CN105237748A - Thiazolyl diketopyrrolopyrrole polymer and preparation method therefor and application thereof - Google Patents
Thiazolyl diketopyrrolopyrrole polymer and preparation method therefor and application thereof Download PDFInfo
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Abstract
The invention discloses a thiazolyl diketopyrrolopyrrole polymer and a preparation method therefor and an application thereof. The structural formula I of the thiazolyl diketopyrrolopyrrole polymer is as shown in the description, wherein R is C1-C60 straight chain or branched chain alkane, m is the number of units, and X is an oxygen family element. The invention further provides the preparation method for the polymer as shown in the formula (I). The synthetic route of the polymer is simple and effective; raw materials are commercial products which are relatively low in price; and the synthetic method is universal. The highest migration rate of an organic field effect transistor prepared by taking 2-thiazolyl diketopyrrolopyrrole as an organic semiconductor layer is 1.43 cm2/V.s and the switch ratio is greater than 10<6>; the polymer has a very wide application prospect in an organic field effect transistor apparatus.
Description
Technical field
The invention belongs to Material Field, relate to a kind of thiazolyl pyrrolo-pyrrole-dione polymkeric substance and preparation method thereof and application.
Background technology
Polymer field effect transistor (Polymerfield-effecttransistors, be called for short PFETs) be using a class by use the polymkeric substance of Pi-conjugated systems do semiconductor material be used for substituting conventional without airport semi-conductor as carrier blocking layers, controlled the active part of the conductive capability of material by control electric field.Due to special solvability and the adhering character of polymkeric substance, PFET device can solution method be processed by flexibility, big area preparation, and cheap, have good compatibility to plastic.Meanwhile, polymkeric substance by modifying the chemical structure of poly-main chain backbone and pendant alkyl group chain and change, thus can regulate and control field effect behavior.Based on above advantage, PFET device promises to be the opto-electronic device of a new generation and the key components of circuit, has high application prospect, causes pay close attention to very widely in recent years, and and achieve larger progress.
P-type (current carrier is hole) and N-shaped material (current carrier is electronics) can be divided into by carrier transmission characteristics field effect transistor semiconductor material.And the core of PFET device i.e. its polymer semiconductor, which dictates that the transport property of whole field-effect transistor.The most important performance index of PFET are mobility, on-off ratio.The structure of pyrrolo-pyrrole-dione is widely used in organic electronics field, thiazole is the common conjugated molecule of a class, its lower molecular entergy level, and cheaper price, make in its small molecules being widely used organic field effect tube and polymer materials, and obtain higher mobility, thus synthetizing thiazolium base pyrrolo-pyrrole-dione polymkeric substance be applied in organic/polymer semiconducting material there is very important Theory and applications meaning.
Summary of the invention
The object of this invention is to provide a kind of thiazolyl pyrrolo-pyrrole-dione polymkeric substance and preparation method thereof and application.
Thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the present invention, its general structure such as formula shown in I,
In described formula I, R is the straight or branched alkyl of C1 ~ C60.
In above-mentioned formula I, m is unit number, is 0 or 1;
In above-mentioned formula I, X is chalcogen atom.
In above-mentioned formula I, R is the straight or branched alkyl of C10-C60, is specially 2-decyl tetradecyl, 4-decyl tetradecyl or 5-decyl pentadecyl.
In above-mentioned formula I, n is 5-100, and concrete n is 19-20,25-26 or 42-43 or 19-43.
In above-mentioned formula I, X is chalcogen atom, is specially S atom or Se atom.
Shown in the described formula I of preparation provided by the invention, the method for polymkeric substance, comprises the steps:
Under the effect of catalyzer and part, by compound 3 shown in formula II, two (the 5-bromethiazole-2-base)-2 of 6-, 5-bis-(alkyl) pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone and reactant a carry out polyreaction, react complete and obtain polymkeric substance shown in described formula I;
In described formula II, the definition of R is identical with the definition of R in formula I;
Described reactant a is (E)-1,2-two (5-(tin trimethyl) thiophene-2-base) ethene, (E)-1, two (5-(tin trimethyl) selenophen-2-base) ethene of 2-or (E)-1,2-pair of (tri-n-butyl tin base) ethene.
In aforesaid method, described catalyzer is selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium and two (dibenzalacetone) palladium;
Described part is selected from least one in triphenylphosphine, three (o-tolyl) phosphines and three (furyl) phosphine.
The molfraction that feeds intake of described reactant a is 0.95 ~ 1.05 part;
The molfraction that feeds intake of compound shown in described formula II is 0.95 ~ 1.05 part;
The molfraction that feeds intake of described catalyzer is 0.01 ~ 0.10 part;
The molfraction that feeds intake of described part is 0.02 ~ 0.30 part;
Described reactant a is specially 1.0:1.0:0.05:0.2 with the mole dosage ratio that feeds intake of compound shown in formula II, catalyzer and part
In described polymerization procedure, temperature is 100 ~ 120 DEG C;
Time is 24 ~ 72 hours;
Described polyreaction is carried out in a solvent; Described solvent is specially at least one in toluene, chlorobenzene and orthodichlorobenzene.
In aforesaid method, as starting raw material formula II shown in two (the 5-bromethiazole-2-bases)-2 of compound 3,6-, 5-bis-(alkyl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone can prepare in accordance with the following steps and obtain:
(1) 2-cyano thiazole and sodium tert-amyl alcohol and diisopropyl ester amber acid react, and obtain two (thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, the 5H)-diketone of 3,6-shown in formula III after completion of the reaction.
(2) by step 1) shown in gained formula III 3, two (thiazol-2-yl) pyrrolo-[3 of 6-, 4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone with react with idoalkane and salt of wormwood, obtain 3 shown in formula IV after completion of the reaction, two (thiazol-2-yl)-2,5-bis-(alkyl) pyrrolo-[3, the 4-c] pyrroles-1 of 6-, 4 (2H, 5H)-diketone;
In above-mentioned formula IV, the definition of R is identical with the definition of R in previously described formula I.
(3) by step 2) 3 shown in gained formula IV, two (thiazol-2-yl)-2,5-bis-(alkyl) pyrrolo-[3, the 4-c] pyrroles-1 of 6-, 4 (2H, 5H)-diketone and N-bromo-succinimide react, and obtain two (the 5-bromo thiophene thiazol-2-yl)-2 of 3,6-shown in formula V, 5-bis-(alkyl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone;
In above-mentioned formula V, the definition of R is identical with the definition of R in previously described formula I.
The step 1 of aforesaid method) in, described 2-bromo thiazole and sodium tert-amyl alcohol and diisopropyl ester amber acid are commercially produced product; The mole dosage ratio that feeds intake of described 2-cyano thiazole, sodium tert-amyl alcohol, diisopropyl ester amber acid is 2.0 ~ 2.5:2.5 ~ 4.0:1, preferred 2.5:3.75:1; In reactions steps, temperature is 90 ~ 120 DEG C, and the time is 3 ~ 6 hours;
Described step 2) in, described idoalkane is the straight or branched idoalkane of C5-C60; The mole dosage ratio that feeds intake of described 3,6-two (thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, idoalkane and salt of wormwood is 1:2.5 ~ 4:1 ~ 3, preferred 1:3:2.5; In reactions steps, temperature is 100 ~ 120 DEG C, and the time is 6 ~ 72 hours;
Described step 3) in, described N-bromo-succinimide is commerical prod; The mole dosage ratio that feeds intake of described 3,6-two (thiazol-2-yl)-2,5-bis-(alkyl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, N-bromo-succinimide is 1:3 ~ 6, preferred 1:4.9; In reactions steps, temperature is 60 ~ 65 DEG C, and the time is 24 ~ 72 hours;
Above-mentioned steps 1) to step 3) described reaction carries out all in a solvent.Described step 1) in, described solvent is tert-pentanol; Described step 2) in, described solvent is pre-dried N, N '-dimethyl methane amide; Described step 3) in, described solvent is trichloromethane.
The synthetic route of aforesaid method as shown in Figure 1.
In addition, the application of polymkeric substance shown in the formula I that the invention described above provides in the organic effect transistor of preparation and the organic field effect tube being semiconductor layer with polymkeric substance shown in formula I, also belong to protection scope of the present invention.
The invention has the advantages that:
1, synthetic method has conventional simple method, and synthetic route is shorter, and reaction yield is higher, simply efficiently; Raw material is commercially produced product, can apply the synthesis in industry;
2, polymer molecule backbone has good solvability, is conducive to the solution method processing of this polymkeric substance, can be used for the organic field effect tube device preparing low cost high mobility;
3, introduce the molecular orbital energy level that thiazole effectively can regulate and control polymkeric substance in the polymer backbone, the coplanarity of stronger skeleton, and higher photo and thermal stability, be expected to be applied in other photoelectric devices;
4. all very high (μ is greater than 0.1cm for the mobility (μ) of the PFET device prepared for semiconductor layer with thiazolyl pyrrolo-pyrrole-dione polymkeric substance with the present invention and on-off ratio
2v
-1s
-1, on-off ratio is greater than 10
4), in organic field effect tube, there is extraordinary application prospect.
Accompanying drawing explanation
Fig. 1 is the synthetic route of compound shown in preparation formula I provided by the invention.
Fig. 2 is with the ultraviolet-visible absorption spectroscopy figure of thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the invention.
Fig. 3 is with the cyclic voltammetry curve figure of thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the invention.
Fig. 4 is with the structural representation of thiazolyl pyrrolo-pyrrole-dione polymer field effect transistor provided by the invention.
Fig. 5 is with the output characteristic curve figure of the thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the invention polymer field effect transistor that is semiconductor layer.
Fig. 6 is with the transfer characteristic curve figure of the thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the invention polymer field effect transistor that is semiconductor layer.
Fig. 7 is with the transfer characteristic curve figure of the thiazolyl pyrrolo-pyrrole-dione polymkeric substance provided by the invention polymer field effect transistor that is semiconductor layer.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
In following embodiment, used pair of tin monomer (E)-1,2-two (5-(tin trimethyl) thiophene-2-base) ethene, (E)-1, two (5-(tin trimethyl) selenophen-2-base) ethene of 2-and (E)-1, two (tri-n-butyl tin base) ethene of 2-is commercially produced product or synthesizes (AdvancedMaterials by the method in document, 2012,24,4618 – 4622).
Embodiment 1, polymer P TDVT-10
1) synthesis of 3,6-two (thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
Tert-pentanol sodium (9.96g, 90.4mmol) is dissolved in 80mL tert-pentanol solution, 110 DEG C of heated and stirred 1h.Cyano thiazole (4g, 36.3mmol) and diisopropyl ester amber acid (2.94g, 14.52mmol) are dissolved in 20mL tert-pentanol, dripped in system in one hour, be added dropwise to complete rear reaction 3 ~ 5h.Poured into by reactant after having reacted in the mixing solutions of acetic acid (8.15mL) and water (200mL), suction filtration also uses a large amount of methanol wash, obtains atropurpureus solid 4.02g.Product directly can throw next step without purification.
2) synthesis of 3,6-two (thiazol-2-yl)-2,5-bis-(the 2-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By two for 3,6-(thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone (1g, 3.3mmol), sodium hydride (0.33g, 8.25mmol) add in 50mL two-mouth bottle, and use nitrogen replacement air.Then in reaction flask, the super dry N of 20mL is added, N '-dimethyl methane amide, 110 DEG C of reaction 2h.System is down to room temperature, drips the 1-iodo-2-decyl tetradecane (4.6g, 9.9mmol), then system is warming up to 120 DEG C of reaction 24h.After reactant is down to room temperature, reactant is poured in large water gaging, three filter methane extractions, organic phase anhydrous sodium sulfate drying.Under reduced pressure after solvent evaporated, with silica gel chromatographic column be separated, elutriant be sherwood oil and: methylene dichloride (2:1).Be spin-dried for solvent and obtain intense violet color solid 1.48g, productive rate 46%.
Structural characterization data are as follows:
Mass spectrum: [HR-MS (TOF)] m/z:974.744457.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 8.05 (d, J=3Hz, 1H), 7.69 (d, J=3Hz, 1H), 4.36 (d, J=9Hz, 2H), 1.87 (s, 1H), 1.1 (br, 40H), 0.88 (t, J=9Hz, 6H).
13c-NMR (75MHz, CDCl
3): δ 160.79,154.80,143.75,137.58,123.37,110.12,46.39,37.45,31.49,31.00,29.60,29.26,29.24,29.21,29.18,28.92,25.94,22.25,13.67.
3) synthesis of 3,6-two (5-bromo thiazole-2-base)-2,5-bis-(the 2-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By 3, two (thiazol-2-yl)-2 of 6-, 5-bis-(the 2-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (1g, 1.02mmol), N-bromo-succinimide (0.9g, 5.02mmol) is dissolved in 50mL chloroformic solution, backflow 36h.After being down to room temperature, solution is poured into water, with dichloromethane extraction, anhydrous magnesium sulfate drying.Be separated with silica gel chromatographic column after solvent evaporate to dryness, elutriant is sherwood oil: methylene dichloride (3:1), is spin-dried for solvent and obtains violet solid 0.62g, productive rate 53%.
Mass spectrum: [HR-MS (TOF)] m/z:1130.566805.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 7.91 (s, 1H), 4.27 (d, J=6Hz2H), 1.86 (s, 2H), 1.22 (br, 40H), 0.87 (t, J=7.5Hz, 6H).
13c-NMR (75MHz, CDCl
3) δ 161.03,156.33,145.73,137.00,115.83,110.73,47.02,37.94,31.94,31.43,30.05,29.72,29.70,29.64,29.38,26.39,22.71,14.13,0.11.
4) synthesis of PTDVT-10
By shown in formula II 3, two (the 5-bromo thiazole-2-base)-2 of 6-, 5-bis-(the 2-decyl-tetradecane-1-base) pyrrolo-[3, 4-c] pyrroles-1, 4 (2H, 5H)-diketone (226.68mg, 0.2mmol), (E)-1, two (tri-n-butyl tin base) ethene (121.2mg of 2-, 0.2mmol), three (dibenzalacetone) two palladium (9mg, 0.01mmol), three (o-tolyl) phosphine (12.3mg, 0.04mmol) join in reaction flask with toluene (5mL), three freezing--thaw cycles deoxygenations of bleeding are carried out in argon gas, then reaction mixture is heated to 110 DEG C of reaction 72h.After cooling, add 200mL methyl alcohol, stirred at ambient temperature 2h, filter.The polymkeric substance obtained loads apparatus,Soxhlet's extracting.First use methyl alcohol, acetone, normal hexane, trichloromethane extracting to colourless, removing small molecules and catalyzer, then obtain final product 170mg, productive rate 75% with chlorobenzene extraction.Resulting polymers molecular formula is such as formula shown in VI.
Molecular weight: GPC:Mn=25.2kDa, PDI=4.47, m=0, n=25 ~ 26.
Nucleus magnetic hydrogen spectrum: 1HNMR (300MHz, CDCl3) δ (ppm): 7.94 (br, 2H), 6.90 (br, 4H), 4.27 (br, 4H), 1.18-1.90 (m, 82H), 0.80 (br, 12H).
Embodiment 2, polymer P TDTVT-320
1) synthesis of 3,6-two (thiazol-2-yl)-2,5-bis-(the 4-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By two for 3,6-(thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone (1g, 3.3mmol), sodium hydride (0.33g, 8.25mmol) add in 50mL two-mouth bottle, and use nitrogen replacement air.Then in reaction flask, the super dry N of 20mL is added, N '-dimethyl methane amide, 110 DEG C of reaction 2h.System is down to room temperature, drips the 1-iodo-4-decyl tetradecane (4.6g, 9.9mmol), then system is warming up to 120 DEG C of reaction 24h.After reactant is down to room temperature, reactant is poured in large water gaging, three filter methane extractions, organic phase anhydrous sodium sulfate drying.Under reduced pressure after solvent evaporated, with silica gel chromatographic column be separated, elutriant be sherwood oil and: methylene dichloride (2:1).Be spin-dried for solvent and obtain intense violet color solid 1.64g, productive rate 51%.
Mass spectrum: [HR-MS (TOF)] m/z:974.744435.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 8.07 (d, J=3Hz, 1H), 7.71 (d, J=3Hz, 1H), 4.36 (d, J=7.5Hz, 2H), 1.68 (s, 1H), 1.24 (br, 40H), 0.88 (t, J=9Hz, 6H).
13c-NMR (75MHz, CDCl
3) δ 160.89,155.35,144.46,137.59,123.91,110.53,42.91,37.33,33.61,33.35,31.94,30.18,29.74,29.68,29.38,26.68,24.03,22.70,14.09.
2) synthesis of 3,6-two (5-bromo thiazole-2-base)-2,5-bis-(the 4-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By 3, two (thiazol-2-yl)-2 of 6-, 5-bis-(5-decyl-pentadecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (1g, 0.99mmol), N-bromo-succinimide (0.86g, 4.95mmol) is dissolved in 50mL chloroformic solution, backflow 36h.After being down to room temperature, solution is poured into water, with dichloromethane extraction, anhydrous magnesium sulfate drying.Be separated with silica gel chromatographic column after solvent evaporate to dryness, elutriant is sherwood oil: methylene dichloride (3:1), is spin-dried for solvent and obtains violet solid 0.55g, productive rate 48%.
Structural characterization data are as follows:
Mass spectrum: [HR-MS (TOF)] m/z:1158.597195.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 7.92 (s, 1H), 4.28 (d, J=9Hz, 2H), 1.66 (s, 1H), 1.25 (br, 40H), 0.88 (d, J=7.5Hz, 6H).
13cNMR (75MHz, CDCl
3): δ 160.66,156.40,145.85,136.65,115.88,110.80,43.34,37.02,33.57,31.94,30.40,30.12,29.74,29.68,29.37,26.61,22.70,14.12.
3) synthesis of polymer P TDTVT-320
By shown in formula II 3, two (the 5-bromo thiazole-2-base)-2 of 6-, 5-bis-(the 4-decyl-tetradecane-1-base) pyrrolo-[3, 4-c] pyrroles-1, 4 (2H, 5H)-diketone (226.68mg, 0.2mmol), (E)-1, two (5-(tin trimethyl) thiophene-2-base) ethene (103.58mg of 2-, 0.2mmol), three (dibenzalacetone) two palladium (9mg, 0.01mmol), three (o-tolyl) phosphine (12.3mg, 0.04mmol) join in reaction flask with toluene (5mL), three freezing--thaw cycles deoxygenations of bleeding are carried out in argon gas, then reaction mixture is heated to 110 DEG C of reaction 72h.After cooling, add 200mL methyl alcohol, stirred at ambient temperature 2h, filter.The polymkeric substance obtained loads apparatus,Soxhlet's extracting.First use methyl alcohol, acetone, normal hexane, trichloromethane extracting to colourless, removing small molecules and catalyzer, then obtain final product 205mg, productive rate 87% with chlorobenzene extraction.Polymer molecule formula is such as formula shown in VII.
Molecular weight: GPC:Mn=22.4kDa, PDI=2.48, m=1, n=19 ~ 20.
Nucleus magnetic hydrogen spectrum: 1HNMR (300MHz, CDCl3) δ (ppm): 7.91 (br, 2H), 6.94 (br, 6H), 4.27 (br, 4H), 1.21-1.60 (m, 82H), 0.79 (br, 12H).
Embodiment 3, polymer P TDSeVSe-420
1) synthesis of 3,6-two (thiazol-2-yl)-2,5-bis-(5-decyl-pentadecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By two for 3,6-(thiazol-2-yl) pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketone (1g, 3.3mmol), sodium hydride (0.33g, 8.25mmol) add in 50mL two-mouth bottle, and use nitrogen replacement air.Then in reaction flask, the super dry N of 20mL is added, N '-dimethyl methane amide, 110 DEG C of reaction 2h.System is down to room temperature, drips 1-iodo-5-decyl pentadecane (4.74g, 9.9mmol), then system is warming up to 120 DEG C of reaction 24h.After reactant is down to room temperature, reactant is poured in large water gaging, three filter methane extractions, organic phase anhydrous sodium sulfate drying.Under reduced pressure after solvent evaporated, with silica gel chromatographic column be separated, elutriant be sherwood oil and: methylene dichloride (2:1).Be spin-dried for solvent and obtain intense violet color solid 1.84g, productive rate 55%.
Mass spectrum: [HR-MS (TOF)] m/z:1002.774326.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 8.08 (d, J=3Hz, 1H), 7.71 (d, J=3Hz, 1H), 4.40 (d, J=7.5Hz, 2H), 1.69 (dd, J=10.5Hz, 9Hz, 1H), 1.25 (br, 42H), 0.88 (t, J=9Hz, 6H).
13c-NMR (75MHz, CDCl
3): δ 160.86,155.35,144.43,137.60,123.91,110.52,63.61,43.22,37.22,37.02,33.57,31.94,30.43,30.13,29.72,29.67,29.36,26.66,22.77,14.12.
2) synthesis of 3,6-two (5-bromo thiazole-2-base)-2,5-bis-(the 4-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone
By 3, two (thiazol-2-yl)-2 of 6-, 5-bis-(the 4-decyl-tetradecane-1-base) pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone (1g, 1.02mmol), N-bromo-succinimide (0.9g, 5.02mmol) is dissolved in 50mL chloroformic solution, backflow 36h.After being down to room temperature, solution is poured into water, with dichloromethane extraction, anhydrous magnesium sulfate drying.Be separated with silica gel chromatographic column after solvent evaporate to dryness, elutriant is sherwood oil: methylene dichloride (3:1), is spin-dried for solvent and obtains violet solid 0.54g, productive rate 47%.
Structural characterization data are as follows:
Mass spectrum: [HR-MS (TOF)] m/z:1131.572167.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1h-NMR (300MHz, CDCl
3): δ (ppm) 7.93 (s, 1H), 4.32 (d, J=7.5Hz, 1H), 1.66 (dd, J=10.5,9Hz, 1H), 1.25 (br, 42H), 0.88 (t, J=7.5Hz, 6H).
13c-NMR (75MHz, CDCl
3): δ 160.68,156.37,145.81,136.63,115.87,110.80,43.02,37.32,33.61,33.34,31.94,30.18,29.74,29.68,29.38,26.69,24.00,22.70,14.1.
3) synthesis of polymer P TDSeVSe-420
By shown in formula II 3, two (the 5-bromo thiazole-2-base)-2 of 6-, 5-bis-(5-decyl-pentadecane-1-base) pyrrolo-[3, 4-c] pyrroles-1, 4 (2H, 5H)-diketone (231.89mg, 0.2mmol), (E)-1, two (5-(tin trimethyl) selenophen-2-base) ethene (122.34mg of 2-, 0.2mmol), three (dibenzalacetone) two palladium (9mg, 0.01mmol), three (o-tolyl) phosphine (12.3mg, 0.04mmol) join in reaction flask with toluene (5mL), three freezing--thaw cycles deoxygenations of bleeding are carried out in argon gas, then reaction mixture is heated to 110 DEG C of reaction 72h.After cooling, add 200mL methyl alcohol, stirred at ambient temperature 2h, filter.The polymkeric substance obtained loads apparatus,Soxhlet's extracting.First use methyl alcohol, acetone, normal hexane, trichloromethane extracting to colourless, removing small molecules and catalyzer, then obtain final product 220mg, productive rate 81% with chlorobenzene extraction.Polymer molecule formula is such as formula shown in VIII.
Molecular weight: GPC:Mn=54.4kDa, PDI=3.38, m=1, n=42 ~ 43.
Nucleus magnetic hydrogen spectrum: 1HNMR (300MHz, CDCl3) δ (ppm): 8.21 (br, 2H), 7.67 (br, 6H), 4.30 (br, 4H), 2.51 (br, 4H), 1.30-1.63 (m, 86H), 0.81 (br, 12H).
The spectrum property of embodiment 4, embodiment 1-3 gained compound PTDVT-10, PTDTVT-320 and PTDSeVSe-420 and field-effect transistor performance
1) spectrum of compound PTDVT-10, PTDTVT-320 and PTDSeVSe-420 and chemical property
Fig. 2 is compound PTDVT-10, PTDTVT-320 and PTDSeVSe-420 ultraviolet-visible absorption spectroscopy in solution and film.
As shown in Figure 2, the optical band gap of the optical band gap of PTDVT-10 to be the optical band gap of 1.35eV, PTDTVT-320 be 1.40eV, PTDSeVSe-420 is 1.44eV.This several polymkeric substance has stronger Intramolecular electron transfer peak, shows that the frontier orbit of this main polymer chain is overlapping better.
Fig. 3 is the cyclic voltammetry curve of compound PTDVT-10, PTDTVT-320 and PTDSeVSe-420.Be determined at CHI660c electrochemical workstation to carry out, test with traditional three-electrode structure.Test is carried out in acetonitrile solution.
2) field-effect transistor performance of compound PTDVT-10, PTDTVT-320 and PTDSeVSe-420
Fig. 4 is the structural representation of organic field effect tube, and as shown in the figure, with highly doped silicon chip for substrate and gate electrode, the silicon-dioxide of 300 nanometer thickness is insulation layer, and gold is source electrode and drain electrode.Source-drain electrode utilizes the method for photoetching to prepare, substrate successively in acetone, intermediate water, ethanol after ultrasonic cleaning in 80 DEG C of vacuum-dryings, and by Cement Composite Treated by Plasma 15 minutes.Then octadecyl tri-chlorination silane (OTS) is used to modify activated silica sphere, shown in polymer P TDVT-10 shown in embodiment 1 gained formula I or embodiment 2 gained formula I, polymer P TDTVT-320 or embodiment 3 gained formula PTDSeVSe-420 is semiconductor layer, and thickness is 50nm.Polymer materials is dissolved in the substrate of being modified at OTS by the method for getting rid of film in orthodichlorobenzene forms film thickness is 40nm), and anneal 5 minutes in thermal station.The electrical properties of prepared FET device is at room temperature measured with Keithley4200SCS semi-conductor test instrument.
Most important two parameters of PFET performance are: the mobility (μ) of current carrier and the on-off ratio (I of device
on/ I
off).Mobility refers to: under unit electric field, and (unit is cm to the average mobility speed of current carrier
2v
-1s
-1), it reflects current carrier under the electric field as hole or electronics transfer ability in the semiconductors.On-off ratio is defined as: the ratio of the electric current of transistor under "On" state and "Off" state, it directly reflects the quality of devices switch performance.One has high-performance and with the field-effect transistor of practical application, can should have mobility high as far as possible and on-off ratio.
Fig. 5 is for based on the transfer characteristic curve of the field-effect transistor prepared by PTDVT-10 and output characteristic curve.
Fig. 6 is for based on the transfer characteristic curve of the field-effect transistor prepared by PTDTVT-320 and output characteristic curve.
Fig. 7 is for for based on the transfer characteristic curve of the field-effect transistor prepared by PTDSeVSe-420 and output characteristic curve.
Show good linear section and saturation region from upper figure, embodiment of the present invention 1-3 gained three polymer field effect transistor, illustrate that the OFET device based on THE and UHE has good field-effect performance of control.
Carrier mobility can be drawn by Equation for Calculating:
I
dS=(W/2L) C
i μ(V
g– V
t)
2(saturation region, V
dS=V
g– V
t)
Wherein, I
dSfor drain current, μ is carrier mobility, V
gfor grid voltage, V
tfor threshold voltage, W is channel width (W=1400 micron), and L is channel length, C
ifor isolator electric capacity (unit-area capacitance (SiO
2relative permittivity 3.9, SiO
2layer 300nm).Utilize (I
dS, sat)
1/2to V
gmapping, and does linear regression, the slope of the tropic thus can extrapolate carrier mobility (μ), try to achieve V by the section of the tropic and X-axis
t.Mobility can calculate according to the slope of formula from transition curve.
On-off ratio can be drawn by the ratio of the maxima and minima of Fig. 5 source-drain current.
With PTDVT-10, PTDTVT-320 and PTDSeVSe-420 polymkeric substance of synthesis for organic layer has made multiple organic field effect tube device, in these devices, the mobility of PTDVT-10 is 0.48cm
2v
-1s
-1, on-off ratio is 10
6; PTDTVT-320 is 1.43cm
2v
-1s
-1, on-off ratio is 10
7; PTDSeVSe-420 is 0.31cm
2v
-1s
-1, on-off ratio is 10
6.
Experimental result shows, the polymkeric substance being framework unit with thiazolyl pyrrolo-pyrrole-dione is excellent polymer semiconducting material.The present invention is not limited to these reported three materials, change different side chain substituents and can obtain a series of polymkeric substance, and the synthetic method that the present invention provides is simple, effective, relation be-tween structure and properties for Study Polymer Melts semiconductor material helps huge, has very important directive significance to designing further and preparing high performance material.
Claims (8)
1. polymkeric substance shown in formula I,
In described formula I, R is C
1~ C
60straight or branched alkyl;
M is 0 or 1;
X is different chalcogen atoms;
N is 5-100.
2. polymkeric substance shown in formula I according to claim 1, is characterized in that: in described formula I, and R is C
10-C
60straight or branched alkyl, be specially 2-decyl tetradecyl, 4-decyl tetradecyl or 5-decyl pentadecyl;
X is S or Se.
3. prepare a method for polymkeric substance shown in the arbitrary described formula I of claim 1 or 2, comprise the steps:
Under the effect of catalyzer and part, compound shown in formula II and reactant a are carried out polyreaction, reacts complete and obtain polymkeric substance shown in described formula I;
In described formula II, the definition of R is identical with the definition of R in claim 1 Chinese style I;
Described reactant a is (E)-1,2-two (5-(tin trimethyl) thiophene-2-base) ethene, (E)-1, two (5-(tin trimethyl) selenophen-2-base) ethene of 2-or (E)-1,2-pair of (tri-n-butyl tin base) ethene.
4. method according to claim 3, described catalyzer is selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium and two (dibenzalacetone) palladium;
Described part is selected from least one in triphenylphosphine, three (o-tolyl) phosphines and three (furyl) phosphine.
5. the method according to claim 3 or 4, is characterized in that: the molfraction that feeds intake of described reactant a is 0.95 ~ 1.05 part;
The molfraction that feeds intake of compound shown in described formula II is 0.95 ~ 1.05 part;
The molfraction that feeds intake of described catalyzer is 0.01 ~ 0.10 part;
The molfraction that feeds intake of described part is 0.02 ~ 0.30 part;
Described reactant a is specially 1.0:1.0:0.05:0.2 with the mole dosage ratio that feeds intake of compound shown in formula II, catalyzer and part.。
6., according to described method arbitrary in claim 3-5, it is characterized in that: in described polymerization procedure, temperature is 100 DEG C ~ 120 DEG C.
Time is 24 hours ~ 72 hours;
Described polyreaction is carried out in a solvent; Described solvent is specially at least one in toluene, chlorobenzene and orthodichlorobenzene.
7. the application of polymkeric substance shown in the arbitrary described formula I of claim 1 or 2 in the organic effect transistor of preparation.
8. an organic field effect tube, is characterized in that: in described organic field effect tube, and the material forming semiconductor layer is polymkeric substance shown in the arbitrary described formula I of claim 1 or 2.
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| CN105968326A (en) * | 2016-05-18 | 2016-09-28 | 中国科学院化学研究所 | Preparation method and application of dipyrrolo-pyrroledione polymer |
| CN107698743A (en) * | 2017-09-28 | 2018-02-16 | 中国科学院化学研究所 | One kind contains the application in fluorostyrene thiophene-structure conjugated polymer and its scene effect transistor |
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|---|---|---|---|---|
| US20130240792A1 (en) * | 2012-03-19 | 2013-09-19 | Xerox Corporation | Semiconductor composition for high performance organic devices |
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| US20130240792A1 (en) * | 2012-03-19 | 2013-09-19 | Xerox Corporation | Semiconductor composition for high performance organic devices |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968326A (en) * | 2016-05-18 | 2016-09-28 | 中国科学院化学研究所 | Preparation method and application of dipyrrolo-pyrroledione polymer |
| CN105968326B (en) * | 2016-05-18 | 2018-09-21 | 中国科学院化学研究所 | The preparation method of double pyrrolo-pyrrole-dione polymer and application |
| CN107698743A (en) * | 2017-09-28 | 2018-02-16 | 中国科学院化学研究所 | One kind contains the application in fluorostyrene thiophene-structure conjugated polymer and its scene effect transistor |
| CN107698743B (en) * | 2017-09-28 | 2020-08-04 | 中国科学院化学研究所 | Conjugated polymer containing fluoro styrene thiophene structure and application thereof in field effect transistor |
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