CN102659752A - Tetracene derivative field effect transistor material and preparation method thereof - Google Patents
Tetracene derivative field effect transistor material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tetracene derivative field effect transistor material and a preparation method thereof. The tetracene derivative field effect transistor material has a general structural formula I, wherein Ar represents aryl, substituted aryl, heterocyclic aryl or substituted heterocyclic aryl and R represents one of alkyl, alkoxy, alkyl sulphanyl and the like. The tetracene derivative field effect transistor material can be synthesized by a Sonogashira coupling reaction and a Bergman cyclization reaction. The tetracene derivative field effect transistor material has high stability and high dissolvability and can improve a mobility ratio of OFETs devices.
Description
Technical field
The present invention relates to one type of condensed ring conjugation material, is one type of tetracene verivate field effect transistor tube material and preparation method thereof specifically.
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Background technology
Organic semiconductor material has that relating to property of structure is strong, solution processable and can be processed in advantage such as flexible substrate, becomes the main body of electronic information material of new generation.Research and develop new and effective organic conjugate semiconductor material and will produce vast market prospect in electronic industry.Its neutral line acene class material (Acenes) is especially noticeable.And benzene material being widely used in photovoltaic cell (OPVs) and organic field effect tube (OFETs); In all OFET materials, one dimension or two-dimentional condensed ring (1D/2D Fusedaceneorheteroacene) material has all shown high device mobility.For example, pentacene (Pentacene), rubrene (Rubrene), tetracene (Tetracene) verivate (has surpassed 5 cm Ji perylene diimide (PDI) type material all has high mobility
2/ Vs).Anthony group obtains a large amount of conjugated polyene class materials with practical value, and these materials mainly are the p-type material, and n-type conjugated polyene material is still less.Especially but the material of air-stable solution method control film growth is few, and this field also becomes worldwide research difficult point.
Pentacene is the one type of p-type organic semiconductor material the most widely of research at present, and the thin-film device hole mobility that it is processed in the substrate deposition of chemically modified is up to 1.5 cm
2/ Vs, but pentacene inherent defective is restricted it in the practical application of FET device.For example: pentacene is insoluble in most of common organic solvents, causes pentacene almost to prepare the OFETs device with the mode through physical vapor deposition only; Have lower highest occupied molecular orbital (HOMO) energy level, oxidation or free radical reaction take place easily and cause stability of material to reduce; Arrange on the limit (Herringbone) of facing that presents " herringbone like " during condensed state, and this mode is unfavorable does pi-conjugated track overlapping, thereby causes device mobility to be difficult to reach the limit that material itself can reach.Overcoming pentacene system defective has many methods, is included in the acene system to introduce long alkyl chain and improve its solvability, also can in the acene system, introduce high electronegative atom or strong electron-withdrawing group group, reduces the HOMO energy level, the raising stability of molecule.Recently, continue to bring out as the novel heteroatoms acene analog derivative molecule that contains of OFETs semiconductor active layer, as 3; 4; 9,10-perylene diimide (PTCDI) and four thieno-anthracenes are introduced heteroatoms that sulphur etc. contains sky d track and can be interacted through Van der Waals force, π rail interaction and S-S and strengthen molecular interaction in the polycyclic aromatic hydrocarbons system; Make the molecular arrangement under solid-state tightr, thereby obtain the OFETs device of high mobility.The present invention has synthesized one type of tetracene verivate field effect transistor tube material cleverly through Sonogashira coupling and Bergman cyclization; And in one dimension and member ring systems, introduce the proper flexibility alkyl chain; The stability and the solvability of material have been improved, the acene material that obtained performance is excellent.And the raw material that uses is pyrene, and is cheap and easy to get, is beneficial to industrialization production.
Summary of the invention
Technical problem:The objective of the invention is to develop one type and have advantages such as high mobility, stability, film-forming properties, solvability, and prepare easy, with low cost tetracene verivate field effect transistor tube material.
Technical scheme:One type of tetracene verivate field-effect transistor preparation methods of the present invention, its structure can be represented by logical formula I:
Wherein Ar representes a kind of in aryl, substituted aryl, heterocyclic aryl or the substituted heterocycle aryl; R is a kind of in the substituting groups such as alkyl, alkoxyl group, alkylthio.
In the formula I general formula, aryl or substituted aryl are a kind of in benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi 、 perylene, fluorenes, the spiral shell fluorenes; Heterocyclic aryl or substituted heterocycle aryl are a kind of in pyrroles, pyridine, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or the benzothiazole; The substituting group of aryl or heterocyclic aryl is a kind of in halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, carboxamido-group, cyanic acid, aryloxy, aromatic base or the heterocyclic substituent, and the number of substituted aryl or substituted heterocycle aryl is single or a plurality of.
The preparation method comprises following synthesis step:
1). the compound of Ar representative is dissolved in organic solvent, in the presence of catalyzer, reacts under 20～100 ℃ with halide reagent, and reaction 1h～2d obtains one type suc as formula the halo Ar shown in (1);
2). Ar is dissolved in organic solvent with halo, adds palladium catalyst, cuprous iodide and trimethylsilyl acetylene, and 20～135 ℃ are stirred 6 h～5 d down, obtain one type suc as formula the substituted Ar compound of the trimethylsilyl acetylene shown in (2);
3). the substituted Ar compound of trimethylsilyl acetylene is dissolved in organic solvent, adds highly basic, 50～120 ℃ are stirred 1～48 h down, obtain one type suc as formula (3) the represented substituted Ar compound of one type of acetylene;
4). pyrene is dissolved in organic solvent, adds aluminum chloride and halohydrocarbon, carry out Fu-Ke alkylated reaction at 10～50 ℃, reaction 5～12 h, obtain suc as formula (4) represented 2,7-dialkyl group pyrene;
5). with 2,7-dialkyl group pyrene is dissolved in organic solvent, drips halide reagent, carries out substitution reaction at 0～50 ℃, reacts 1 h～2 d, obtain suc as formula (5) represented 2,7-dialkyl group-4,5,9,10-four halo pyrenes;
6). with 2,7-dialkyl group-4,5; 9; 10-four halo pyrenes and ethynyl are dissolved in organic solvent for the Ar compound, add palladium catalyst and cuprous iodide, and 60～135 ℃ are carried out Sonogashira coupling and Bergman cyclization; Reaction 8～24 h obtain the tetracene verivate field effect transistor tube material shown in logical formula I;
The compound of the described Ar representative of step 1) is aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; Described aryl or substituted aryl are benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi 、 perylene, fluorenes or spiral shell fluorenes; Substituted heterocycle aryl or substituted heterocycle aryl are pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; Described halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-iodo succimide (NIS), liquid bromine, iodine+Periodic acid 99, potassiumiodide+Periodic acid 99 etc.; Described organic solvent is methylene dichloride, trichloromethane, tetracol phenixin etc.; X in the formula (1)
1Be halogen atoms such as Cl, Br, I; Step 2) said palladium catalyst is tetrakis triphenylphosphine palladium, palladium, dichloro two triphenylphosphine palladiums etc.; Described organic solvent is THF, Diisopropylamine, toluene, benzene etc.; The said organic solvent of step 3) is methyl alcohol, ethanol etc.; Said highly basic is Pottasium Hydroxide, sodium hydroxide etc.; The described halohydrocarbon of step 4) can be hydrochloric ether, hydrobromic ether and idohydrocarbon.Said organic solvent is methylene dichloride, trichloromethane etc.; R is alkyl, alkoxyl group, alkylthio etc. in the formula (4); The said halide reagent of step 5) is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-iodo succimide (NIS), liquid bromine, iodine+Periodic acid 99, potassiumiodide+Periodic acid 99 etc.; Said organic solvent is methylene dichloride, trichloromethane and tetracol phenixin etc.; R in the formula (5) is alkyl, alkoxyl group, alkylthio etc.; X
2Be halogen atoms such as Cl, Br, I; The described palladium catalyst of step 6) is tetrakis triphenylphosphine palladium, palladium, dichloro two triphenylphosphine palladiums etc.; Said organic solvent is THF, Diisopropylamine, toluene etc.
Beneficial effect:Compared with prior art, tetracene verivate field effect transistor tube material of the present invention, synthetic through Sonogashira coupling and Bergman cyclization, simple to operate, by product is few, be easy to separate; The employing pyrene is a raw material, and is not only cheap and easy to get, and strengthened pi-conjugatedly, helps molecular assembly and piles up; The introducing of alkyl chain has improved stability, the solvability of material, thus the excellent tetracene field effect transistor tube material of obtained performance.
The present invention has obtained one type of tetracene verivate field effect transistor tube material, through nucleus magnetic resonance, mass spectrum etc. compound structure is characterized.Utilize the optical physics of methods such as ultraviolet, fluorescence spectrum, cyclic voltammetric, thermogravimetric analysis to them then, electrochemical properties and thermostability are studied.
Advantages such as tetracene verivate of the present invention has good stability, solvability is good, mobility is high, synthesis technique is simple, with low cost are a kind of OFET materials of excellent performance.
Description of drawings
Fig. 1. tetracene verivate A-1, B-1, the thermogravimetric analysis of C-1 (DTG) curve.
Fig. 2. tetracene verivate A-1, B-1, C-1 uv-absorbing and the fluorescent emission curve in chloroform soln.
Fig. 3. tetracene verivate A-1, B-1, C-1 cyclic voltammetric (CV) curve in dichloromethane solution.
Embodiment
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1:
In single necked round bottom flask (250 mL), add pyrene (10 g, 49.5 mmol), aluminum trichloride (anhydrous) (0.65 g, 4.92 mmol) and methylene dichloride (100 mL), nitrogen protection is stirred under the room temperature.Then, (10.05 g, 108.4 mmol) are dissolved in dichloromethane solution (15 mL) with tertiary butyl chloride, join in the reaction system slowly.After dropwising, continue stirring at room 6 h.With the aluminum chloride in cryosel acid (3 M) neutralization reaction system, dichloromethane extraction, organic phase water, saturated sodium bicarbonate, saturated nacl aqueous solution washing; Anhydrous magnesium sulfate drying concentrates, and ethyl alcohol recrystallization gets 9 g 2; 7-di-t-butyl pyrene, productive rate 57.5%.
1H?NMR(400?MHz,?CDCl
3)δ?(ppm)：8.18(s,?4H)，8.02(s,?4H)，1.58(s,?18H).
In two mouthfuls of round-bottomed flasks (250 mL), add 2,7-di-t-butyl pyrene (7.32 g, 20 mmol), iron powder (2.5 g, 44.6 mmol) and chloroform (100 mL), stirring at room.The chloroform soln (20 mL) of dripping bromine (19.2 g, 120 mmol) then.Dropwise back room temperature reaction 1.5 h, add the reaction of going out of sodium sulfite solution collection.Dichloromethane extraction concentrates, and the sherwood oil resedimentation gets 10g 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene.Productive rate 79.1%.
1H?NMR?(400?MHz,?CDCl
3)δ(ppm):?8.86(s,?4H),?1.62(s,?18H).
In single port bottle (50 mL), add 1-dodecyl thiophene (1.262 g, 5 mmol), I
2(0.544 g, 2.14 mmol), HIO
4(0.137 g, 0.72 mmol) and 80% acetate (12 mL).65
oC stirs 8h.Dichloromethane extraction, organic phase is with NaOH and hypo solution washing.Concentrate, silica gel chromatographic column separate 1 g 1-dodecyl-4-iodo-thiophene, productive rate 53%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.03-7.04(d,?1H),?6.47-6.48(d,?1H),?2.77-2.81(t,?2H),?1.60-1.67(m,?2H),?1.27-1.45(m,?18H),?0.87-0.91(t,?3H).?GC-MS(m/z):?387(M
+).
In two-mouth bottle (50 mL), add Pd (PPh
3)
4(28.99 mg, 0.025 mmol) and CuI (10 mg, 0.025 mmol); Nitrogen protection; Then 1-dodecyl-4-iodo-thiophene (398 mg, 1 mmol) and trimethylsilyl acetylene (120 mg, 1.1 mmol) are dissolved in (v/v=1/1) in Diisopropylamine and the THF mixing solutions; Splash in the reaction system, continue reaction 8 h then.Be cooled to room temperature, filter, concentrated filtrate, silica gel chromatographic column separate purify 243 mg 1-dodecyls-4-trimethylsilyl acetylene base thiophene, productive rate 70%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.04-7.05(d,?1H),?6.60-6.61(d,?1H),?2.74-2.77(t,?2H),?1.60-1.67(m,?2H),?1.26(s,?18H),?0.86-0.90(t,?3H),?0.23(s,?9H).
In single port bottle (50 mL), add 1-dodecyl-4-trimethylsilyl acetylene base thiophene (1.5 g, 4.5 mmol), KOH (336 mg, 6 mmol) and methyl alcohol (15 mL), 80
oC is reaction 1h down, is cooled to room temperature, and dichloromethane extraction concentrates, and silica gel chromatographic column separates purification and obtains 1 g 1-dodecyl-4-thiophene acetylene, productive rate 83.3%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.09-7.10(d,?1H),?6.63-6.64(d,?1H),?3.29(s,?1H),?2.75-2.79(t,?2H),?1.62-1.69(m,?2H),?1.27(s,?18H),?0.88-0.91(t,3H).
In two-mouth bottle (50 mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (500 mg, 0.79 mmol), Pd (PPh
3)
4(120 mg, 0.1 mmol) and CuI (20 mg, 0.1 mmol), nitrogen protection drips the Diisopropylamine and the THF mixing solutions (v/v=1/1) of 1-dodecyl-4-thiophene acetylene (1.1 g, 3.9 mmol) down, after dropwising, 80
oC reacts 8 h.Be cooled to room temperature, filter, concentrated filtrate gets, through silica gel chromatographic column separate purify 200 mg tetracene verivate A-1, productive rate 18%.
1H?NMR?(400?MHz,?CDCl
3)δ(ppm):?8.85(s,?4H),?8.79(s,?4H),?7.36(d,?4H),?6.80(d,?4H),?2.86-2.90(t,?8H),?1.70-1.78(m,?8H),?1.64(s,?18H),?1.27(s,?72H),?0.86-0.89(t,?12H).
Embodiment 2:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g, 1 mmol) and CuI (189 mg, 1 mmol); Nitrogen protection drips 1 down, 4-dimethyl--4-bromobenzene (7.4 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg; 44 mmol) Diisopropylamine and THF mixing solutions (150 mL; V/v=1/1), dropwise 80
oC reacts 12 h.Cooling is filtered, and concentrated filtrate, silica gel chromatography column separating purification get 5 g 1,2-dimethyl--4-trimethylsilyl acetylene base benzene, productive rate 61.9%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.26(s,?1H),?7.20-7.22(d,?1H),?7.05-7.07(d,?1H),?2.23-2.25(t,?3H),?0.25(s,?9H).
In single port bottle (500 mL), add 1,2-dimethyl--4-trimethylsilyl acetylene base benzene (5 g, 25 mmol), KOH (6.72 g, 120 mmol) and methyl alcohol (300 mL), 80
oC reacts 1 h, cooling, and dichloromethane extraction concentrates, and the silica gel chromatography column separating purification gets 2.4 g 1,2-dimethyl--4-acetylenylbenzene, productive rate 74.5%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.29(s,?1H),?7.23-7.26(d,?1H),?7.08-7.09(d,?1H),?3.02(s,?1H),?2.27(s,?3H),?2.24(s,?3H).
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (1.264 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI (40 mg, 0.2 mmol), nitrogen protection down drips 1, the Diisopropylamine of 2-dimethyl--4-acetylenylbenzene (1.04 g, 8 mmol) and THF mixing solutions (80 mL, v/v=1/1), then 80
oC reacts 8 h.Cooling is filtered, concentrated filtrate, silica gel chromatographic column separate purify 210 mg tetracene verivate B-1, productive rate 12%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?8.97(s,?4H),?8.80(s,?4H),?7.53-7.54(d,?4H),?7.21-7.23(d,?4H),?2.35(s,?12H),?2.33(s,?12H),?1.66(s,?18H).
Embodiment 3:
In two-mouth bottle (250 mL), add 1; 2-two octyloxy benzene (6.68 g, 20 mmol) and acetate (100 mL), stirring and dissolving; Divide six times and add N-bromo-succinimide (NBS) (3.6 g; 20 mmol), add NBS (0.5 g), room temperature reaction 1 h after at room temperature reacting 1h.Reaction is used NaHCO after finishing
3The aqueous solution is regulated PH to neutral, and dichloromethane extraction concentrates, and acetone recrystallization gets 7 g 1,2-two octyloxies-4-bromobenzene, productive rate 84.6%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?6.97-6.99（d,?1H）,?6.97(s,?1H),?6.72-6.74(d,?1H),?3.94-3.96(t,?4H),?1.77-1.82(m,?4H),?1.45(s,?4H),1.28-1.30(d,16H),?0.87-0.88(t,?6H).
In two-mouth bottle (100 mL), add 1,4-two octyloxies-4-bromobenzene (4.13 g, 10 mmol), Pd (PPh
3)
4(300 mg, 0.25 mmol) and CuI (48 mg, 0.25 mmol), and the Diisopropylamine of dropping trimethylsilyl acetylene (4.32 mg, 44 mmol) and THF mixing solutions under the nitrogen protection (40 mL v/v=1/1), dropwise, and 80
oC stirs 12 h.Cooling is filtered, and concentrated filtrate directly drops into next step reaction without purifying.
In single port flask (250 mL), put into product, KOH (2.8 g, 50 mmol) and methyl alcohol (120 mL) that step reaction obtains, stir and make it to dissolve, then 80
oC reacts 2 h, cooling, dichloromethane extraction concentrates, silica gel chromatographic column separate purify 1.25g 1,2-two octyloxies-4-acetylenylbenzene, productive rate 35%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?7.05-7.07(d,?1H),?7.00(s,?1H),?6.78-6.80(d,?1H),?3.96-4.00(m,?4H),?2.99(s,?1H),1.78-1.85(m,?4H),1.43-1.48(m,4H),?1.29(s,?16H),?0.87-0.91(t,?6H).
In two-mouth bottle (250mL), add 4,5,9,10-tetrabromobisphenol, 7-di-t-butyl pyrene (550 mg, 0.87 mmol), Pd (PPh
3)
4(150 mg, 0.125 mmol) and CuI (30 mg, 0.15 mmol); Nitrogen protection drips 1 down, the Diisopropylamine of 2-two octyloxies-4-acetylenylbenzene (1.25 g, 3.49 mmol) and THF mixing solutions (80 mL; V/v=1/1), after dropwising, 80
oC reacts 8 h.Cooling is filtered, concentrated filtrate, silica gel chromatographic column separate purify 180 mg tetracene verivate C-1, productive rate 11.8%.
1H?NMR(400?MHz,?CDCl
3)δ(ppm):?8.94(s,?4H),?8.80(s,?4H),?7.33-7.35(d,?4H),?7.26(s,?4H),?6.90-6.93(d,?4H),?4.04-4.07(t,?8H),?3.97-4.00(t,?8H),?1.81-1.88(m,?16H),?1.65(s,?18H),?1.44-1.50(m,?16H),?1.25-1.31(d,?64H),?0.89-0.90(d,?24H).
Embodiment 4:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g, 1 mmol) and CuI (189 mg, 1 mmol); Nitrogen protection drips the Diisopropylamine and THF mixing solutions (150 mL of bromobenzene (6.28 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg, 44 mmol) down; V/v=1/1), dropwise 80
oC reacts 12 h.Cooling is filtered, and concentrated filtrate, silica gel chromatography column separating purification get 4 g trimethylsilyl acetylene base benzene, productive rate 57.5%.
In single port bottle (500 mL), add trimethylsilyl acetylene base benzene (4 g, 23 mmol), KOH (6.72 g, 120 mmol) and methyl alcohol (300 mL), 80
oC reacts 1 h, cooling, and dichloromethane extraction concentrates, and the silica gel chromatography column separating purification gets 1.7 g acetylenylbenzenes, productive rate 74 %.
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-dimethoxy pyrene (1.156 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI (40 mg, 0.2 mmol), nitrogen protection drip down acetylenylbenzene (0.816 g, 8 mmol) Diisopropylamine and THF mixing solutions (80 mL, v/v=1/1), then 80
oC reacts 8 h.Cooling is filtered, concentrated filtrate, silica gel chromatographic column separate purify 200 mg tetracene verivate D-1, productive rate 15%.
Embodiment 5:
In two-mouth bottle (250 mL), add Pd (PPh
3)
4(1.2 g, 1 mmol) and CuI (189 mg, 1 mmol); Nitrogen protection drips the Diisopropylamine and THF mixing solutions (150 mL of 2-bromothiophene (6.52 g, 40 mmol) and trimethylsilyl acetylene (4.32 mg, 44 mmol) down; V/v=1/1), dropwise 80
oC reacts 12 h.Cooling is filtered, and concentrated filtrate, silica gel chromatography column separating purification get 4.4 g 2-trimethylsilyl acetylene base thiophene, productive rate 61.11%.
In single port bottle (500 mL), add 2-trimethylsilyl acetylene base thiophene (4.4 g, 24.44 mmol), KOH (5.6 g, 100 mmol) and methyl alcohol (290 mL), 80
oC reacts 1 h, cooling, and dichloromethane extraction concentrates, and the silica gel chromatography column separating purification gets 2 g 2-thiophene acetylenes, productive rate 75.76 %.
In two-mouth bottle (250 mL), add 4,5,9,10-tetrabromobisphenol, 7-diformazan sulfenyl pyrene (1.22 g, 2 mmol), Pd (PPh
3)
4(240 mg, 0.2 mmol) and CuI (40 mg, 0.2 mmol), nitrogen protection drip down 2-thiophene acetylene (0.864 g, 8 mmol) Diisopropylamine and THF mixing solutions (80 mL, v/v=1/1), then 80
oC reacts 8 h.Cooling is filtered, concentrated filtrate, silica gel chromatographic column separate purify 190 mg tetracene verivate F-1, productive rate 13.1%.
Claims (9)
1. one type of tetracene verivate field effect transistor tube material is characterized in that this material is the compound of following formula I general formula:
Wherein Ar representes aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; R is a kind of in alkyl, alkoxyl group or the alkylthio.
2. one type of tetracene verivate field effect transistor tube material according to claim 1 is characterized in that in the formula I general formula, and aryl or substituted aryl are a kind of in benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, pyrene, perylene, fluorenes, the spiral shell fluorenes; Heterocyclic aryl or substituted heterocycle aryl are a kind of in pyrroles, pyridine, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or the benzothiazole; The substituting group of aryl or heterocyclic aryl is a kind of in halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, carboxamido-group, cyanic acid, aryloxy, aromatic base or the heterocyclic substituent, and the substituting group number of substituted aryl or substituted heterocycle aryl is single or a plurality of.
3. tetracene verivate field-effect transistor preparation methods as claimed in claim 1 is characterized in that this type preparation methods comprises following synthesis step:
A. the compound of Ar representative is dissolved in organic solvent, in the presence of catalyzer, reacts under 20～100 ℃ with halide reagent, and reaction 1h～48h obtains one type suc as formula the halo Ar shown in (1);
B. halo Ar is dissolved in organic solvent, adds palladium catalyst, cuprous iodide and trimethylsilyl acetylene, 20～135 ℃ are stirred 6 h～5 day down, obtain one type suc as formula the substituted Ar compound of the trimethylsilyl acetylene shown in (2);
C. the substituted Ar compound of trimethylsilyl acetylene is dissolved in organic solvent, adds highly basic, 50～120 ℃ are stirred 1～48 h down, obtain one type suc as formula (3) the represented substituted Ar compound of one type of acetylene;
D. pyrene is dissolved in organic solvent, adds aluminum chloride and halohydrocarbon, carry out Fu-Ke alkylated reaction at 10～50 ℃, reaction 5～12 h, obtain suc as formula (4) represented 2,7-dialkyl group pyrene;
E. with 2,7-dialkyl group pyrene is dissolved in organic solvent, drips halide reagent, carries out substitution reaction at 0～50 ℃, reacts 1 h～48h, obtain suc as formula (5) represented 2,7-dialkyl group-4,5,9,10-four halo pyrenes;
F. with 2,7-dialkyl group-4,5; 9; 10-four halo pyrenes and ethynyl are dissolved in organic solvent for the Ar compound, add palladium catalyst and cuprous iodide, and 60～135 ℃ are carried out Sonogashira coupling and Bergman cyclization; Reaction 8～24 h obtain the tetracene verivate field effect transistor tube material shown in logical formula I.
4. one type of tetracene verivate field-effect transistor preparation methods according to claim 3, the compound that it is characterized in that the described Ar representative of step a is aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; Described aryl or substituted aryl are benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi 、 perylene, fluorenes or spiral shell fluorenes; Substituted heterocycle aryl or substituted heterocycle aryl are pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; Described halide reagent is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-iodo succimide (NIS), liquid bromine, iodine+Periodic acid 99 or potassiumiodide+Periodic acid 99; Described organic solvent is methylene dichloride, trichloromethane or tetracol phenixin; X in the formula (1)
1Be Cl, Br or I atom.
5. one type of tetracene verivate field-effect transistor preparation methods according to claim 3 is characterized in that the said palladium catalyst of step b is tetrakis triphenylphosphine palladium, palladium or dichloro two triphenylphosphine palladiums; Described organic solvent is THF, Diisopropylamine, toluene or benzene.
6. one type of tetracene verivate field-effect transistor preparation methods according to claim 3 is characterized in that the said organic solvent of step c is methyl alcohol or ethanol; Said highly basic is Pottasium Hydroxide or sodium hydroxide.
7. one type of tetracene verivate field-effect transistor preparation methods according to claim 3 is characterized in that the described halohydrocarbon of steps d is hydrochloric ether, hydrobromic ether or idohydrocarbon; Said organic solvent is methylene dichloride or trichloromethane; R is alkyl, alkoxyl group or alkylthio in the formula (4).
8. one type of tetracene verivate field-effect transistor preparation methods according to claim 3 is characterized in that the said halide reagent of step e is N-bromo-succinimide (NBS), N-chlorosuccinimide (NCS), N-iodo succimide (NIS), liquid bromine, iodine+Periodic acid 99 or potassiumiodide+Periodic acid 99; Said organic solvent is methylene dichloride, trichloromethane or tetracol phenixin; R in the formula (5) is alkyl, alkoxyl group or alkylthio; X
2Be Cl, Br, I atom.
9. one type of tetracene verivate field-effect transistor preparation methods according to claim 3 is characterized in that the described palladium catalyst of step f is tetrakis triphenylphosphine palladium, palladium or dichloro two triphenylphosphine palladiums; Said organic solvent is THF, Diisopropylamine or toluene.
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