CN114456355B - Double-pyridine triazole semiconductor polymer and preparation and application thereof - Google Patents
Double-pyridine triazole semiconductor polymer and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a bipyridyl triazole polymer and a preparation method and application thereof. The structural general formula of the bipyridyl triazole polymer is shown as a formula I. In the formula I, R is a straight chain or branched chain alkyl with the total number of carbon atoms of 1-40; ar is selected from any one of the following groups:
the invention designs and synthesizes a novel bis-pyridyltriazole (BTP) receptor and a polymer, and researches the application of the BTP receptor and the polymer in an organic field effect transistor. The test result shows that the polymer shows excellent p-type semiconductor property. The bipyridyl triazole polymer further expands the variety of semiconductor polymer materials and has good application prospect in organic photoelectric devices.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a bispyrido triazole polymer, and a preparation method and application thereof.
Background
Organic field effect transistors (OFETs for short) are active photoelectric devices which take organic semiconductor materials as semiconductor layers and control the conductivity of the materials through a vertical electric field. OFETs have the advantages of solution-soluble processing, good flexibility, easy adjustment of photoelectric properties and the like, and have important application prospects in devices such as logic circuits, sensors, electronic skins and the like.
The OFETs semiconductor material comprises organic small molecule materials and organic polymer materials. The organic polymer material has the advantages of light weight, good flexibility, large-area printing and processing and the like, and is widely applied to photoelectric devices. The design and synthesis of novel semiconducting polymer materials is of great significance to the development of the field.
Disclosure of Invention
The invention aims to provide a double-pyridotriazole receptor, a polymer and a preparation method thereof.
The structural general formula of the bipyridyl triazole polymer provided by the invention is shown as formula I:
in the formula I, R is a straight chain or branched chain alkyl group with the total number of carbon atoms of 1-40 (specifically 10-35, more specifically 15-35);
ar is selected from any one of the following groups:
wherein the content of the first and second substances,
all represent a substitution;
in the formula I, R can be 5-decyl pentadecyl specifically;
n represents polymerization degree, n can be an integer of 5-100, and n can be 24 specifically;
specifically, the polymer represented by the formula I has the following structural formula:
wherein R is a linear or branched alkyl group having a total number of carbon atoms of 1 to 40 (specifically 10 to 35, more specifically 15 to 35).
More specifically, the polymer represented by the formula I has the following structural formula:
wherein R is 5-decylpentadecyl.
The polymer shown in the formula I is prepared by a method comprising the following steps:
carrying out polymerization reaction on a compound shown in a formula VII and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown in a formula I;
r is as defined for R in formula I above.
In the above method, the di-tin compound is selected from any one of the following compounds:
the catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
the ligand is at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine.
The feeding mole part ratio of the compound shown in the formula VII to the double-tin compound, the catalyst and the mixture ratio can be 1: 0.95-1.05: 0.01 to 0.10:0.04 to 0.80; specifically, 1.00:1.00:0.03:0.24;
in the polymerization reaction, the temperature can be 80-140 ℃; specifically, the temperature can be 130 ℃;
the reaction time can be 1-80 hours; specifically, the time can be 12 hours;
the polymerization reaction is carried out in an organic solvent, wherein the organic solvent can be at least one selected from toluene, chlorobenzene and xylene;
the polymerization reaction is carried out in an inert atmosphere, which may be provided by nitrogen.
The method can further comprise the following purification steps:
after the polymerization reaction is finished, cooling the obtained reaction system, adding methanol, stirring and filtering at room temperature, sequentially extracting the obtained precipitate with methanol, acetone and n-hexane until the precipitate is colorless, removing micromolecules and a catalyst, and extracting with chloroform.
In addition, the starting material of the compound represented by formula VII in the above reaction also belongs to the protection scope of the present invention:
r is as defined for R in formula I.
The compound shown in the formula VII can be prepared according to the method comprising the following steps:
a) Carrying out bromination reaction on the 3, 4-diaminopyridine in a mixed solution of liquid bromine and hydrobromic acid to obtain 2, 5-dibromopyridine-3, 4-diamine shown in a formula II;
b) Reacting the 2, 5-dibromopyridine-3, 4-diamine shown in the formula II obtained in the step a) with sodium nitrite in an acetic acid solution to obtain pyridotriazole shown in the formula III;
c) Reacting the pyridotriazole shown in the formula III obtained in the step b) with R-I and potassium carbonate to obtain a compound shown in a formula IV;
R-I, wherein R is as defined for R in formula I;
d) Carrying out coupling reaction on the compound shown in the formula IV obtained in the step c) and 2-tributylstannyl thiophene under the catalysis of bis (triphenylphosphine) palladium dichloride to obtain pyridotriazole-thiophene (namely TP-T) shown in the formula V;
r is as defined for R in formula I;
e) Coupling the pyridotriazole-thiophene shown in the formula V and hexamethyl-ditin obtained in the step d) under the catalysis of tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine to obtain the bipyridyl triazole-dithiophene (namely BTP-2T) shown in the formula VI;
r is as defined for R in formula I;
f) Brominating the bipyridyl triazole-dithiophene shown in the formula VI obtained in the step e) to obtain bipyridyl triazole-dithiophene-dibromo (BTP-2T-2 Br) shown in the formula VII.
In step a) of the method, the feeding molar ratio of the 3, 4-diaminopyridine to the liquid bromine can be 1:2 to 4, specifically 1:2.6; in the reaction step, the temperature can be 70-130 ℃, and the time can be 1-24 hours;
in step b), the molar ratio of the 2, 5-dibromopyridine-3, 4-diamine to the sodium nitrite can be 1:0.8 to 3, specifically 1:1.5; in the reaction step, the temperature can be 0-50 ℃, and the time can be 1-24 hours;
in the step c), R-I has the same definition as R in the formula I;
the feeding molar ratio of the pyridotriazole shown in the formula III to the R-I can be 1.8-4, specifically 1.2; in the reaction step, the temperature can be 50-130 ℃, and the time can be 4-48 hours;
in the step d), the feeding molar ratio of the compound shown in the formula IV to 2-tributylstannyl thiophene and bis (triphenylphosphine) palladium dichloride can be 1.8-4: 1:0.05; in the reaction step, the temperature can be 70-130 ℃, and the time can be 2-72 hours;
in the step e), the feeding molar ratio of the pyridotriazole-thiophene, hexamethylditin, tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine of the formula V can be 0.5-4; in the reaction step, the temperature can be 80-140 ℃ and the time can be 2-72 hours;
in the step f), the bromination reaction is realized by reacting the bipyridyl triazole-dithiophene shown in the formula VI with N-bromosuccinimide (namely NBS) in a trichloromethane solution;
wherein, the feeding molar usage ratio of the bispyrido triazole-dithiophene shown in the formula VI to the N-bromosuccinimide can be 1.0-5, and specifically can be 1:3.7; in the reaction step, the temperature can be-10-40 ℃, and the time can be 2-48 hours;
the synthetic route of the above method is shown in FIG. 1.
The application of the polymer shown in the formula I in the preparation of the organic field effect transistor also belongs to the protection scope of the invention, and the organic field effect transistor can be a p-type field effect transistor device.
The organic field effect transistor using the polymer shown in the formula I as an organic semiconductor layer also belongs to the protection scope of the invention.
The invention has the advantages that:
1. the raw materials are commercial products, the synthetic route is simple, monomers and polymers are new molecules, and the method can be popularized to the synthesis of various linear chain or branched chain bipyridyl triazole polymers;
2. the HOMO energy level of the double-pyridotriazole polymer is matched with that of a gold electrode, so that the double-pyridotriazole polymer can be used for preparing a high-performance p-type field effect transistor device;
3. the organic field effect transistor prepared by using the double-pyridine triazole polymer as a semiconductor layer has higher mobility (the highest hole mobility is 0.2 cm) 2 V -1 s -1 ) And the method has good application prospect in OFET devices.
The invention designs and synthesizes a novel bis-pyridyltriazole (BTP) receptor and a polymer, and researches the application of the BTP receptor and the polymer in an organic field effect transistor. The test result shows that the polymer shows excellent p-type semiconductor property. The bipyridyl triazole polymer further expands the variety of semiconductor polymer materials and has good application prospect in organic photoelectric devices.
Drawings
FIG. 1 is a synthetic scheme for the preparation of compounds of formula I as provided by the present invention.
FIG. 2 is a diagram showing the UV-VIS absorption spectrum of a bispyridotriazole polymer provided by the present invention.
FIG. 3 is a plot of cyclic voltammetry of a bis-pyridotriazole polymer provided by the present invention.
FIG. 4 is a schematic structural view of a double pyridotriazole polymer field effect transistor provided by the present invention.
FIG. 5 is a graph showing an output characteristic and a transfer characteristic of a polymer field effect transistor using a bis-pyridotriazole polymer provided by the present invention as a semiconductor layer.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 Polymer PBTP-2FBT
The polymer PBTP-2FBT was prepared according to the synthetic scheme shown in FIG. 1.
a) 2, 5-dibromopyridine-3, 4-diamine
To a 500mL two-necked flask were added 3, 4-diaminopyridine (8.0g, 73.3mmol) and 160mL of hydrobromic acid (48%), and 9.8mL of liquid bromine (30.6 g, 191.5mmol) was added dropwise at room temperature. The mixture was reacted at 110 ℃ for 4h and cooled to 0 ℃. Filtering the mixed solution to obtain filter residue. Sequentially adding Na to filter residues 2 S 2 O 3 ，NaHCO 3 And deionized water washing. The residue was extracted with ethyl acetate and water, and the organic phase was collected, dried and spin-dried to give a solid (8.0 g, 41%).
The structural characterization data is as follows:
1 H NMR(300MHz,(CD 3 ) 2 SO)δ7.53(s,1H),6.00(s,2H),5.05(s,2H). 13 C NMR(75MHz,(CD 3 ) 2 SO)δ139.7,138.9,129.3,126.4,105.0.HREI:[M] + calcd for C 5 H 5 Br 2 N 3 :266.8830,found:266.8833.
b) Pyridotriazoles
2, 5-dibromopyridine-3, 4-diamine (15.0 g, 56.2mmol) and 250mL of acetic acid were added to a 500mL two-necked flask and dissolved by sonication. A solution of sodium nitrite (5.82g, 84.3 mmol) in water (90 mL) was added dropwise. The mixture was reacted at 25 ℃ for 12h. The mixture was filtered, and the residue was washed with water and ethanol in this order and dried to give a solid (11.0 g, 71%). The product was used in the next reaction without further purification.
c) 2- (5-decylpentadecyl) -pyridotriazoles
A500 mL two-necked flask was charged with pyridotriazole (8.0 g,28.8 mmol), potassium carbonate (7.96g, 57.6 mmol), 1-iodo-5-decylpentadecane (16.54g, 34.6 mmol), 250mL of anhydrous N, N-dimethylformamide, and purged with nitrogen. The mixture was reacted at 90 ℃ for 24h. Extracted with water and dichloromethane and dried. The solution was spun dry and passed through a column (eluent petroleum ether: dichloromethane = 5).
The structural characterization data is as follows:
1 H NMR(300MHz,CDCl 3 )δ8.34(s,1H),4.83(t,J＝7.5Hz,2H),2.15(m,2H),1.60–1.00(m,41H),0.88(m,6H). 13 C NMR(75MHz,CDCl 3 )δ146.4,143.3,141.7,132.7,108.1,58.1,37.2,33.5,32.9,31.9,30.5,30.1,29.7,29.6,29.4,26.6,23.6,22.7,14.1.HR-MALDI-TOF:[M+H] + calcd for C 30 H 53 Br 2 N 4 :629.26166,found:629.26116.
d) Pyridinotriazole-thiophenes
2- (5-Decylpentadecyl) -pyridotriazole (4.8g, 7.6 mmol), 2-tributylstannyl thiophene (2.85g, 7.6 mmol) and bis (triphenylphosphine) palladium dichloride (267 mg) were added to the flask in this order under nitrogen. 150mL of gas-depleted chlorobenzene was then added. The mixture was stirred at 110 ℃ for 48 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and passing through a column. Eluent (petroleum ether: dichloromethane =3. Finally, an oily liquid (2.16g, 45%) was obtained.
The structural characterization data is as follows:
1 H NMR(300MHz,CD 2 Cl 2 )δ8.53(d,J＝3.3Hz,1H),8.44(s,1H),7.59(d,J＝4.8Hz,1H),7.25(t,1H),4.86(t,J＝7.2Hz,2H),2.17(m,2H),1.60–1.05(m,41H),0.88(m,6H). 13 C NMR(75MHz,CDCl 3 )δ147.1,145.7,143.3,141.0,138.3,130.9,129.9,128.6,105.1,57.6,37.2,33.5,33.0,31.9,30.5,30.1,29.7,29.6,29.4,26.7,23.7,22.7,14.1.HR-MALDI-TOF:[M+H] + calcd for C 34 H 56 BrN 4 S:631.34091,found:631.34030.
e) Bis-pyridotriazole-dithiophenes
To a two-necked flask were added pyridotriazole-thiophene (1.8g, 2.8mmol), hexamethylditin (0.56g, 1.7mmol), tris (dibenzylideneacetone) dipalladium (130.5 mg) and tris (o-tolyl) phosphine (347.3 mg) in this order under nitrogen. Then 80mL of gas-depleted chlorobenzene was added. The mixture was stirred at 110 ℃ for 48 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and passing through a column. Eluent (petroleum ether: dichloromethane =3. A yellow solid (0.68g, 44%) was obtained.
The structural characterization data are as follows:
1 H NMR(300MHz,CDCl 3 )δ9.86(s,2H),8.74(br,2H),7.65(s,2H),7.31(t,2H),4.92(t,J＝6.9Hz,4H),2.24(m,4H),1.60–1.00(m,82H),0.87(m,12H). 13 C NMR(75MHz,CDCl 3 )δ145.8,145.4,143.5,142.1,138.5,130.9,129.7,128.7,118.0,57.4,37.3,33.6,33.1,31.9,30.5,30.1,29.7,29.6,29.4,26.7,23.7,22.7,14.1.HR-MALDI-TOF:[M+H] + calcd for C 68 H 111 N 8 S 2 :1103.83732,found:1103.83566.
f) Bis-pyridotriazole-dithienyl-dibromide
Bis-pyridotriazole-bithiophene (0.6 g, 0.54mmol) was dissolved in 36mL of chloroform, the mixture was ice-cooled, stirred, and N-bromosuccinimide (0.327g, 1.83mmol) in DMF (7 mL) was added in portions, and the mixture was aerated and protected. The mixture was stirred at room temperature for 24 hours. N-bromosuccinimide (28.8mg, 0.162mmol) in DMF (1 mL) was added thereto under ice-cooling, and the mixture was stirred at room temperature for 8 hours. Adding water for quenching. Extracting with chloroform, spin-drying, and purifying with column. Eluent (petroleum ether: chloroform = 4. A blue solid (0.48g, 71%) was obtained.
The structural characterization data is as follows:
1 H NMR(300MHz,CD 2 Cl 2 )δ9.70(s,2H),8.35(d,J＝3.6Hz,2H),7.24(d,J＝3.6Hz,2H),4.92(t,J＝6.9Hz,4H),2.23(m,4H),1.60–1.00(m,82H),0.86(m,12H). 13 C NMR(75MHz,CDCl 3 )δ145.1,144.6,143.6,143.5,138.0,131.6,130.9,118.0,117.9,57.4,37.3,33.5,33.1,31.9,30.5,30.1,29.7,29.6,29.4,26.7,23.8,22.7,14.1.HR-MALDI-TOF:[M+H] + calcd for C 68 H 109 Br 2 N 8 S 2 :1261.65630,found:1261.65410.
g) Polymer PBTP-2FBT
Bipyridotriazole-dithienyl-dibromo (100.0mg, 0.079mmol), 5' -bis (trimethyltin) -3,3' -difluoro-2, 2' -bithiophene (41.8mg, 0.079mmol), tris (dibenzylideneacetone) dipalladium (2.2 mg) as a catalyst, tris (o-tolyl) phosphine (5.8 mg) as a ligand, and chlorobenzene (6 mL) were charged into a reaction flask, subjected to three freeze-pump-thaw cycles to remove oxygen under nitrogen, and the mixture was heated to 130 ℃ to conduct polymerization for 12 hours. After cooling, 100mL of methanol was added, stirred at room temperature for 3h, and filtered. The obtained precipitate is loaded into a Soxhlet extractor for extraction. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product of 97mg, wherein the yield is 94%.
The structural characterization data is as follows:
molecular weight: mn =32.3kDa, mw =125.3kDa, PDI =3.88,n =24.
Elemental analysis: anal, calcd, for C 76 H 110 F 2 N 8 S 4 :C 70.11,H 8.52,N 8.61；found:C 68.17,H8.46,N 8.20.
As can be seen from the above, the compound has a correct structure and is a compound PBTP-2FBT shown in formula I, and the structural formula is shown as follows:
wherein R is 5-decylpentadecyl.
Example 2 spectral, electrochemical and field Effect transistor Performance of Polymer PBTP-2FBT
1) Spectral and electrochemical Properties of Polymer PBTP-2FBT
FIG. 2 shows the UV-visible absorption spectra of polymer PBTP-2FBT in solution and in film.
As can be seen from FIG. 2, the optical band gap of the polymer PBTP-2FBT is 1.79eV (the optical band gap is shown in accordance with equation E) g =1240/λ calculation, where E g Is the optical band gap, and λ is the boundary value of the ultraviolet absorption curve). As can be seen from FIG. 2, the polymer has a strong intramolecular charge transfer peak, indicating that the intermolecular force of the polymer is strong.
FIG. 3 is a cyclic voltammogram of a polymer PBTP-2FBT film. The measurement was carried out in the electrochemical workstation CHI660c, using the conventional three-electrode structure for the test, platinum as the working electrode, platinum wire as the counter electrode, silver/silver chloride as the reference electrode, tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The test was performed in acetonitrile solution. The cyclic voltammetry conditions were: the scan range was-1.8 to 1.8 volts (vs. ag/AgCl) and the scan rate was 50 millivolts per second. The polymer has only oxidation peak, and is a p-type semiconductor material. According to the cyclic voltammogram, the HOMO energy levels of the PBTP-2FBT polymers are respectively-5.44 eV. The LUMO level can be calculated to be-3.65 eV by combining the optical bandgap and the HOMO level.
2) Field effect transistor performance of polymer PBTP-2FBT
Fig. 4 is a schematic structural view of an organic field effect transistor, and as shown in the figure, glass is used as a substrate, and the substrate is subjected to ultrasonic cleaning in secondary water, ethanol and acetone and then is dried in vacuum at 80 ℃. The source and drain electrodes are mask plates, and gold with the thickness of 30nm is used as a source electrode and a drain electrode through thermal evaporation, and the width and the length of a channel are 4500 and 20 mu m respectively. The polymer obtained in example 1 was a semiconductor layer, and an active layer was formed on a glass substrate by a spin coating method using an o-dichlorobenzene solution having a concentration of 10mg/mL, and annealed at a hot stage of 150 ℃ for 10 minutes.
Then, forming 700 nm-thick polymethyl methacrylate on the surface of the polymer film obtained in the embodiment 1 through glue spreading to be used as a dielectric layer of the field effect tube, and removing the solvent for 30 minutes at 90 ℃; and thermally evaporating 90nm thick aluminum on the insulating layer through a mask plate to be used as a gate electrode, and finishing the preparation of the field effect transistor.
The electrical properties of the field effect devices prepared were measured at room temperature with a Keithley 4200SCS semiconductor tester. Two key parameters that determine the performance of OFETs are: carrier mobility (μ) and on-off ratio (I) of the device on /I off ). The mobility refers to the average drift velocity of a carrier (unit is cm) under the action of a unit electric field 2 V -1 s -1 ) It embodies the mobility of holes or electrons in the semiconductor under an electric field. The on-off ratio is defined as: the ratio of the current in the "on" state and the "off" state of the transistor reflects the performance of the device switch. For a high performance field effect transistor, the mobility and switching ratio should be as high as possible.
FIG. 5 is a transfer characteristic curve and an output characteristic curve of a field effect transistor fabricated based on PBTP-2FBT. The polymer field effect transistor exhibits p-type transfer characteristics.
The carrier mobility can be calculated from the equation:
I DS ＝(W/2L)C i μ(V G –V T ) 2 (saturation region)
Wherein, I DS Is the drain current, μ is the carrier mobility, V G Is the gate voltage, V T Is the threshold voltage, W is the channel width, L is the channel length, C i Is an insulator capacitor. By means of I DS 1/2 To V G Plotting, and performing linear regression to obtain carrier mobility (μ) from the slope of the regression line, and determining V from the intercept of the regression line and the X-axis T 。
The mobility can be calculated from the slope of the transfer curve according to the formula, and the device properties of the polymer field effect transistor prepared in each of the above examples are shown in table 1. The switching ratio can be derived from the ratio of the maximum to minimum of the side source-drain currents of fig. 5.
The experimental result shows that the bipyridyl triazole polymer is an excellent novel p-type material. The invention is not limited to the reported materials, a series of polymers can be obtained by changing different side chain substituents, and the synthesis method provided by the invention is simple and efficient, and has good reference significance for synthesizing new semiconductor materials.
TABLE 1 device Performance of Polymer field Effect transistors
Claims (10)
1. The structural general formula of the bipyridyl triazole polymer is shown as formula I:
in the formula I, R is a straight chain or branched chain alkyl with the total number of carbon atoms of 1-40;
ar is selected from any one of the following groups:
wherein the content of the first and second substances,
all represent substitution positions;
n represents the degree of polymerization, and n is an integer of 5 to 100.
2. The bis-pyridotriazole polymer of claim 1, wherein: the structural formula of the polymer shown in the formula I is shown as follows:
wherein R is a linear or branched alkyl group having a total number of carbon atoms of 1 to 40.
3. The bis-pyridotriazole polymer of claim 1 or 2, wherein: r is 5-decyl pentadecyl.
4. The process for preparing a bis-pyridotriazole polymer of claim 1, wherein: the preparation method comprises the following steps:
carrying out polymerization reaction on a compound shown in a formula VII and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown in a formula I;
in formula VII, R is as defined for R in formula I in claim 1;
the double tin compound is selected from any one of the following compounds:
5. the method of claim 4, wherein: the catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine;
the molar ratio of the compound shown in the formula VII to the double-tin compound, the catalyst and the mixture ratio is 1:0.95 to 1.05:0.01 to 0.10: 0.04-0.80.
6. The production method according to claim 4 or 5, characterized in that: in the polymerization reaction, the temperature is 80-140 ℃; the reaction time is 1-80 hours.
7. A compound of formula VII according to claim 4:
in formula VII, R is as defined for R in formula I in claim 1.
8. A process for the preparation of a compound of formula VII as claimed in claim 7, comprising the steps of:
a) Carrying out bromination reaction on the 3, 4-diaminopyridine in a mixed solution of liquid bromine and hydrobromic acid to obtain 2, 5-dibromopyridine-3, 4-diamine shown in a formula II;
b) Reacting the 2, 5-dibromopyridine-3, 4-diamine shown in the formula II obtained in the step a) with sodium nitrite in an acetic acid solution to obtain pyridotriazole shown in the formula III;
c) Reacting the pyridotriazole shown in the formula III obtained in the step b) with R-I and potassium carbonate to obtain a compound shown in a formula IV;
R-I, formula IV, wherein R is as defined for R in formula I of claim 1;
d) Carrying out coupling reaction on the compound shown in the formula IV obtained in the step c) and 2-tributylstannyl thiophene under the catalysis of bis (triphenylphosphine) palladium dichloride to obtain pyridotriazole-thiophene shown in the formula V;
in formula V, R is as defined for R in formula I in claim 1;
e) Coupling the pyridotriazole-thiophene and hexamethyl-ditin obtained in the step d) and shown in the formula V under the catalysis of tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine to obtain the bipyridyl triazole-dithiophene shown in the formula VI;
in formula VI, R is as defined for R in formula I in claim 1;
f) Carrying out bromination reaction on the bipyridyl triazole-bithiophene shown in the formula VI obtained in the step e) to obtain bipyridyl triazole-bithiophene-dibromide shown in the formula VII.
9. Use of a bis-pyridotriazole polymer as claimed in any of claims 1 to 3 in the preparation of an organic field effect transistor.
10. An organic field effect transistor comprising the bis-pyridotriazole polymer of any one of claims 1 to 3 as an organic semiconductor layer.
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| Highly fluorescent triazolopyridine–thiophene D–A–D oligomers for efficient pH sensing both in solution and in the solid state;Jian NN, et al.;《Phys. Chem. Chem. Phys.》;20190304(第21期);7174-7182 * |
| Natural-Killer-Cell-Inspired Nanorobots with Aggregation-Induced Emission Characteristics for Near-Infrared-II Fluorescence-Guided Glioma Theranostics;Deng GJ, et al;《ACS Nano》;20200821(第14期);11452-11462 * |
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