CN105061463A - Nine-membered fused ring derivatives as well as synthesis method and application thereof - Google Patents

Nine-membered fused ring derivatives as well as synthesis method and application thereof Download PDF

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CN105061463A
CN105061463A CN201510504626.0A CN201510504626A CN105061463A CN 105061463 A CN105061463 A CN 105061463A CN 201510504626 A CN201510504626 A CN 201510504626A CN 105061463 A CN105061463 A CN 105061463A
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yuan
fused
ring derivatives
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field effect
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CN105061463B (en
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张斌
杨勇
杨伟
曹镛
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South China University of Technology SCUT
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract

The invention relates to nine-membered fused ring derivatives as well as a synthesis method and application thereof. According to the synthesis method, five-membered ring units are coupled with phenyl sulfoxide units for ring-fused reactions, so that aromatic compounds adopting the nine-membered macrocyclic structures are obtained. The nine-membered fused ring derivatives are high in thermal stability and hole mobility, and can serve as active layers applied to organic field-effect transistors, so that the organic field-effect transistors with high performance and stability are obtained.

Description

One class nine yuan fused-ring derivatives and synthetic method thereof and application
Technical field
The invention belongs to organic photoelectric technical field, be specifically related to a class nine yuan of fused-ring derivatives and synthetic method thereof and application.
Background technology
The report of organic field effect tube can trace back to the eighties in last century the earliest, and the people such as Ando in 1986 have synthesized the p-N-type semiconductorN material based on Polythiophene unit by electrochemical method, but at that time, the hole mobility of material only has 10 -5cm 2v -1s -1, current on/off ratio also only has 100 (Appl.Phys.Lett., 1986,49 (18), 1210-1212).Pentacene is micromolecular finally occurs that the development of OFET material has been had to be leaped significantly, and the people such as Jackson prepared the regular pentacene small molecules OFET device of packing structure in 1997, obtain up to 1.5cm 2v -1s -1hole mobility and 10 8switch current ratio (IEEEElectr.DeviceL., 1997,18 (12), 606-608).But after this more the report of the OFET material of high mobility is more rare, and the report of OFET material in threshold voltage and stability is more rarely seen, therefore in raising mobility, reduce threshold voltage, the stability aspect increasing device also has very large excavation space.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, synthesized the small molecule organic semiconductor material of the large conjugate planes having nonatomic ring structure, this type of material has higher mobility, is applicable in organic field effect tube.
The object of the present invention is to provide a kind of nine yuan of condensed ring analog derivative structure small molecules of high mobility.
Nine yuan of fused-ring derivatives of the present invention are obtained by ring-closure reaction and oxidizing reaction.
A class of the present invention nine yuan of fused-ring derivatives, chemical structural formula is as follows:
Wherein nine yuan of condensed ring form large conjugate planes structure
R 1for C 1~ C 30straight chain or branched-chain alkyl;
R 2for H, C 1~ C 30straight chain or branched-chain alkyl, OC 1~ OC 30straight chain or branched-chain alkyl;
R 3, R 4, R 5, R 6identical or different, be H, C 1~ C 30straight chain or branched-chain alkyl, OC 1~ OC 30straight chain or
Person's branched-chain alkyl, F, CF 3or (wherein R 7for H, C 1~ C 30straight chain or branched-chain alkyl, OC 1~ OC 30straight chain or branched-chain alkyl, F or CF 3);
X, Y comprise following combination: X=S, Y=O; Or X=S, Y be not containing any element;
Z=O, S, Se, N, P, C, Si, Ge or Sn.
A described class nine yuan of fused-ring derivatives, synthetic route is as follows:
Wherein compound 4 and compound 5 are described nine yuan of fused-ring derivatives;
The synthesis step of a described class nine yuan of fused-ring derivatives is as follows:
(1) 1 molar equivalent alkylating 3,9-dibromo five yuan of fused ring compounds are dissolved in dioxane, the Potassium ethanoate of the two tetramethyl ethylene ketone boric acid ester of 2 ~ 5 molar equivalents and 5 ~ 10 molar equivalents is added in inert gas environment, stir, 1 of 0.01-0.055 molar equivalent is added during raised temperature to 50 ~ 120 DEG C, the two Diphenyl phosphino ferrocene palladium chloride reaction of 1'-5 ~ 24 hours, reaction terminates rear cool to room temperature and suction filtration, and filtrate obtains product 2 after column chromatography is purified;
(2) 1 molar equivalent product 2 is dissolved in toluene, add 2-bromine (methanesulfinyl) benzene of 2 ~ 4 molar equivalents, the Tetrabutyl amonium bromide of 0.05 ~ 0.2 molar equivalent and the tetrakis triphenylphosphine palladium of 0.02-0.1 molar equivalent, heating reflux reaction 2 ~ 24 hours, after reaction terminates, cool to room temperature, extraction, drying, column chromatography is purified and is obtained product 3;
(3) 1 molar equivalent product 3 is joined in trifluoromethanesulfonic acid or trifluoroacetic acid, add the Vanadium Pentoxide in FLAKES of 1.5-4.0 molar equivalent simultaneously, room temperature reaction 5 ~ 24 hours under air tight condition, after reaction terminates reaction solution to be added drop-wise in water and suction filtration, after filter residue dries in pyridine reflux 2 ~ 12 hours, reaction terminates rear extraction, column chromatography is purified, recrystallization, obtains product 4;
(4) 1 molar equivalent product 4 is dissolved in methylene dichloride, add the 3-chloroperoxybenzoic acid of 4 ~ 30 molar equivalents, react 5 ~ 10 hours under ice bath, reaction terminates rear soda lye wash, extraction, drying, column chromatography purification, recrystallization, obtain nine yuan of fused-ring derivatives small molecules products 5.
Such nine yuan of fused-ring derivatives have high with stable hole mobility, and its mobility is per second between 0.1 ~ 5.0 centimeters per volt.Can as the application of active coating in organic field effect tube device; The thickness of the active coating of organic field effect tube device is 20-1000 nanometer; The active coating of described organic field effect tube device is realized by solution processing method, comprises spin coating, brushing, spraying, dip-coating, roller coat, silk screen printing, printing or inkjet printing methods; Wherein solvent for use is organic solvent; The preparation of the active coating of described organic field effect tube device carries out in atmosphere.
Compared with prior art, the advantage that has of the present invention and technique effect as follows:
Provide a kind of synthetic method of large condensed ring class aromatic compound; Due to and the introducing of ring, increase rigidity and the planarity of molecule, the conjugacy of molecule is increased, thus the thermostability that not only can improve material also can improve material conduction hole ability.At present; most organic field effect tube materials is all prepare in the glove box of protection of inert gas and obtain; but the large condensed ring class aromatic compound synthesized by the present invention can be prepared the active coating of organic field effect tube device in atmosphere, and show good hole migration performance and stability.By enforcement of the present invention, for the organic effect tube material of futuristic design and synthesis high mobility, low cost and high stability provides certain guidance basis.
Accompanying drawing explanation
Fig. 1 is compound 4 differential scanning calorimetric curve figure.
Fig. 2 is compound 4 thermal gravimetric analysis curve figure.
Fig. 3 is compound 4 solution absorption spectra figure.
Fig. 4 is the abosrption spectrogram of compound 4 film.
Fig. 5 is compound 4 solution utilizing emitted light spectrogram.
Fig. 6 is compound 4 film utilizing emitted light spectrogram.
Fig. 7 is compound 4 Cyclic voltamogram graphic representation.
Fig. 8 is compound 4 transfer characteristic curve figure.
Embodiment
Be described each constituent monomers proposed by the invention below in conjunction with embodiment, the present invention is not limited to this example.
The synthesis of bromo-5, the 11-double hexadecyl indole carbazoles (1) of embodiment 13,9-bis-
By 3,9-dibromo indole carbazole (1.0g, 2.4mmol) be dissolved in and fill in the 250mL there-necked flask of 40mL dimethyl sulfoxide (DMSO), add potassium hydroxide solution (1.4mL) and Tetrabutyl amonium bromide (77mg that massfraction is 50% simultaneously, 0.24mmol), hexadecyl bromine (2.2g, 7.2mmol) is added after stirring 30min in nitrogen atmosphere.Reaction is warmed up to 65 DEG C and reacts 4h.Afterwards reaction cool to room temperature is poured in 300mL methyl alcohol and stirs.Suction filtration also uses DMF, methyl alcohol and washing with acetone 1-3 time, finally obtains pale yellow powder shape solid 1.5g, productive rate 72%.
The synthesis of two (4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-base)-5, the 11-double hexadecyl indole carbazoles (2) of embodiment 23,9-
By 3,9-bis-bromo-5,11-double hexadecyl indole carbazole (1.0g, 1.1mmol), Potassium ethanoate (1.08g, 11mmol) and two tetramethyl ethylene ketone boric acid ester (0.9g, 3.5mmol) to be dissolved in 100mL tri-mouthfuls of round-bottomed flasks that 50mL dioxane is housed and to stir in nitrogen atmosphere.Temperature adds the two Diphenyl phosphino ferrocene palladium chloride (40mg, 0.055mmol) of 1,1'-fast when rising to 80 DEG C.React cool to room temperature after carrying out 24h and suction filtration.Filtrate head product silica gel/methylene dichloride column chromatography obtains yellow needle-like crystals 0.7g, productive rate 63%.
The synthesis of embodiment 33,9-bis-(2-methylsulfinyl phenyl)-5,11-double hexadecyl indole carbazole (3)
By the K of 10mL2M 2cO 3solution, 3,9-two (4; 4; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-base)-5; 11-double hexadecyl indole carbazole (2.0g, 2.1mmol) and 2-bromine (methanesulfinyl) benzene (1.42g, 6.5mmol) are dissolved in 100mL toluene solution; add tetrakis triphenylphosphine palladium (100mg) and Tetrabutyl amonium bromide (60mg), reaction reflux 24h simultaneously.Afterwards reaction cool to room temperature is used dichloromethane extraction.Organic phase is dry, underpressure distillation with silica gel, and ethyl acetate/petroleum ether (volume ratio is 1:2) carries out column chromatography for moving phase, obtains clear yellow viscous oily liquid (1.25g, 61%).
Embodiment 45,11-double hexadecyl two [2-b, 3; 8-b, 9] synthesis of benzo [d] thiophene indole [3,2-b] carbazole (4)
3,9-bis-(2-methylsulfinyl phenyl)-5,11-double hexadecyl indole carbazoles (2.1g, 2.2mmol) join 15mL trifluoromethanesulfonic acid, and add 1.0g Vanadium Pentoxide in FLAKES.Reaction stirred at ambient temperature 24h, is slowly added drop-wise to reaction solution in frozen water afterwards, suction filtration dry filter residue obtains pale yellow powder solid.Pale yellow powder is dissolved in 100mL pyridine, reflux 12h demethylation in nitrogen atmosphere.Cool to room temperature will be reacted afterwards, neutralize with hydrochloric acid and use dichloromethane extraction, crude product purified by silica gel, sherwood oil/methylene dichloride (volume ratio is 2:1) carries out chromatography column for moving phase, yellow powdery solid (0.8g, 40%) is obtained again by re-crystallizing in ethyl acetate.Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8 are respectively differential scanning calorimetric curve figure, the thermal gravimetric analysis curve figure of compound 4, solution absorption spectra figure, the abosrption spectrogram of film, solution utilizing emitted light spectrogram, film utilizing emitted light spectrogram, Cyclic voltamogram graphic representation and transfer characteristic curve figure.Can be learnt by test, compound 4 has higher thermostability, and heat decomposition temperature is close to 400 degrees Celsius; Optical property shows that compound 4 is for comparing broad-band gap macromole, and if be polar compound, there is more weak solvent polarizing effect in polar solvent; The minimum non-occupied orbital energy level of electrochemical Characterization surface compound 4 is close to-5.0 electron-volts; Characterized by organic field effect tube, the hole mobility of compound is per second more than 0.1 centimeters per volt.
Embodiment 55,11-double hexadecyl two [2-b, 3; 8-b, 9] synthesis of benzo [d]-S, S-dioxy thiophene indoles [3,2-b] carbazole (5)
By 5,11-double hexadecyl two [2-b, 3; 8-b, 9] benzo [d] thiophene indole [3,2-b] carbazole (156mg, 0.17mmol) and 3-chloroperoxybenzoic acid (570mg, 3.3mmol) to be dissolved in 10mL methylene dichloride and to stir 10h under condition of ice bath.Afterwards reaction solution is poured in the aqueous sodium hydroxide solution of 10% cold mass concentration and stir 30min, extraction, drying.Organic layers with water is washed (150mL × 3), concentrates and crosses chromatography column, and eluent polarity is methylene dichloride/tetrahydrofuran (THF) (volume ratio is 10:1), obtains pale yellow powder (117mg, 70%) afterwards with ethyl alcohol recrystallization.
Embodiment 66, the synthesis of 6 ', 12,12 '-four octyl group indenofluorene (6)
By indenofluorene (254mg, 1.0mmol) join in 150mL tri-mouthfuls of flasks, and add the dissolving of 60mL anhydrous tetrahydro furan, now the temperature of reaction solution is dropped to-78 DEG C, slowly drip 2.4Mn-BuLi (4.2mL, 10mmol) after temperature-stable, be incubated 2h afterwards, the disposable 1-of adding bromooctane (2.9g, 15mmol) and reaction spend the night.Stopped reaction, concentrate reaction solution, washes with water 2-3 time afterwards with dichloromethane extraction, cross chromatography column, eluent polarity is sherwood oil/methylene dichloride (volume ratio is 5:1), obtains white solid (390mg afterwards with ethyl alcohol recrystallization, 0.56mmol), productive rate 56%.
Embodiment 72,8-bis-bromo-6, the synthesis of 6 ', 12,12 '-four octyl group indenofluorene (7)
Cupric bromide (10g, 44.8mmol) is diluted in 100mL water, and emerging alumina powder (20g) in adding, by moisture underpressure distillation after stirring, finally can brown ceramic powder be obtained for subsequent use.By 6,6 ', 12,12 '-four octyl group indenofluorene (0.7g, 1mmol) is dissolved in 30mL carbon tetrachloride solution, and adds the brown ceramic powder 3g prepared, reflux 10h.Stopped reaction cool to room temperature afterwards, reaction solution suction filtration use carbon tetrachloride extraction filtrate, and mistake chromatography column, eluent polarity sherwood oil/methylene dichloride (volume ratio is 6:1), finally obtains white powder (516mg, 60%).
The synthesis of embodiment 82,8-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-base)-6,6 ', 12,12 '-four octyl group indenofluorene (8)
By 2,8-bis-bromo-6,6 ', 12,12 '-four octyl group indenofluorene (0.86g, 1.0mmol), Potassium ethanoate (0.93g, 10mmol) and two tetramethyl ethylene ketone boric acid ester (0.9g, 3.5mmol) to be dissolved in 100mL tri-mouthfuls of round-bottomed flasks that 50mL dioxane is housed and to stir in nitrogen atmosphere.Temperature adds the two Diphenyl phosphino ferrocene palladium chloride (40mg, 0.055mmol) of 1,1'-fast when rising to 80 DEG C.React cool to room temperature after carrying out 24h and suction filtration.Filtrate head product silica gel/methylene dichloride column chromatography, obtains white solid (477mg, 50%) by recrystallizing methanol afterwards.
The synthesis of embodiment 92,8-bis-(2-methylsulfinyl phenyl)-6,6 ', 12,12 '-four octyl group indenofluorene (9)
By the K of 10mL2M 2cO 3solution, 2,8-bis-(4; 4,5,5-tetramethyl--1; 3,2-dioxy boron penta ring-2-base)-6,6 '; 12; 12 '-four octyl group indenofluorene (0.96g, 1.0mmol) and 2-bromine (methanesulfinyl) benzene (660mg, 3.0mmol) are dissolved in 100mL toluene solution; add tetrakis triphenylphosphine palladium (70mg) and Tetrabutyl amonium bromide (40mg), reaction reflux 24h simultaneously.Afterwards reaction cool to room temperature is used dichloromethane extraction.Organic phase is dry, and underpressure distillation also uses silica gel, and ethyl acetate/petroleum ether (volume ratio is 1:2) is carried out column chromatography for moving phase and obtained yellow solid (0.6g, 61%).
Embodiment 106,6 ', 12,12 '-four octyl group two [2,3-b; 8,9-b] synthesis of benzo [d] thiophene indenofluorene (10)
2,8-bis-(2-methylsulfinyl phenyl)-6,6 ', 12,12 '-four octyl group indenofluorene (0.98g, 1.0mmol) joins 5mL trifluoromethanesulfonic acid, and adds 0.5g Vanadium Pentoxide in FLAKES.Reaction stirred at ambient temperature 24h, is slowly added drop-wise to reaction solution in frozen water afterwards, suction filtration dry filter residue obtains pale yellow powder solid.Pale yellow powder is dissolved in 50mL pyridine, reflux 12h demethylation in nitrogen atmosphere.Cool to room temperature will be reacted afterwards, neutralize with hydrochloric acid and use dichloromethane extraction, organic phase crude product crosses chromatography column, eluent polarity sherwood oil/methylene dichloride (volume ratio is 3:1), white powdery solids (0.36g, 40%) is obtained again with ethyl alcohol recrystallization.
Embodiment 116,6 ', 12,12 '-four octyl group two [2,3-b; 8,9-b] synthesis of benzo [d]-S, S-dioxy thiophene indenofluorene (11)
By 6,6 ', 12,12 '-four octyl group two [2,3-b; 8,9-b] benzo [d] thiophene indenofluorene (0.92g, 1.0mmol) and 3-chloroperoxybenzoic acid (3.46g, 20mmol) to be dissolved in 100mL methylene dichloride and to stir 10h under condition of ice bath.Afterwards reaction solution is poured in the aqueous sodium hydroxide solution of 10% cold mass concentration and stir 30min.Organic layers with water is washed (150mL × 3), concentrates and crosses chromatography column, and eluent polarity is methylene dichloride/tetrahydrofuran (THF) (volume ratio is 10:1), obtains pale yellow powder (0.69g, 70%) afterwards with ethyl alcohol recrystallization.
Embodiment 125,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (12)
By 2,2 ", 4 '; 6 '-four bromo-1,1 ': 3 ', 1 " and-ortho-terphenyl (546mg, 1.0mmol) join in 250mL flask, dissolve with anhydrous diethyl ether (300 milliliters), cool to 0 DEG C, slow dropping 2.4Mn-BuLi (4.2mL, 10mmol), insulation 2h, by dimethyldichlorosilane(DMCS) (1.94g, 15mmol) dilute with 10mL normal hexane and join in reaction solution, under room temperature, reacting 12h.Stopped reaction, reaction solution dichloromethane extraction is also washed, and crosses chromatography column with sherwood oil/methylene dichloride (volume ratio is for 1:1) for moving phase, obtains white solid (137mg, 40%).
Embodiment 133,9-bis-bromo-5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (13)
By 5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene coughs up [3,2-f] [1] benzo thiophene coughs up (0.34g, 1.0mmol) and is dissolved in 50mL tetrahydrofuran (THF), slowly drips bromine (0.3mL under condition of ice bath, 5.0mmol), stopped reaction after reaction 8h.Reaction solution is concentrated, washes with dichloromethane extraction, obtain crude product (0.25g, 50%) with ethyl alcohol recrystallization afterwards.
Embodiment 143,9-bis-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-base)-5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (14)
By 3,9-bis-bromo-5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene is coughed up [3,2-f] [1] benzo thiophene and is coughed up (0.5g, 1.0mmol), Potassium ethanoate (0.93g, 10mmol) and two tetramethyl ethylene ketone boric acid ester (1.02g, 4mmol) to be dissolved in 100mL tri-mouthfuls of round-bottomed flasks that 50mL dioxane is housed and to stir in nitrogen atmosphere.Temperature adds the two Diphenyl phosphino ferrocene palladium chloride (40mg, 0.055mmol) of 1,1'-fast when rising to 80 DEG C.React cool to room temperature after carrying out 24h and suction filtration.Filtrate head product silica gel/methylene dichloride column chromatography, obtains faint yellow solid (226mg, 38%) by recrystallizing methanol afterwards.
Embodiment 153,9-bis-(2-methylsulfinyl phenyl)-5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (15)
By the K of 10mL2M 2cO 3solution; 3; 9-bis-(4; 4; 5; 5-tetramethyl--1,3,2-dioxy boron penta ring-2-base)-5; 5 '; 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene is coughed up [3,2-f] [1] benzo thiophene and is coughed up (1.20g; 2.0mmol) with 2-bromine (methanesulfinyl) benzene (1.31g; 6.0mmol) be dissolved in 100mL toluene solution, add tetrakis triphenylphosphine palladium (100mg) and Tetrabutyl amonium bromide (50mg) simultaneously, reaction reflux 24h.Afterwards reaction cool to room temperature is used dichloromethane extraction.Organic phase is dry, underpressure distillation with silica gel, and ethyl acetate/petroleum ether (volume ratio is 1:1) carries out column chromatography for moving phase, obtains faint yellow solid (0.7g, 56%).
Embodiment 165,5 ', 7,7 '-tetramethyl-two [2-b, 3; 9,10-b] benzo [d] thiophene benzo [b] [1] benzo thiophene coughs up the synthesis that [3,2-f] [1] benzo thiophene coughs up (16)
3,9-bis-(2-methylsulfinyl phenyl)-5,5 ', 7,7 '-tetramethyl-benzo [b] [1] benzo thiophene is coughed up [3,2-f] [1] benzo thiophene and is coughed up (1.24g, 2.0mmol) join 8mL trifluoromethanesulfonic acid, and add 0.5g Vanadium Pentoxide in FLAKES.Reaction stirred at ambient temperature 24h, is slowly added drop-wise to reaction solution in frozen water afterwards, suction filtration dry filter residue obtains pale yellow powder solid.Pale yellow powder is dissolved in 100mL pyridine, reflux 8h demethylation in nitrogen atmosphere.Cool to room temperature will be reacted afterwards, neutralize with hydrochloric acid and use dichloromethane extraction, organic phase crude product crosses chromatography column, eluent polarity sherwood oil/methylene dichloride (volume ratio is 1:1), white powdery solids (0.67g, 60%) is obtained again with ethyl alcohol recrystallization.
Prepared by embodiment 17 FET device
Prepare field-effect transistor and measure the field effect behavior of compound, device is for contacting type, and with gold as source electrode and drain electrode, concrete device architecture is Al/AlO x: Nd/PMMA/ICzBT/Au.Using glass as substrate, sputter one deck aluminium as grid at glass surface, simultaneously plate one deck aluminum oxide as gate insulation layer (preparation of above substrate has manufacturer to complete, can directly business purchase) in the performance of aluminium.Because the surface of aluminum oxide is comparatively coarse, be unfavorable for the film forming of compound, therefore at gate electrode insulation surface spin coating one deck polymethylmethacrylate (PMMA, be made into the n-butyl acetate solution that massfraction is 3%, get rid of film rotating speed 2000rpm, thickness 130nm, 220 DEG C of anneal 30min in nitrogen glove box) improve interracial contact, compound is mixed with the toluene solution of massfraction 0.7%, 2000rpm rotating speed gets rid of film (thickness 30 ~ 40nm) on PMMA, 100 DEG C of anneal 10min in air, afterwards 3 × 10 -4evaporation one deck molybdenum oxide (MoO in the vacuum tightness of Pa 3, evaporation rate 0.01 ~ 0.05nm/s, thickness is about 45nm), then under similarity condition gold evaporation as the source electrode of device and drain electrode.Device is about in humidity in the atmospheric environment of 70% in not encapsulating situation to be tested.Transistor device length and width raceway groove ratio (W/L) of preparation is 500/70 μm.The photoelectric properties of transistor are tested on Semiconductor Parameter Analyzer (Aglient4155C) and step instrument, and test environment is atmosphere at room temperature atmosphere.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.

Claims (8)

1. a class nine yuan of fused-ring derivatives, it is characterized in that, the chemical structural formula of these nine yuan of fused-ring derivatives is as follows:
Wherein nine yuan of condensed ring form large conjugate planes structure,
R 1for C 1~ C 30straight chained alkyl or C 1~ C 30branched-chain alkyl;
R 2for H, C 1~ C 30straight chained alkyl, C 1~ C 30branched-chain alkyl, OC 1~ OC 30straight chained alkyl or OC 1~ OC 30branched-chain alkyl;
R 3, R 4, R 5, R 6identical or different, be H, C 1~ C 30straight chained alkyl, C 1~ C 30branched-chain alkyl, OC 1~ OC 30straight chained alkyl, OC 1~ OC 30branched-chain alkyl, F, CF 3or wherein R 7for H, C 1~ C 30straight chained alkyl, C 1~ C 30branched-chain alkyl, OC 1~ OC 30straight chained alkyl, OC 1~ OC 30branched-chain alkyl, F or CF 3; X, Y comprise following combination: X=S, Y=O; Or X=S, Y be not containing any element;
Z=O, S, Se, N, P, C, Si, Ge or Sn.
2. synthesize the method for a class according to claim 1 nine yuan of fused-ring derivatives, it is characterized in that, synthetic route is as follows:
Wherein compound 4 and compound 5 are described nine yuan of fused-ring derivatives.
3. synthetic method according to claim 2, is characterized in that, synthesis step is as follows:
(1) 1 molar equivalent alkylating 3,9-dibromo five yuan of fused ring compounds are dissolved in dioxane, the Potassium ethanoate of the two tetramethyl ethylene ketone boric acid ester of 2 ~ 5 molar equivalents and 5 ~ 10 molar equivalents is added in inert gas environment, stir, 1 of 0.01-0.055 molar equivalent is added during raised temperature to 50 ~ 120 DEG C, the two Diphenyl phosphino ferrocene palladium chloride reaction of 1'-5 ~ 24 hours, reaction terminates rear cool to room temperature and suction filtration, and filtrate obtains product 2 after column chromatography is purified;
(2) 1 molar equivalent product 2 is dissolved in toluene, add 2-bromine (methanesulfinyl) benzene of 2 ~ 4 molar equivalents, the Tetrabutyl amonium bromide of 0.05 ~ 0.2 molar equivalent and the tetrakis triphenylphosphine palladium of 0.02-0.1 molar equivalent, heating reflux reaction 2 ~ 24 hours, after reaction terminates, cool to room temperature, extraction, drying, column chromatography is purified and is obtained product 3;
(3) 1 molar equivalent product 3 is joined in trifluoromethanesulfonic acid or trifluoroacetic acid, add the Vanadium Pentoxide in FLAKES of 1.5-4.0 molar equivalent simultaneously, room temperature reaction 5 ~ 24 hours under air tight condition, after reaction terminates reaction solution to be added drop-wise in water and suction filtration, after filter residue dries in pyridine reflux 2 ~ 12 hours, reaction terminates rear extraction, column chromatography is purified, recrystallization, obtains product 4;
(4) 1 molar equivalent product 4 is dissolved in methylene dichloride, add the 3-chloroperoxybenzoic acid of 4 ~ 30 molar equivalents, react 5 ~ 10 hours under ice bath, reaction terminates rear soda lye wash, extraction, drying, column chromatography purification, recrystallization, obtain nine yuan of fused-ring derivatives small molecules products 5.
4. a class according to claim 1 nine yuan of fused-ring derivatives, is characterized in that, such nine yuan of fused-ring derivatives have high with stable hole mobility, and its mobility is per second between 0.1 ~ 5.0 centimeters per volt.
5. a class nine yuan of fused-ring derivatives described in claim 1 are as the application of active coating in organic field effect tube device.
6. a class according to claim 5 nine yuan of fused-ring derivatives are as the application of active coating in organic field effect tube device, it is characterized in that: the thickness of the active coating of organic field effect tube device is 20-1000 nanometer.
7. a class according to claim 5 nine yuan of fused-ring derivatives are as the application of active coating in organic field effect tube device, it is characterized in that: the active coating of described organic field effect tube device is realized by solution processing method, comprises spin coating, brushing, spraying, dip-coating, roller coat, silk screen printing, printing or inkjet printing methods; Wherein solution processing solvent for use is organic solvent.
8. a class according to claim 5 nine yuan of fused-ring derivatives are as the application of active coating in organic field effect tube device, it is characterized in that: the preparation of the active coating of described organic field effect tube device carries out in atmosphere.
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