CN105237747B - 2 (3 alkyl) 1,4-Dithiapentalene base ethene polymers and preparation method and application - Google Patents
2 (3 alkyl) 1,4-Dithiapentalene base ethene polymers and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of 2 (3 alkyl) 1,4-Dithiapentalene base ethene polymers and preparation method and application.The structure of 2 (3 alkyl) the 1,4-Dithiapentalene base ethene is as shown in formula I.Present invention also offers the preparation method of polymer shown in formula (I).The synthetic route of the present invention is simple, effective；Raw material is less expensive commercially produced product；Synthetic method has universality.The mobility of the organic field effect tube prepared using 2 (3 alkyl) 1,4-Dithiapentalene base ethene polymers of the invention as organic semiconductor layer is more than 3cm2V‑1s‑1, on-off ratio is more than 106；There is extraordinary application prospect in organic field effect tube device.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of 2- (3- alkyl) 1,4-Dithiapentalene base ethene polymers and preparation method thereof
With application.
Background technology
Field-effect transistor (FET), is a kind of active device for the conductive capability that material is controlled by controlling electric field,
Areas of information technology have been obtained for application widely.Used at present it is most be it is traditional be that inorganic field effect is brilliant
Body pipe, the core of this transistorlike is the semiconductor layer using inorganic material as semiconductor.Organic field effect tube
(Organic field-effect transistors, abbreviation OFETs) is that the organic compound containing Pi-conjugated systems is half
Conductor material is carrier blocking layers.For inorganic field effect collective pipe, organic field effect tube have it is flexible, can
The features such as being prepared, can be processed with solwution method with large area, and possess with low cost, plastic supporting base and have good compatibility etc.
Many good characteristics, promise to be a new generation opto-electronic device and circuit key componentses, smart card, Electronic Paper,
In terms of memory, sensor, electronic trademark, Active Matrix Display, there is high application prospect.Pole is caused in recent years
Pay close attention to, and and achieve than larger progress to be extensive.Organic field effect tube is according to its organic semi-conductor point
Son constitutes difference, can be divided into organic molecule field-effect transistor and organic polymer field-effect transistor.Relative to small point
For son, polymer has adhesion big, the advantages of heat endurance is good, thus has obtained more extensive concern (this master of primary track
Compile functional material chemical progress Beijing：Chemical Industry Press, 2005；Hu Wenping organic field effect tubes Science Press
2011)。
As the core of polymer field effect transistor, the physicochemical property of organic polymer semiconductor material is determined
The transport property of field-effect transistor, we can carry out so as to regulate and control by the structure to polymer in MOLECULE DESIGN
The transport property of polymer field effect transistor.According to carrier transmission characteristics, field effect transistor semiconductor material can be divided into p
Type (carrier is hole) and n-type material (carrier is electronics).The most important performance indications of OFETs include mobility, switch
Than etc..Mobility is to weigh the most important parameter of transmission performance of material carrier, and to be then field-effect transistor exist on-off ratio
A performance indications in practical application.Pass through the polymer backbone to organic polymer semiconductor material and pendant alkyl group chain
The chemical constitution modification and change thought, can be with the mobility of Effective Regulation transistor, on-off ratio, so as to very
Many-side obtains practical application.1,4-Dithiapentalene is the common conjugated molecule of a class, because it possesses higher coplanarity, and
The rigidity of polymer backbone structure can be increased, so as to improve the accumulation of polymer, carrier mobility performance is lifted.Meanwhile, and two
The compounds process for production thereof of thiophene-based is simple and cheap, be widely used the small molecule of organic field effect tube with
And in polymeric material, and obtain the high mobility of comparison (J.Shin, T.R.Hong, T.W.Lee, A.Kim,
Y.H.Kim, M.J.Cho, D.H.Choi, Adv.Mater.2014,26,6031), thus synthesize 1,4-Dithiapentalene derivative and apply
There is highly important theoretical and application value into organic/polymer semiconducting material.
The content of the invention
It is an object of the invention to provide a kind of 2- (3- alkyl) 1,4-Dithiapentalene base ethene polymers and preparation method thereof with answering
With.
2- (3- alkyl) 1,4-Dithiapentalene base ethene polymers provided by the present invention, its general structure shown in formula I,
In the Formulas I, n is 5-100, specially 11-12 or 54-55 or 11-55.
R is C1~C60 straight or branched alkyl, and R' is that the straight or branched alkyl that length is C3~C60 connects.
In above-mentioned Formulas I, R is C10-C60 straight or branched alkyl, specially 2- octyldodecyls, 4- decyls 14
Alkyl.
In above-mentioned Formulas I, R' is that the straight or branched alkyl that length is C3~C60 connects, specially heptyl, octyl group, hendecyl.
The method that what the present invention was provided prepare polymer shown in the Formulas I, comprises the following steps：
By double (5- bromo thiophene -2- bases) -2,5- two (alkyl) pyrrolo- [3,4-c] pyrroles -1,4 of 3,6- shown in Formula II
Ethene is in catalyst and matches somebody with somebody with (E) -1,2- shown in formula III double (5- tin trimethyl -3- alkylthrophene -2- bases) for (2H, 5H)-diketone
Body effect is lower to carry out polymerisation, and reaction, which is finished, obtains polymer shown in the Formulas I；
In the Formula II and formula III, R and R' definition are identical with R in Formulas I and R' definition.
The catalyst is selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides and two (dibenzalacetone) palladiums
At least one of；
The part is selected from least one of triphenylphosphine, three (o-tolyl) phosphines and three (furyl) phosphines.
The molfraction that feeds intake of double (5- tin trimethyl -3- alkylthrophene -2- bases) ethylene reagents of formula III (the E) -1,2-
For 0.95~1.05 part；
Double (5- bromo thiophene -2- bases) -2,5- two (alkyl) pyrrolo- [3,4-c] pyrroles -1,4 of 3,6- shown in the Formula II
The molfraction that feeds intake of (2H, 5H)-diketone is 0.95~1.05 part；
The molfraction that feeds intake of the catalyst is 0.01~0.10 part；
The molfraction that feeds intake of the part is 0.02~0.30 part；
Double (the 5- bromos of 3,6- shown in formula III (the E) -1,2- double (5- tin trimethyl -3- alkylthrophene -2- bases), Formula II
Thiophene -2- bases) -2,5- two (alkyl) pyrrolo- [3,4-c] pyrroles -1,4 (2H, 5H)-diketone, catalyst and feeding intake for part rub
Your amount ratio is specially 1.0：1.0：0.05：0.2.
In the polymerization procedure, temperature is 90~130 DEG C, specially 110 DEG C；
Time is 12 hours~72 hours；
The polymerisation is carried out in a solvent；The solvent is toluene.
In the above method, the double (5- tin trimethyl -3- alkyl of compound shown in the formula III of initiation material (E) -1,2- are used as
Thiophene -2- bases) ethene can be prepared in accordance with the following steps：
(1) 3 bromo thiophene, alkyl acyl chlorides are reacted using aluminum trichloride (anhydrous) as catalyst in chloroform soln, instead
It should finish and obtain 1- (3- bromo thiophene -2- bases) straight chain alkane -1- ketone shown in formula IV；
In above-mentioned formula IV, R' definition is identical with the definition of R' in previously described formula I.
(2) by step 1) 1- (3- bromo thiophene -2- bases) straight chain alkane -1- ketone and ethyl thioglycolate shown in gained formula IV exist
Reacted in the solution of potassium carbonate, reaction, which is finished, obtains simultaneously [3,2-b] the thiophene -2-carboxylic acid ethyl esters of 3- alkylthrophenes shown in Formula V；
In above-mentioned Formula V, R' definition is identical with the definition of R' in previously described formula I.
(3) by step 2) simultaneously [3,2-b] thiophene -2-carboxylic acid ethyl ester and sodium hydroxide exist 3- alkylthrophenes shown in gained Formula V
Reacted in solution, end product obtained after being finished with hydrochloric acid acidizing reaction 3- alkylthrophenes shown in Formula IV simultaneously [3,2-b] thiophene-
2- formic acid；
In above-mentioned Formula IV, R' definition is identical with the definition of R' in previously described formula I.
(4) by step 3) simultaneously [3,2-b] thiophene -2-carboxylic acid is used as catalyst to 3- alkylthrophenes shown in gained Formula IV using copper powder
Reaction, obtains 3- alkylthrophenes shown in Formula VII simultaneously [3,2-b] thiophene after completion of the reaction；
In above-mentioned Formula VII, R' definition is identical with the definition of R' in previously described formula I.
(5) by step 4) simultaneously [3,2-b] thiophene and N- bromo-succinimides are anti-for 3- alkylthrophenes shown in gained Formula VII
Should, bromo- 3- alkylthrophenes of 2- shown in Formula VIII simultaneously [3,2-b] thiophene is obtained after completion of the reaction；
In above-mentioned Formula VIII, R' definition is identical with the definition of R' in previously described formula I.
(6) by step 5) gained Formula VIII shown in the bromo- 3- alkylthrophenes of 2- simultaneously [3,2-b] thiophene with the conditions of -78 DEG C
Reacted with n-BuLi in anhydrous solution, itself and N- formyl piperidines are then obtained into 3- alkylthrophenes shown in Formula IX simultaneously
[3,2-b] thiophene -2-formaldehyde；
In above-mentioned Formula IX, R' definition is identical with the definition of R' in previously described formula I.
(7) by step 6) 3- alkylthrophenes shown in gained Formula IX simultaneously [3,2-b] thiophene -2-formaldehyde and titanium tetrachloride and zinc powder
Intermediate after reaction is reacted in anhydrous solution, and (E) -1, the 2- obtained shown in Formula X is double (3- alkylthrophene -2- bases)
Ethene；
In above-mentioned Formula X, R' definition is identical with the definition of R' in previously described formula I.
8) by step 7) double (3- alkylthrophene -2- bases) ethene of (E) -1,2- shown in the Formula X are -78 in anhydrous solution
Lithium salts after being reacted at DEG C with n-BuLi reacts the double (5- tri- of (E) -1,2- obtained shown in formula III with trimethyltin chloride
Methyl tin -3- alkylthrophene -2- bases) ethene.
The step 1 of the above method) in, the 3 bromo thiophene is commercially produced product, the alkyl acyl of selection with alkyl acyl chlorides
Chlorine is positive caprylyl chloride, positive lauroyl chloride；The 3 bromo thiophene, alkyl chlorine, the mole dosage ratio that feeds intake of aluminum trichloride (anhydrous) are
1：0.9~1.1：0.8~1.0, preferably 1：1.0:0.93；In reactions steps, temperature is 0~5 DEG C, and the time is 1-6 hours；
The step 2) in, 1- (3- bromo thiophene -2- bases) straight chain alkane -1- ketone shown in the formula IV is 1- (3- bromos
Thiophene -2- bases) octane -1- ketone is at least one of to 1- (3- bromo thiophene -2- bases) dodecane -1- ketone.1- (the 3- bromos
Thiophene -2- bases) straight chain alkane -1- ketone and ethyl thioglycolate, the mole dosage ratio that feeds intake of potassium carbonate be 1:1.0~1.1:1.9~
2.1, preferably 1:1.06:2；In reactions steps, temperature is 0~25 DEG C, and the time is 12~48 hours；
The step 3) in, simultaneously [3,2-b] thiophene -2-carboxylic acid ethyl ester is 3- heptyl to the 3- alkylthrophenes shown in the Formula V
Base thieno [3,2-b] thiophene -2-carboxylic acid ethyl ester into 3- undecyls thieno [3,2-b] thiophene -2-carboxylic acid ethyl ester extremely
Few one kind；Simultaneously [3,2-b] thiophene -2-carboxylic acid ethyl ester, the mole dosage ratio that feeds intake of sodium hydroxide are 1 to the 3- alkylthrophenes:2.0
~2.2, preferably 1:2.1；In reactions steps, temperature is 70~120 DEG C, and the time is 5~24 hours, the process being acidified with hydrochloric acid
In, pH is adjusted to 0~1；
The step 4) in, simultaneously [3,2-b] thiophene -2-carboxylic acid is 3- heptyl thiophene to the 3- alkylthrophenes shown in the Formula IV
And [3,2-b] thiophene -2-carboxylic acid is at least one of to 3- undecyls thieno [3,2-b] thiophene -2-carboxylic acid；The 3- alkane
The mole dosage ratio that feeds intake of base thieno [3,2-b] thiophene -2-carboxylic acid and copper powder is 1:2~3, preferably 1:2.75, the reaction time
For 0.5~5h；
The step 5) in, 3- alkylthrophenes shown in the Formula VII simultaneously [3,2-b] thiophene be 3- heptyl thieno [3,
2-b] thiophene is at least one of to 3- hendecyls thieno [3,2-b] thiophene；The 3- alkylthrophenes simultaneously [3,2-b] thiophene with
The mole dosage ratio that feeds intake of N- bromo-succinimides is 1:0.9~1.1, preferably 1:0.97, the reaction time is 2~5h；
The step 6) in, simultaneously [3,2-b] thiophene is 2- bromo- 3- heptan to the bromo- 3- alkylthrophenes of 2- shown in the Formula VIII
Base thieno [3,2-b] thiophene is at least one of to bromo- 3- hendecyls thieno [3,2-b] thiophene of 2-；The bromo- 3- alkane of 2-
Base thieno [3,2-b] thiophene, n-BuLi, the mole dosage ratio that feeds intake of N- formyl piperidines are 1:0.9~1.1：1.2~
1.6, preferably 1:1:1.3, the reaction time is 5-15h；
The step 7) in, simultaneously [3,2-b] thiophene -2-formaldehyde is long alkyl chains to the 3- alkylthrophenes shown in the Formula IX
From C3~C11 i.e. from 3- propyl group thieno [3,2-b] thiophene -2-formaldehyde to 3- hendecyls thieno [3,2-b] thiophene -2-formaldehyde
At least one of；The mole dosage ratio that feeds intake of the 3- alkylthrophenes simultaneously [3,2-b] thiophene -2-formaldehyde, titanium tetrachloride, zinc powder
For 1:1.9~2.1:3.9~4.1, preferably 1:2:4；
The step 8) in, double (3- alkylthrophene -2- bases) ethene of (E) -1,2- shown in the Formula X are (E) -1,2- double
(3- heptyl thiophene -2- bases) ethene is at least one of to double (the 3- hendecyl thiophene -2- bases) ethene of (E) -1,2-；(E)-
Double (3- alkylthrophene -2- bases) ethene of 1,2-, n-BuLi, the mole dosage ratio that feeds intake of trimethyltin chloride are 1:1.0~
2.5:1~5, preferably 1:2.1:4.2, the reaction time is 10-25h.
Above-mentioned steps 1) to step 8) reaction carries out in a solvent.The step 1) in, the solvent is trichlorine
Methane；The step 2) in, the solvent is N, N '-dimethyl formamide；The step 3) in, the solvent is ethanol；Institute
State step 4) in, the solvent is quinoline；The step 5) in, the solvent is chloroform；The step 6) to step 8)
In, the solvent is anhydrous tetrahydro furan.
The synthetic route of the above method is as shown in Figure 6.
In addition, application of the polymer in organic effect transistor is prepared shown in the Formulas I that the invention described above is provided and with Formulas I
Shown polymer is the organic field effect tube of semiconductor layer, falls within protection scope of the present invention.
The advantage of the invention is that：
1st, synthetic method has universality, simple efficient；Raw material is commercially produced product；Can be with the conjunction in popularization and application industry
Into；
2nd, polymer molecule backbone has good dissolubility, is conducive to the solwution method of the polymer to process, available for making
The organic field effect tube device of standby low cost high mobility；
3rd, 2- (3- alkyl) 1,4-Dithiapentalene base polyvinyl molecules have smaller band gap, and stronger the common of skeleton is put down
Face property, and higher photo and thermal stability, are expected to be applied in other photoelectric devices；
4. it is brilliant using the organic effect that 2- of the present invention (3- alkyl) 1,4-Dithiapentalene base ethene polymers is prepared as semiconductor layer
The mobility (μ) and on-off ratio of body pipe are all very high, and (μ is more than 3cm2V-1s-1, on-off ratio is more than 104), in organic effect crystal
There is extraordinary application prospect in pipe.
Brief description of the drawings
Fig. 1 is with 2- (3- alkyl) the 1,4-Dithiapentalene bases polyvinyl ultraviolet-visible absorption spectroscopy of the invention provided
Figure.
Fig. 2 is with 2- (3- alkyl) the 1,4-Dithiapentalene base polyvinyl cyclic voltammetry curve figure of the invention provided.
The structure of 2- (3- alkyl) the 1,4-Dithiapentalene base ethene polymers field-effect transistors of Fig. 3 to be provided with the present invention is shown
It is intended to.
Fig. 4 is the polymerization object field using 2- (3- alkyl) the 1,4-Dithiapentalene base ethene polymers of the invention provided as semiconductor layer
The output characteristic curve figure of effect transistor.
Fig. 5 is the polymerization object field using 2- (3- alkyl) the 1,4-Dithiapentalene base ethene polymers of the invention provided as semiconductor layer
The transfer characteristic curve figure of effect transistor.
The synthetic route of compound shown in the formula I that Fig. 6 provides for the present invention.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.
In following embodiments, double (5- bromo thiophene -2- bases) -2,5- bis- (alkyl) pyrrolo-es of 3,6- in the Formula II used
[3,4-c] pyrroles -1,4 (2H, 5H)-diketone synthesis step synthesize according to literature method (Advanced Materials, 2012,
24,4618–4622)。
Double (2- the octyldodecyls)-pyrrolo-es of double (5- bromothiophene -2- the bases) -2,5- of embodiment 1, polymer poly 3,6-
Double (the 3- heptyl thiophene -2- bases) ethene (PD-8-THE) of [3,4-c] pyrroles -1,4- diketone (E) -1,2-
1) synthesis of 1- (3- bromo thiophene -2- bases) octane -1- ketone
Under ice bath, 3 bromo thiophene (24.6g, 151mmol), positive caprylyl chloride (24.58g, 151mmol) are dissolved in 300mL
Added in batches in chloroform, in 0.5h under aluminum trichloride (anhydrous) (18.7g, 140mmol), ice bath and stir 2h, remove ice bath,
5h is stirred at room temperature, reaction is poured into substantial amounts of frozen water, is filtered, and filtrate is extracted with dichloromethane, then uses saturated aqueous common salt
Washing three times, is spin-dried for obtaining light yellow liquid 1- (3- bromo thiophene -2- bases) nonane -1- ketone (22.42g, 77.5mmol), the production
Thing can directly cast single step reaction without purification.Under the atmosphere of nitrogen, by 1- (3- bromo thiophene -2- bases) nonane -1-
Ketone, ethyl thioglycolate (9.86mL, 82.1mmol), potassium carbonate (20g, 145mmol) is dissolved in 150mL DMF, system room temperature
24h is stirred, reaction system is changed into yellow.Reaction solution is poured into a large amount of water, ethyl acetate extraction, saturated sodium-chloride water solution
Washing.Organic phase after anhydrous sodium sulfate drying with being spin-dried for, and crude product over-subtraction compression leg is crossed out forward position impurity with petroleum ether, finally used
Ethyl acetate rinse, obtains light yellow liquid 16.8g, and yield 70%, product can directly throw next step without purification.
2) synthesis of 3- heptyl thieno [3,2-b] thiophene
By 3- octyl thiophenes simultaneously [3,2-b] thiophene -2-carboxylic acid ethyl ester (12.3g, 39.6mmol), sodium hydroxide (3.30g,
82.5mmol) add in 125mL ethanol, flow back 12h, is subsequently poured into a large amount of water, with the aqueous hydrochloric acid solution of 1 mole every liter (1M)
PH to 1 is neutralized, reactant mixture is filtered, filtrate is washed with a large amount of cold water, is dried in vacuo at 70 DEG C, obtains yellow solid 3-
Octyl thiophene simultaneously [3,2-b] thiophene -2-carboxylic acid 9.84g, yield 88%.Into 200mL single port bottles, 3- octyl thiophenes are added simultaneously
[3,2-b] thiophene -2-carboxylic acid, copper powder (6.24g, 96mmol), 70mL quinoline, flow back 1h, is down to after room temperature solution pouring into 1M
Aqueous hydrochloric acid solution in, with petroleum ether extraction, anhydrous sodium sulfate drying.Solvent uses silica gel chromatograph post separation, eluent after being evaporated
For petroleum ether, it is spin-dried for solvent and obtains colourless oil liquid 7.90g, yield 88%.
Structural characterization data are as follows：
Mass spectrum：[MS(EI)]m/z:238.0851.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 7.39 (dd, J=5.1,1.5Hz, 1H),
6.99 (d, J=5.4Hz, 1H), 2.73 (t, J=7.5Hz, 2H), 1.75 (tt, J=7.5,7.5Hz, 2H), 1.29-1.34
(br, 8H), 0.88 (t, J=6.9Hz, 3H) .13C-NMR (75MHz, CD2Cl2):δ139.95,138.69,134.98,
126.63,121.78,119.87,31.80,29.86,29.31,29.06,28.65,22.67,13.86.
3) synthesis of bromo- 3- heptyl thieno [3,2-b] thiophene of 2-
Under ice cooling, 4, by 3- octyl thiophenes simultaneously [3,2-b] thiophene (1.48g, 6.20mmol) to be dissolved in 50mL chloroforms molten
In liquid, N- bromo-succinimides (1.07g, 6.01mmol) are then added portionwise into solution.The lower stirring 1h of ice bath cooling, is removed
Go that 2h is stirred at room temperature after ice bath.Solution is poured into water, extracted with dichloromethane, anhydrous magnesium sulfate is dried.After solvent is evaporated
Silica gel chromatograph post separation is used, eluent is petroleum ether, be spin-dried for solvent and obtain colourless oil liquid 1.53g, yield 78%.
Mass spectrum：[HR-MS(EI)]m/z：315.9958(79Br),317.9953(81Br)。
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(400MHz,CD2Cl2):δ (ppm) 7.48 (d, J=8Hz, 1H), 7,24 (d, J
=8Hz, 1H), 2.81 (t, J=7.5Hz, 2H), 1.75 (tt, J=8,8Hz, 2H), 1.29-1.34 (br, 8H), 0.94 (t, J
=16Hz, 3H) .13C-NMR (101MHz, CD2Cl2):δ138.35,136.61,134.32,125.93,119.54,109.92,
31.85,29.20,29.09,28.99,27.87,22.62,13.82.
4) synthesis of 3- heptyl thieno [3,2-b] thiophene -2-formaldehyde
Under nitrogen atmosphere, by the bromo- 3- octyl thiophenes of 2- simultaneously [3,2-b] thiophene (7.1g, 22.3mmol) be dissolved in it is anhydrous
In 250mL tetrahydrofurans.The system is down to -78 DEG C, 2.5M n-BuLis 8.95mL (22.3mmol), system is added dropwise
Stirred at -78 DEG C after 1h, disposably squeeze into N- formyl piperidines (3.3g, 28.99mmol).Reaction nature is warming up to room temperature,
Stir 12h.Add water quenching to go out reaction, ethyl acetate is extracted, anhydrous sodium sulfate drying.Solvent is divided after being evaporated with silica gel chromatographic column
From eluent is petroleum ether：Ethyl acetate=6:1, it is spin-dried for solvent and obtains pale yellowish oil liquid 4.93g, yield 83%.
Mass spectrum：[HR-MS(EI)]m/z:266.0801.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(400MHz,CD2Cl2):δ (ppm) 10.11 (s, 1H), 7.66 (d, J=
5.4Hz, 1H), 7,31 (d, J=5.4Hz, 1H), 2.77 (t, J=7.5Hz, 2H), 1.76 (tt, J=5.4,8Hz, 2H),
1.29-1.34 (br, 8H), 0.88 (t, J=7.8Hz, 3H) .13C-NMR (75MHz, CD2Cl2):δ145.08,144.36,
141.10,139.93,132.92,120.53,36.33,31.56,31.20,30.99,29.67,26.73,15.92.
5) synthesis of double (the 3- heptyl thiophene -2- bases) ethene of (E) -1,2-
Under nitrogen atmosphere, zinc powder (2.35g, 36mmol) is added in 100mL anhydrous tetrahydro furans.Then by the body
System is down to 0 DEG C, is slowly dropped into 19mL 1M titanium tetrachlorides (19mmol).Room temperature is down to after solution backflow 5h, 3- is disposably added
Octyl thiophene simultaneously [3,2-b] thiophene -2-formaldehyde (2.4g, 9mmol), is then refluxed for 12h.It is down to after room temperature, is added into system
The aqueous solution of saturated sodium carbonate, mixture suction filtered through kieselguhr, filtrate is extracted with dichloromethane, anhydrous sodium sulfate drying.Solvent
Silica gel chromatograph post separation is used after being evaporated, eluent is petroleum ether, be spin-dried for solvent and obtain light yellow solid 1.35g, yield 60%.
Mass spectrum：[HR-MS(EI)]m/z:500.169582.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 7.31 (d, J=5.1Hz, 2H), 7.14 (d,
J=5.1Hz, 2H), 7.01 (s, 2H), 2.75 (t, J=7.5Hz, 4H), 1.75 (tt, J=7.5,7.2Hz, 4H), 1.21-
1.29 (br, 16H), 0.79 (t, J=6.6Hz, 6H) .13C NMR (75MHz, CD2Cl2):δ141.48,138.33,135.76,
133.02,127.07,119.89,119.82,31.78,29.39,29.29,29.07,28.17,22.67,13.85。
6) synthesis of double (5- tin trimethyl -3- heptyl thiophene -2- bases) ethene of (E) -1,2-
Under nitrogen atmosphere, by (E) -1, double (3- octyl thiophene -2- bases) ethene (1g, 1.99mmol) of 2- be dissolved in 40mL without
In water tetrahydrofuran, the system is then cooled to -78 DEG C, 1.67mL 2.5M n-BuLis (4.19mmol) are added dropwise.
Then system is warming up at -60 DEG C, after stirring 1h, is cooled to -78 DEG C, disposably squeezes into 8.2mL 1M trimethyl chlorine
Change tin (8.2mmol).System is warmed to room temperature after reaction 12h, reaction, mixed liquor ether is quenched in the aqueous solution for adding potassium fluoride
Extraction, anhydrous sodium sulfate drying.It is spin-dried for solvent recrystallization and obtains glassy yellow needle-like solid 1.16g, yield 70%.
Mass spectrum：[HR-MS(EI)]m/z:826.099745.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ(ppm)7.16(s,2H),6.99(s,2H),2.74
(t, J=7.5Hz, 4H), 1.65 (tt, J=7.2,7.5Hz, 4H), 1.21-1.29 (br, 16H), 0.80 (t, J=6.9Hz,
6H),0.33(s,18H).13C NMR(75MHz,CD2Cl2):δ146.98,141.62,138.33,137.54,132.54,
126.94,119.83,31.80,29.41,29.32,29.08,28.28,22.69,13.87,-8.53.
7) PD-8-THE synthesis (n=54~55)
By double (5- bromothiophene -2- bases) -2,5- two (octyldodecyl) pyrrolo- [3,4-c] pyrroles of 3,6- shown in Formula II
Cough up the double (5- tin trimethyl -3- octyl group thiophenes of -1,4- diketone (BrTDPP) (203.8mg, 0.2mmol), (E) -1,2- shown in formula III
Fen -2- bases) ethene (163.3mg, 0.2mmol), three (dibenzalacetone) two palladium (9mg, 0.01mmol), three (o-tolyls)
Phosphine (12.3mg, 0.04mmol) and toluene (5mL) are added in reaction bulb, and three freezing-pumping-defrostings are carried out in argon gas and are followed
Ring deoxygenation, is then heated to 110 DEG C of reaction 24h by reactant mixture.After cooling, 200mL methanol/6M HCl mixtures are added
(v/v 20:1) 2h, is stirred at room temperature, is filtered.Obtained polymer loads apparatus,Soxhlet's extracting.First with methanol, acetone, just
Hexane, chloroform are extracted to colourless, remove small molecule and catalyst, then obtain final product 333.5mg with chlorobenzene extraction, are produced
Rate 91%.Polymer architecture is as shown in Formula X I.
Molecular weight：GPC:Mn=74kDa, PDI=2.75.
Nucleus magnetic hydrogen spectrum：1H NMR(300MHz,CDCl3)δ(ppm):8.98(br,2H),6.99(br,1H),6.69(br,
1H),0.89-1.32(m,55H)。
Double (2- decyls the myristyl)-pyrrolo-es of double (5- bromothiophene -2- the bases) -2,5- of embodiment 2, polymer poly 3,6-
Double (the 3- hendecyl thiophene -2- bases) ethene (PD-10-UHE) of [3,4-c] pyrroles -1,4- diketone (E) -1,2-
1) synthesis of 1- (3- bromo thiophene -2- bases) dodecane -1- ketone
Under ice bath, 3 bromo thiophene (24.6g, 151mmol), positive lauroyl chloride (33.03g, 151mmol) are dissolved in
Added in batches in 300mL chloroforms, in 0.5h under aluminum trichloride (anhydrous) (18.7g, 140mmol), ice bath and stir 2h, removed
Ice bath, stirs 5h at room temperature, and reaction is poured into substantial amounts of frozen water, and filtering, filtrate is extracted with dichloromethane, then eaten with saturation
Salt water washing three times, is spin-dried for obtaining light yellow liquid 1- (3- bromo thiophene -2- bases) nonane -1- ketone (24.96g, 72.3mmol),
The product can directly cast single step reaction without purification.Under the atmosphere of nitrogen, by 1- (3- bromo thiophene -2- bases) nonyl
Alkane -1- ketone, ethyl thioglycolate (8.68mL, 72.3mmol), potassium carbonate (20g, 145mmol) is dissolved in 150mL DMF, system
24h is stirred at room temperature, reaction system is changed into yellow.Reaction solution is poured into a large amount of water, ethyl acetate extraction, saturated sodium-chloride water
Solution is washed.Organic phase after anhydrous sodium sulfate drying with being spin-dried for, and crude product over-subtraction compression leg crosses out forward position impurity with petroleum ether, most
Ethyl acetate rinse is used afterwards, light yellow liquid is obtained, and product can directly throw next step 17.27g, yield without purification
65%.
2) synthesis of 3- hendecyls thieno [3,2-b] thiophene
By 3- hendecyls thieno [3,2-b] thiophene -2-carboxylic acid ethyl ester (14.51g, 39.6mmol), sodium hydroxide
(3.30g, 82.5mmol) is added in 125mL ethanol, and flow back 12h, is subsequently poured into a large amount of water, with the salt of 1 mole every liter (1M)
With pH to 1 in aqueous acid, reactant mixture is filtered, filtrate is washed with a large amount of cold water, be dried in vacuo at 70 DEG C, obtain Huang
Color solid 3- octyl thiophenes simultaneously [3,2-b] thiophene -2-carboxylic acid 11.39g, yield 85%.Into 200mL single port bottles, 3- is added pungent
Base thieno [3,2-b] thiophene -2-carboxylic acid, copper powder (6.02g, 92.7mmol), 70mL quinoline, flow back 1h, and being down to after room temperature will
Solution is poured into 1M aqueous hydrochloric acid solution, with petroleum ether extraction, anhydrous sodium sulfate drying.Solvent is divided after being evaporated with silica gel chromatographic column
From eluent is petroleum ether, is spin-dried for solvent and obtains colourless oil liquid 7.89g, yield 80%.
Structural characterization data are as follows：
Mass spectrum：[HR-MS(EI)]m/z:294.1472.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 7.34 (d, J=3.9Hz, 1H), 7.23 (d,
J=5.1Hz, 1H), 2.71 (t, J=4.5Hz, 2H), 1.35 (tt, J=7.2,7.5Hz, 2H), 1.26-1.33 (br, 16H),
0.88 (t, J=4.5Hz, 6H) .13C NMR (75MHz, CD2Cl2):δ139.97,138.72,134.97,126.61,
121.79,119.86,31.97,29.91,29.62,29.43,29.40,28.67,22.74,13.94。
3) synthesis of bromo- 3- hendecyls thieno [3,2-b] thiophene of 2-
Under ice cooling, 4,3- hendecyls thieno [3,2-b] thiophene (1.83g, 6.20mmol) is dissolved in 50mL chloroforms
In solution, N- bromo-succinimides (1.07g, 6.01mmol) are then added portionwise into solution.The lower stirring 1h of ice bath cooling,
Remove and 2h is stirred at room temperature after ice bath.Solution is poured into water, extracted with dichloromethane, anhydrous magnesium sulfate is dried.Solvent is evaporated
Silica gel chromatograph post separation is used afterwards, eluent is petroleum ether, be spin-dried for solvent and obtain colourless oil liquid 1.94g, yield 84%.
Mass spectrum：[HR-MS(EI)]m/z:372.0586(79Br),374.0567(81Br)。
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 7.47 (d, J=5.1Hz, 1H), 7.23 (d,
J=5.1Hz, 1H), 2.78 (t, J=7.5Hz, 2H), 1.74 (tt, J=7.2,7.5Hz, 2H), 1.30-1.38 (br, 16H),
0.92 (t, J=6.6Hz, 6H) .13C NMR (75MHz, CD2Cl2):δ:138.37,136.85,134.26,125.98,
119.44,109.93,31.92,29.63,29.52,29.34,29.25,29.10,28.01,22.70,13.90。
4) synthesis of 3- hendecyls thieno [3,2-b] thiophene -2-formaldehyde
Under nitrogen atmosphere, by the bromo- 3- octyl thiophenes of 2-, simultaneously [3,2-b] thiophene (8.33g, 22.3mmol) is dissolved in 250mL
In anhydrous tetrahydro furan.The system is down to -78 DEG C, 2.5M n-BuLis 8.95mL (22.3mmol), system is added dropwise
Stirred at -78 DEG C after 1h, disposably squeeze into N- formyl piperidines (3.3g, 28.99mmol).Reaction nature is warming up to room temperature,
Stir 12h.Add water quenching to go out reaction, ethyl acetate is extracted, anhydrous sodium sulfate drying.Solvent is divided after being evaporated with silica gel chromatographic column
From eluent is petroleum ether：Ethyl acetate=6:1, it is spin-dried for solvent and obtains pale yellowish oil liquid 5.39g, yield 75%.
Mass spectrum：[HR-MS(EI)]m/z:322.1427.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 10.11 (s, 1H), 7.66 (d, J=
5.1Hz, 1H), 7.31 (d, J=5.1Hz, 1H), 3.12 (t, J=7.5Hz, 2H), 1.81 (tt, J=7.2,7.5Hz, 2H),
1.25-1.31 (br, 16H), 0.87 (t, J=6.3Hz, 3H) .13C NMR (75MHz, CD2Cl2):δ:182.74,145.39,
144.75,141.76,131.28,120.74,33.97,30.63,29.72,29.64,29.35,29.17,28.99,22.70,
14.31。
5) synthesis of double (the 3- hendecyl thiophene -2- bases) ethene of (E) -1,2-
Under nitrogen atmosphere, zinc powder (2.35g, 36mmol) is added in 100mL anhydrous tetrahydro furans.Then by the body
System is down to 0 DEG C, is slowly dropped into 19mL 1M titanium tetrachlorides.Room temperature is down to after solution backflow 5h, it is disposable to add 3- hendecyl thiophenes
Fen simultaneously [3,2-b] thiophene -2-formaldehyde (2.9g, 9mmol), is then refluxed for 12h.It is down to after room temperature, saturated carbon is added into system
The aqueous solution of sour sodium, mixture suction filtered through kieselguhr, filtrate is extracted with dichloromethane, anhydrous sodium sulfate drying.After solvent is evaporated
Silica gel chromatograph post separation is used, eluent is petroleum ether, be spin-dried for solvent and obtain light yellow solid 1.85g, yield 67%.
Mass spectrum：[HR-MS(EI)]m/z:612.294658.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ (ppm) 7.38 (d, J=5.1Hz, 1H), 7.21 (d,
J=5.4Hz, 1H), 7.09 (s, 1H), 2.83 (t, J=7.5Hz, 2H), 1.73 (tt, J=7.2,7.5Hz, 2H), 1.25-
1.36 (br, 16H), 0.86 (t, J=6.3Hz, 6H) .13C NMR (75MHz, CD2Cl2):δ:144.31,137.79,
135.28,133.97,129.97,123.90,116.82,31.87,29.65,29.59,29.53,29.37,29.32,29.20,
28.29,22.62,14.07。
6) synthesis of double (5- tin trimethyl -3- hendecyl thiophene -2- bases) ethene of (E) -1,2-
Under nitrogen atmosphere, by (E) -1, double (the 3- hendecyl thiophene -2- bases) ethene (1.23g, 1.99mmol) of 2- are dissolved in
In 40mL anhydrous tetrahydro furans, the system is then cooled to -78 DEG C, 1.67mL 2.5M n-BuLis are added dropwise
(4.19mmol).Then system is warming up at -60 DEG C, after stirring 1h, is cooled to -78 DEG C, disposably squeezes into 8.2mL 1M
Trimethyltin chloride (8.2mmol).System is warmed to room temperature after reaction 12h, reaction is quenched in the aqueous solution for adding potassium fluoride, mixed
Close liquid to be extracted with ether, anhydrous sodium sulfate drying.It is spin-dried for solvent recrystallization and obtains glassy yellow needle-like solid 1.27g, yield 68%.
Mass spectrum：[HR-MS(EI)]m/z:938.224637.
Nucleus magnetic hydrogen spectrum and carbon spectrum：1H-NMR(300MHz,CDCl3):δ(ppm)7.24(d,1H),7.07(d,1H),2.82
(t, J=7.2Hz, 2H), 1.70 (tt, J=7.2,7.5Hz, 2H), 1.25-1.37 (br, 16H), 0.87 (t, J=3.3Hz,
3H).13C NMR(75MHz,CD2Cl2):δ:147.10,141.01,138.48,137.47,132.34,126.94,119.88,
31.89,29.67,29.62,29.55,29.40,29.35,29.21,28.31,22.67,14.10,-8.21。
7) PD-10-UHE synthesis (n=11~12)
By double (5- bromothiophene -2- bases) -2,5- two (decyl myristyl) pyrrolo- [3,4-c] pyrroles of 3,6- shown in Formula II
Cough up the double (5- tin trimethyl -3- hendecyls of -1,4- diketone (BrTDPP) (226.3mg, 0.2mmol), (E) -1,2- shown in formula III
Thiophene -2- bases) ethene (187.7mg, 0.1mmol), three (dibenzalacetone) two palladium (9mg, 0.01mmol), three (adjacent toluene
Base) phosphine (12.3mg, 0.04mmol) and toluene (5mL) is added in reaction bulb, and three freezing-pumping-solutions are carried out in argon gas
Freeze circulation deoxygenation, reactant mixture is then heated to 110 DEG C of reaction 24h.After cooling, 200mL methanol/6M HCl mixing is added
Thing (v/v 20:1) 2h, is stirred at room temperature, is filtered.Obtained polymer loads apparatus,Soxhlet's extracting.First with methanol, acetone,
N-hexane, chloroform are extracted to colourless, remove small molecule and catalyst, then obtain final product 234.7mg with chlorobenzene extraction,
Yield 93%.Polymer architecture is as shown in Formula X II.
Molecular weight：GPC:Mn=18.2kDa, PDI=2.91.
Nucleus magnetic hydrogen spectrum：1H NMR(300MHz,CDCl3)δ(ppm):9.04(br,2H),7.10(br,1H),6.65(br,
1H),0.81-1.32(m,71H)。
Embodiment 3, the gained compound PD-8-THE of embodiment 1 and the gained PD-10-UHE of embodiment 2 spectrum property and field
Effect transistor performance
1) compound PD-8-THE and PD-10-UHE spectrum and chemical property
Fig. 1 is the ultraviolet-visible absorption spectroscopy of compound PD-8-THE and PD-10-UHE in solution and film.
As shown in Figure 1, PD-8-THE optical band gap is 1.56eV, and PD-10-UHE optical band gap is 1.60eV.This is several
Planting polymer has stronger Intramolecular electron transfer peak, shows that the frontier orbit of the main polymer chain is overlapping more preferably.
Fig. 2 is compound PD-8-THE and PD-10-UHE cyclic voltammetry curve.Determine in CHI660c electrochemical operations
Stand progress, tested with traditional three-electrode structure.Test is carried out in dichloromethane solution.
2) compound PD-8-THE and PD-10-UHE field-effect transistor performance
Fig. 3 is the structural representation of organic field effect tube, as illustrated, using highly doped silicon chip as substrate and grid electricity
Pole, the silica of 300 nanometer thickness is insulating barrier, and gold is source electrode and drain electrode.Source-drain electrode is prepared using the method for photoetching,
Substrate is cleaned by ultrasonic in acetone, secondary water, ethanol after 80 DEG C of vacuum drying successively, and with corona treatment 15 minutes.
Then activated silica surface is modified with octadecyl tri-chlorination silane (OTS), the gained Formulas I of embodiment 1
Polymer P D-10-UHE shown in shown polymer P D-8-TH or the gained Formulas I of embodiment 2 is semiconductor layer.Polymeric material is molten
Film thickness is formed for 40nm in the substrate that OTS is modified by the method for rejection film in o-dichlorohenzene), and annealed in thermal station
5 minutes.The electrical properties of prepared FET device use the SCS semiconductor tests of Keithley 4200 at room temperature
Instrument is measured.
Most important two parameters of OFET performances are：The mobility (μ) and the on-off ratio (I of device of carrieron/Ioff)。
Mobility refers to：Under unit electric field, (unit is cm to the average mobility speed of carrier2V-1s-1), it is reflected under the electric field
Carrier such as hole or electronics transfer ability in the semiconductors.The definition of on-off ratio is：Transistor in "On" state and
The ratio between electric current under "Off" state, it directly reflects the quality of devices switch performance.One has high-performance and can use real
The field-effect transistor of border application, should be with as high as possible mobility and on-off ratio.
Fig. 4 is transfer characteristic curve and output characteristic curve based on the field-effect transistor prepared by PD-8-THE.Fig. 5
For transfer characteristic curve and output characteristic curve based on the field-effect transistor prepared by PD-10-UHE.Two polymerization object fields
Effect transistor shows good linear zone and saturation region, illustrates that there is the OFET devices based on THE and UHE good field to imitate
Answer performance of control.
Carrier mobility can be calculated by equation：
IDS=(W/2L) Ciμ(VG–VT)2(saturation region, VDS=VG–VT)
Wherein, IDSFor drain current, μ is carrier mobility, VGFor grid voltage, VTFor threshold voltage, W is that raceway groove is wide
Spend (W=1400 microns), L is channel length, CiFor insulation body capacitance (unit-area capacitance (SiO2Relative dielectric constant 3.9,
SiO2Layer 300nm).Utilize (IDS, sat)1/2To VGMapping, and make linear regression, can the slope of the thus tropic extrapolate current-carrying
Transport factor (μ), V is tried to achieve by the section of the tropic and X-axisT.Mobility can be calculated according to formula from the slope of transfer curve
Draw, the device performance of the polymer field effect transistor prepared in above-mentioned each example is as shown in table 1.
On-off ratio can be drawn by the ratio between maxima and minima of Fig. 4 source-drain currents.
Multiple organic field effect tube devices have been made by organic layer of PD-8-THE the and PD-10-UHE polymer of synthesis
Part, in these devices, PD-8-THE mobility is 4.70cm2V-1s-1, PD-10-UHE is 3.09cm2V-1s-1。
Test result indicates that using the polymer of 2- (3- alkyl) 1,4-Dithiapentalene base ethene as framework unit be excellent polymerization
Thing semi-conducting material.The present invention is not limited to the two materials reported, one can be obtained by changing different side chain substituents
The polymer of series, and the synthetic method that provides of the present invention is simple, effectively, for Study Polymer Melts semi-conducting material structure with
The relation of performance helps huge, has highly important directive significance to further designing and preparing high performance material.
Claims (11)
1. polymer shown in Formulas I,
In the Formulas I, R is C1~C60Straight or branched alkyl, R' is the straight or branched alkyl chain that length is C3~C60；
N is 5-100.
2. polymer according to claim 1, it is characterised in that：In the Formulas I, R is C10-C60Straight or branched alkane
Base；
R' is heptyl, octyl group, nonyl or hendecyl.
3. polymer according to claim 2, it is characterised in that：In the Formulas I, R is 2- octyldodecyls or the 4- last of the ten Heavenly stems
Base myristyl.
4. a kind of method for preparing polymer shown in Formulas I described in claim 1, comprises the following steps：
Formula II compound and compound shown in formula III are subjected to polymerisation under catalyst and part effect, reaction is finished
To polymer shown in the Formulas I；
In the Formula II and formula III, R and R' definition are identical with R in Formulas I in claim 1 and R' definition.
5. method according to claim 4, the catalyst is selected from tetrakis triphenylphosphine palladium, three (dibenzalacetones) two
At least one of palladium and two (dibenzalacetone) palladiums；
The part is selected from least one of triphenylphosphine, three (o-tolyl) phosphines and three (furyl) phosphines.
6. the method according to claim 4 or 5, it is characterised in that：The molfraction that feeds intake of compound shown in the formula III
For 0.95~1.05 part；
The molfraction that feeds intake of compound shown in the Formula II is 0.95~1.05 part；
The molfraction that feeds intake of the catalyst is 0.01~0.10 part；
The molfraction that feeds intake of the part is 0.02~0.30 part.
7. method according to claim 6, it is characterised in that：Compound shown in shown formula III, compound shown in Formula II,
The mole dosage ratio that feeds intake of catalyst and part is 1.0：1.0：0.05：0.2.
8. the method according to claim 4 or 5, it is characterised in that：In the polymerization procedure, temperature be 90 DEG C~
130℃；
Time is 12 hours~72 hours；
The polymerisation is carried out in a solvent.
9. method according to claim 8, it is characterised in that：The solvent is selected from least one of toluene and chlorobenzene.
10. application of the polymer in organic effect transistor is prepared shown in any Formulas I of claim 1-3.
11. a kind of organic field effect tube, it is characterised in that：In the organic field effect tube, semiconductor layer is constituted
Polymeric material is polymer shown in any Formulas I of claim 1-3.
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