toluene dissolved chromatographic column, and precipitating is filtered in methanol again, obtain fibrous polymer (P1) (150mg, 60%).1H NMR(500MHz,CDCl3)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,CH2),1.36-1.02(br,CH2),0.90-0.77(br,CH3).
Polymer P 2：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (131.5mg, 0.24mmol) and bis- bromo- S of 3,9-, S- bis- Oxygen-dibenzothiophenes indenes (41.2mg, 0.06mmol), the same P1 of preparation process；Yield：70%.1H NMR(500MHz,CDCl3) 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,CH2),1.36-0.96(br,CH2),0.90-0.77(br,CH3).
Polymer P 3：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (115.1mg, 0.21mmol) and bis- bromo- S of 3,9-, S- bis- Oxygen-dibenzothiophenes indenes (61.8mg, 0.09mmol), the same P1 of preparation process；Yield：60%.1H NMR(500MHz,CDCl3) 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,CH2),1.34-1.01(br,CH2),0.90-0.75(br,CH3).
Polymer P 4：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (98.6mg, 0.18mmol) and bis- bromo- S of 3,9-, S- bis- Oxygen-dibenzothiophenes indenes (82.4mg, 0.12mmol), the same P1 of preparation process；Yield：75%.1H NMR(500MHz,CDCl3) 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,CH2),1.32-1.01(br,CH2),0.91-0.76(br,CH3).
Polymer P 5：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes Bis- bromo- S of (192.6mg, 0.3mmol) and 3,9-, S- dioxo-dibenzothiophenes indenes (206.1mg, 0.3mmol), preparation process Same P1；Obtain fibrous polymer (P5) (200mg, 72%)；Mn:147.9kDa,PDI:2.33。
Embodiment 8
Poly- (3,9-S, S- dioxo-dibenzothiophene indenes) preparation (P6)
By bis- bromo- S of 3,9- in nitrogen glove box, simultaneously indenes (412.2mg, 0.6mmol) is added S- dioxo-dibenzothiophenes To in 30mL tetrahydrofurans, while adding double (1, the 5- cyclo-octadiene) nickel of 1g, 1,5- cyclo-octadiene 0.5g and bipyridyl 0.8g, temperature Degree is stable to react at 80 DEG C 4 days, adds 0.5mL bromobenzenes end-blocking afterwards and reacts at 80 DEG C 20 hours, stops reaction afterwards Room temperature is cooled to, in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane) afterwards will polymerization for precipitating Thing chloroform dissolved chromatographic column, and precipitating is filtered in methanol again, obtained powder solid, yield：40%.Mn:3.8kDa, PDI:2.12。
Embodiment 9
Poly- (N-9 '-heptadecyl carbazole-co-3,9-S, S- dioxo-dibenzothiophenes indenes) preparation (P7-P10)
Polymer P 7：By 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.1mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (152.0mg, 0.27mmol) and 3,9- bis- bromo- S, S- Simultaneously indenes (20.6mg, 0.03mmol) is added in 8mL toluene dioxo-dibenzothiophene, while adding 1mg palladium, tri- rings of 2mg Hexyl phosphine and 0.8mL tetraethyl ammonium hydroxides, temperature stabilization are reacted at 80 DEG C 36 hours, add 25mg phenylboric acids to block simultaneously afterwards React 12 hours at 80 DEG C, add 0.2mL bromobenzenes and block for second and react 12 hours at 80 DEG C, afterwards reaction is stopped Room temperature is cooled to only, in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane) afterwards will be poly- for precipitating Compound toluene dissolved chromatographic column, and precipitating is filtered in methanol again, obtained fibrous polymer (P7), yield：67%. Mn:47.7kDa,PDI:1.80.
Polymer P 8：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.1mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (135.1mg, 0.24mmol) and 3,9- bis- bromo- S, S- Dioxo-dibenzothiophene indenes (41.2mg, 0.06mmol), the same P7 of preparation process；Yield：65%.Mn:62.9kDa,PDI: 1.87.
Polymer P 9：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.1mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (118.2mg, 0.21mmol) and 3,9- bis- bromo- S, S- Dioxo-dibenzothiophene indenes (61.8mg, 0.09mmol), the same P7 of preparation process；Yield：70%.Mn:316.1kDa,PDI: 2.40.
Polymer P 10：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.1mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (101.3mg, 0.18mmol) and 3,9- bis- bromo- S, S- Dioxo-dibenzothiophene indenes (82.4mg, 0.12mmol), the same P7 of preparation process；Yield：69%.Mn:147.7kDa,PDI: 2.18.
Polymer P 11：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.1mg, 0.3mmol), 3,9- bis- bromo- S, S- dioxo-dibenzothiophenes indenes (206.1mg, 0.3mmol), obtain fiber Shaped polymer (P11), the same P7 of preparation process；Yield：66%.Mn:58.8kDa,PDI:1.91。
Embodiment 10
Poly- (9,9- di-n-octyl fluorenes-co-3,8-S, S- dioxo-dibenzothiophene diindyls) preparation (P12)
By 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7-, bis- bromo- 9,9- di-n-octyls fluorenes (131.5mg, 0.24mmol) and bis- bromo- S of 3,8-, S- dioxies-dibenzo Thiophene diindyl (48.0mg, 0.06mmol) is added in 8mL toluene, at the same add 1mg palladium, 2mg tricyclohexyl phosphines and 0.8mL tetraethyl ammonium hydroxides, temperature stabilization are reacted at 80 DEG C 36 hours, add 25mg phenylboric acids end-blocking afterwards and at 80 DEG C Reaction 12 hours, adds 0.2mL bromobenzenes and blocks for second and react at 80 DEG C 12 hours, be cooled to reaction stopping afterwards Room temperature, precipitating in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane), afterwards by polymer first Benzene dissolved chromatographic column, and precipitating is filtered in methanol again, obtained fibrous polymer (P12), yield：62%.Mn: 46.8kDa,PDI:1.89。
Embodiment 11
Poly- [9,9- di-n-octyl fluorenes-co-3,9- is double (S, S- dioxo-dibenzothiophene)] preparation (P13)
By 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7-, bis- bromo- 9,9- di-n-octyls fluorenes (131.5mg, 0.24mmol) and bis- bromo- S of 3,8-, S- dioxies-dibenzo Thiophene diindyl (44.2mg, 0.06mmol) is added in 8mL toluene, at the same add 1mg palladium, 2mg tricyclohexyl phosphines and 0.8mL tetraethyl ammonium hydroxides, temperature stabilization are reacted at 80 DEG C 36 hours, add 25mg phenylboric acids end-blocking afterwards and at 80 DEG C Reaction 12 hours, adds 0.2mL bromobenzenes and blocks for second and react at 80 DEG C 12 hours, be cooled to reaction stopping afterwards Room temperature, precipitating in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane), afterwards by polymer first Benzene dissolved chromatographic column, and precipitating is filtered in methanol again, obtained fibrous polymer (P13), yield：64%.Mn: 67.3kDa,PDI:1.99。
Embodiment 12
Poly- (3,8-S, S- dioxo-dibenzothiophene diindyl) preparation (P14)
By bis- bromo- S of 3,9- in nitrogen glove box, simultaneously indenes (412.2mg, 0.6mmol) is added S- dioxo-dibenzothiophenes To in 30mL tetrahydrofurans, while double (1, the 5- cyclo-octadiene) nickel of 1.0g are added, 1,5- cyclo-octadiene 0.5g and bipyridyl 0.8g, Temperature stabilization is reacted at 80 DEG C 4 days, is added 0.5mL bromobenzenes end-blocking afterwards and is reacted 20 hours at 80 DEG C, stops reaction afterwards Room temperature is cooled to only, in methanol, surname extraction after filtration (successively with methanol, acetone and normal hexane) afterwards will be poly- for precipitating Compound chloroform dissolved chromatographic column, and precipitating is filtered in methanol again, obtained fibrous polymer (P14), yield：33%. Mn:3.0kDa,PDI:2.7。
Embodiment 13
Poly- [bis- n-octyloxy benzene-alt-3,9- of 2,5- are double (S, S- dioxo-dibenzothiophene)] preparation (P15)
By 1,4- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) two n-octyloxy benzene of -2,5- (175.8mg, 0.3mmol) He 3,9- bis- bromo- double (S, S- dioxo-dibenzothiophene) (220.9mg, 0.3mmol) is added in 10mL toluene, 1mg palladium, 2mg tricyclohexyl phosphines and 0.8mL tetraethyl ammonium hydroxides are added simultaneously, and temperature stabilization is little in 80 DEG C of reactions 36 When, 25mg phenylboric acids end-blocking is added afterwards and is reacted 12 hours at 80 DEG C, add 0.2mL bromobenzenes and block for second and 80 React at DEG C 12 hours, reaction stopping is cooled to into room temperature afterwards, precipitating in methanol, (successively use after filtration by surname extraction Methanol, acetone and normal hexane), polymer toluene was dissolved into chromatographic column afterwards, precipitating is filtered in methanol again, obtains fibre Dimension shaped polymer (P15), yield：53%.Mn:19.1kDa,PDI:2.21。
Embodiment 14
The preparation of polymer electroluminescent device
On tin indium oxide (ITO) glass of well in advance, its square resistance is 15 Ω, first successively with acetone, detergent, Deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；The poly- second for having polystyrolsulfon acid is mixed in the spin coating on ITO Epoxide thiophene (PEDOT:PSS) film, thickness are 150nm；PEDOT:PSS films are dried 8 hours at 80 DEG C in vacuum drying oven；Subsequently The xylene solution (1wt.%) of polymer is spin-coated on into PEDOT:The surface of PSS films, thickness are 80nm；Finally on luminescent layer The thick metal Al layers of one layer of 1.5nm thick CsF and 120nm are deposited with successively.
The structure of the electroluminescent device for obtaining is：ITO/PEDOT:PSS/ polymer/CsF/Al.
Polymer P 1, P2, P3 thin film uv-visible absorption spectra as shown in figure 1, as shown in Figure 1, polymer P 1, P2 With the absorption peak of P3 near equal 395nm, the transition absorption of molecular backbone π-π * is absorbed as herein.
The thin film photoluminescence spectra of polymer P 1, P2 and P3 as shown in Fig. 2 as shown in Figure 2, polymer P 1, P2 and P3 Transmitting increase no obvious red shift and widthization with five yuan of sulfuryl condensed hetero ring unit contents.
Polymer P 1, the voltage-current density-brightness curve of P2 and P3 thin film are as shown in figure 3, from the figure 3, it may be seen that polymer P1, P2 and P3 have it is relatively low open bright voltage and higher brightness, illustrate material filming preferably, energy level is relative to be matched, and has Good fluorescent characteristic.
The device EL curves of spectrum of polymer P 1, P2 and P3 as shown in figure 4, as shown in Figure 4, send out by polymer P 1, P2, P3's Penetrate and increase no obvious red shift and widthization with five yuan of sulfuryl condensed hetero ring unit contents.
The performance of electroluminescent device prepared by polymer is as shown in table 1.
1 polymer device luminescent properties of table
As shown in Table 1, the polymer for containing five yuan of sulfuryl condensed hetero ring units has and relatively low opens bright voltage, higher electricity Stream efficiency and brightness and comparatively ideal chromaticity coordinates, illustrate that material has the energy level of preferable film property and relative matching, with very Good fluorescent characteristic.

Claims (10)

1. five yuan of sulfuryl condensed hetero ring monomers, it is characterised in that with following chemical structural formula：
In formula：X is Br or I atoms；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 SO2；R1、R2, R be independently expressed as H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxyl, carbonyl Base, sulfuryl, the alkyl of carbon number 1～30, the cycloalkyl of carbon number 3～30, the aromatic hydrocarbyl that carbon number is 6～60 Or the aromatic heterocycle that carbon number is 3～60.
2. the method for preparing five yuan of sulfuryl condensed hetero ring monomers described in claim 1, it is characterised in that comprise the steps：
(1), under nitrogen protection, halo -2- fluoro- iodobenzene is dissolved in DMF, potassium carbonate and ethyl mercaptan is added, Reaction obtains the iodo- second sulfydryl benzene of halo -2-；
(2) solvent is made with acetic acid, under ice bath, with the iodo- second sulfydryl benzene of hydrogen peroxide oxidation halo -2-, obtains the iodo- second of halo -2- sub- Sulphonyl benzene；
(3) under inert gas shielding, the iodo- second iodosobenzenes of halo -2- and 0.9～1.1 times of molar equivalent are well prepared in advance Heteroaromatic boron ester containing substituent group carries out coupling reaction, obtains the halo-second iodosobenzene derivant of non-cyclization；
(4) and then under trifluoromethanesulfonic acid environment, after phosphorus pentoxide reaction is added under room temperature, it is slowly added in frozen water, sucking filtration, During the solid that obtains adds pyridine, refluxed under nitrogen, with dilute hydrochloric acid solution and pyridine after cooling, obtains the condensed hetero ring after cyclization Compound；
(5) solvent is made with dichloromethane, adds metachloroperbenzoic acid to aoxidize 10～24 hours at 0～5 DEG C, after reaction terminates, With the metachloroperbenzoic acid in the sodium hydrate aqueous solution of 10～30% cold mass concentrations with excess, the list containing sulfuryl is obtained Halo fused heterocyclic compound；
(6) the monohaloalkyl fused heterocyclic compound containing sulfuryl is dissolved in into trifluoroacetic acid-chloroform or N,N-dimethylformamide-three In the mixed solution of chloromethanes, under the conditions of lucifuge, Deca concentration is the trichlorine of the N- bromo-succinimides of 1～1.5mol/L The chloroform soln of dichloromethane or bromine, reaction, obtains the monomer of five yuan of sulfuryls condensed hetero ring unit.
3. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that in step (1), institute The fluoro- iodobenzenes of halo -2- are stated for the fluoro- iodobenzenes of bromo -2- or the fluoro- iodobenzenes of iodo -2-；The potassium carbonate and ethyl mercaptan and halo -2- The mol 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.
4. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that in step (2), institute Ice bath temperature is stated for 0～5 DEG C；The hydrogen peroxide concentration is 30～50wt%；The time of the oxidation is 8～12h.
5. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that in step (3), institute It is 24～36h of reaction at 60～70 DEG C to state coupling reaction, and reaction four (triphenylphosphine palladiums) of addition and tetra-n-butyl ammonium bromide are made Catalyst；Four (triphenylphosphine palladiums) and tetra-n-butyl ammonium bromide are respectively 1 with the mol ratio of the fluoro- iodobenzenes of halo -2-:20～ 34 and 1:10～17；The noble gases include argon or nitrogen.
6. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that in step (4), institute The mol ratio that phosphorus pentoxide is stated with halo-second iodosobenzene derivant is 10～20：1；The time of the reaction is 24～36 Hour；The backflow is flowed back 12～24 hours at 110～120 DEG C.
7. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that in step (6), institute The mol ratio that N- bromo-succinimides and bromine are stated with the monohaloalkyl fused heterocyclic compound containing sulfuryl is respectively 1:1～1.3 He 1:1～1.2；During the chloroform soln of the chloroform soln or bromine of Deca N- bromo-succinimide, temperature is below 5 ℃；The reaction is reacted 5～8 hours at 60～70 DEG C.
8. it is according to claim 2 prepare five yuan of sulfuryl condensed hetero ring monomers method, it is characterised in that omit step (6), Five yuan of sulfuryl condensed hetero ring monomers that Y is sulfuryl are prepared directly by step (1)～(5).
9. the polymer containing five yuan of sulfuryl condensed hetero ring units based on five yuan of sulfuryl condensed hetero ring monomers described in claim 1, which is special Levy and be, with following chemical structural formula：
In formula：The molar fraction of x, y for unit component, meets:0<X≤1, x+y=1, n=1～300；R1、R2Independently table It is shown as H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxyl, carbonyl, sulfuryl, the alkane of carbon number 1～30 Base, the cycloalkyl of carbon number 3～30, the aromatic hydrocarbyl that carbon number is 6～60 or the aromatic series that carbon number is 3～60 Heterocyclic radical；
Ar is the compound or derivant of following structure：
2,7- substituted fluorenes；
3,6- substituted fluorenes；
2,7- replaces spiro fluorene；
2,7- replaces silicon fluorene；
2,7- replaces germanium fluorenes；
2,7- substituted carbazoles；
3,6- substituted carbazoles；
3,9- substituted indole carbazoles；
2,8- substituted indole carbazoles；
3,9- substituted indene fluorenes；
2,8- substituted indene fluorenes；
1,4- substituted benzenes；
4,7- replaces 2,1,3- diazosulfides；
4,7- replaces -2,1,3- selenoles；
4,7- bis- (4- substituted-phenyls) -2,1,3- diazosulfides；
4,7- bis- (4- substituted-phenyls) -2,1,3- selenoles；
4,7- bis- (5- replaces -4- alkylthrophene -2- bases) -2,1,3- diazosulfides；
4,7- bis- (5- replaces -4- alkylthrophene -2- bases) -2,1,3- selenoles；
4,7- bis- (N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amido) -2,1,3- diazosulfides；
4,7- bis- (N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amido) -2,1,3- selenoles；
4,7- bis- (4- (N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amido) phenyl) -2,1,3- diazosulfides；
4,7- bis- (4- (N- (4- substituted-phenyls)-N- (4- alkyl phenyls) amido) phenyl) -2,1,3- selenoles；
Wherein, Z1、Z2、R3Independently be expressed as H, D, F, CN, thiazolinyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxyl, Carbonyl, sulfuryl, the alkyl of carbon number 1～30, the cycloalkyl of carbon number 3～30, the aromatic hydrocarbon that carbon number is 6～60 Base or carbon number are 3～60 aromatic heterocycle.
10. the polymer containing five yuan of sulfuryl condensed hetero ring units described in claim 9 is in organic electroluminescent, organic solar electricity Apply in pond and organic field effect tube.
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