CN102816297A - Polymer based on biphenyl thiadiazole, and preparation method and application thereof - Google Patents
Polymer based on biphenyl thiadiazole, and preparation method and application thereof Download PDFInfo
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- UCPSYIFWVQSBJN-UHFFFAOYSA-N Cc1cc([Si+](C)c2c-3[s]c(C)c2)c-3[s]1 Chemical compound Cc1cc([Si+](C)c2c-3[s]c(C)c2)c-3[s]1 UCPSYIFWVQSBJN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a polymer based on biphenyl thiadiazole, a preparation method and application of the polymer serving as an active layer material to organic electronic devices such as solar batteries, field effect transistors and light-emitting diodes. The polymer based on the biphenyl thiadiazole can be processed in a solution method and has good carrier transmission capability, sunlight capturing capability and heat stability, and accordingly the polymer is an ideal material for the organic electronic devices. The structure of the polymers is represented as general formula as follows.
Description
Technical field
The present invention relates to one type based on polymkeric substance of biphenyl and thiadiazoles and preparation method thereof and this base polymer as the application of active layer material in organic electronic devices such as solar cell (OPV), field-effect transistor (OFET) and photodiode (OLED).
Background technology
The history in existing more than 30 year of organic semi-conductor development is compared with traditional inorganic semiconductor device with the device that they are processed, and has following several advantage: but low-cost, ultra-thin, in light weight, the simple large-area preparation of manufacture craft etc.In view of these advantages, people entertain great interest to organic semi-conductor research.Organic semi-conductor research generally comprises the synthetic and preparation of devices of design of semiconductor material.Organic semiconductor device mainly includes the machine solar cell, organic field effect tube, Organic Light Emitting Diode, device for non-linear optical and storer etc.Organic solar batteries research begins relatively early, but the efficient of early stage battery is not high, once is not expected.Invented the organic solar batteries of double-deck heterojunction structure up to Tang in 1986, its device efficiency has reached 1%, and this indicates that just the development of organic solar batteries has got into a new stage.Subsequently, people have developed the more effectively organic solar batteries of body heterojunction structure of chargeseparated again, and its device efficiency has obtained further raising.Up to the present, with polymkeric substance for to body, with fullerene derivate (like PC
71BM) be the organic solar batteries of the body heterojunction structure of acceptor, its top efficiency is 7～8% (Y.Liang, Z.Xu, J.Xia; S-T. Tsai, Y.Wu, G.Li; C.Ray, L.Yu, " For the Bright Future-Bulk Heterojunction Polymer Solar Cells with Power Conversion Efficiency of 7.4% "; Adv.Mater.2010,22, E135; H-Y.Chen, J.Hou, S.Zhang, Y.Liang, G.Yang; Y.Yang, L.Yu, Y. Wu, G.Li, " Polymer solar cells with enhanced open-circuit voltage and efficiency "; Nature Photonics, 2009,3,649; S.C.Price, A.C.Stuart, L.Yang; H. Zhou, W.You, " Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer-Fullerene Solar Cells "; J.Am.Chem.Soc.; 2011,133,4625; T-Y.Chu, J.Lu, S.Beaupr é, Y. Zhang, J-R.Pouliot, S.Wakim; J.Zhou, M.Leclerc, Z.Li, J.Ding, Y.Tao, " Bulk Heterojunction Solar Cells Using Thieno [3; 4-c] pyrrole-4,6-dione and Dithieno [3,2-b:2 ', 3 '-d] silole Copolymer with a Power Conversion Efficiency of 7.3% ", J.Am.Chem.Soc.; 2011,133,4250), be to body with small molecules, PC
71BM is that its top efficiency of organic solar batteries of the body heterojunction structure of acceptor also can reach 4～5% (H.Shang, H.Fan, Y.Liu; W.Hu, Y.Li, X; Zhan, " A Solution-Processable Star-Shaped Molecule for High-Performance Organic Solar Cell ", Adv.Mater.; 2011,23,1554; B.Walker, A.B.Tamayo, X-D.Dang, P.Zalar; J.H.Seo, A.Garcia, M.Tantiwiwat, T-Q.Nguyen; " Nanoscale Phase Separation and High Photovoltaic Efficiency in Solution-Processed, Small-Molecule Bulk Heterojunction Solar Cell ", Adv.Funct.Mater.; 2009,19,3063.).The solar cell material of high conversion efficiency generally has D (giving body)-A (acceptor) type structure (M.C.Scharber, M.Koppe, J.Gao, F.Cordella; M.A.Loi, P.Denk, M.Morana; H-J.Egelhaaf, " Influence of the Bridging Atom on the Performance of a Low-Bandgap Bulk Heterojunction Solar Cell ", Adv.Mater.; 2010,22,367; Y.Zou, A.Najari, P.Berrouard; S.Beaupr é, B.R.
Y.Tao, M.Leclerc; " AThieno [3,4-c] pyrrole-4,6-dione-Based Copolymer for Efficient Solar Cells "; J.Am.Chem.Soc.; 2010,132,5330; Y.Zhang, S.K.Hau, H-L, Yip; Y.Sun, O.Acton, A.K.-Y.Jen, " Efficient Polymer Solar Cells Based on the Copolymers of Benzodithiophene and Thienopyrroledione "; Chem.Mater., 2010,22,2696; R.Qin, W.Li, C.Li, C.Du; C.Veit, H-F.Schleiermacher, M.Andersson; Z.Bo, Z.Liu, O.
U.Wuerfel; F.Zhang, " A Planar Copolymer for High Efficiency Polymer Solar Cells ", J.Am.Chem.Soc.; 2009,131,14612; C-P.Chen, S-H.Chan, T-C.Chao; C.Ting, B-T.Ko, " Low-Bandgap Poly (Thiophene-Phenylene-Thiophene) derivatives with Broaden Absorption Spectra for Use in High-Performance Bulk-Heterojunction Polymer Solar Cells "; J.Am.Chem.Soc.; 2008,130,12828; A.V.Patil, W-H.Lee, E.Lee, K.Kim; I-N.Kang, S-H.Lee, " Synthesis and Photovoltaic Properties of a Low-Band-Gap Copolymer of Dithieno [3,2-b:2 '; 3 '-d] thiophene and Dithienylquinoxaline ", Macromolecules, 2011; 44,1238.), this is because 1) intramolecular charge can take place and shift in D-A type molecular material; Make its absorption region to the long wavelength region red shift, thereby improve its utilization ratio, and then improve the short-circuit current of battery device sunshine; 2) contain acceptor (A) unit in the molecular structure, it can reduce the HOMO energy level of molecule, and then can improve the open circuit voltage of battery device.
The polymer organic field-effect transistor of first report is Polythiophene OFET, and its mobility was merely 10 at that time
-5Cm
2/ Vs (A.Tsumura, H.Koezuka, T.Ando; " Macromolecular electronic device:Field-effect transistor with a polythiophene thin film ", Appl.Phys.Lett., 1986; 49; 1210.), through the development of two more than ten years, nowadays the mobility mxm. of polymkeric substance OFET can reach 1.95cm
2/ Vs (H.Bronstein, Z.Chen, R.S.Ashraf, W.Zhang, J.Du; J.R.Durrant, P.S.Tuladhar, K.Song, S.E.Watkins, Y.Geerts; M.M.Wienk, R.A.J.Janssen, T.Anthopoulos, H.Sirringhaus; M.Heeney, I.McCulloch, " Thieno [3,2-b] thiophene-Siketopyrrolopyrrole-Containing Polymers for High-Performance Organic Field-Effect Transistors and Organic Photovoltaic Deviecs "; J.Am.Chem.Soc., 2011,133,3272.).The higher polymkeric substance of device mobility generally also has D-A type structure (T.Lei, Y.Cao, Y.Fan; C-J.Liu, S-C.Yuan, J.Pei; " High-Performance Air-Stable Organic Field-Effect Transistors:Isoindigo-Based Conjugated Polymers ", J.Am.Chem.Soc., 2011; 133,6099; J.A.Letizia, A.Facchetti, C.L.Stern; M.A.Ratner, T.J.Marks, " High Electron Mobility in Solution-Cast and Vapor-Deposited Phenacyl-Quaterthiophene-Based Field-Effect Transistors:Toward N-Type Polythiophenes "; J.Am.Chem.Soc.; 2005,127,13476; L.B ü rgi, M.Turbiez, R.Pfeiffer; F.Bienewald, H-J.Kirner, C.Winnewisser; " High-Mobility Ambipolar Near-Infrared Light-Emitting Polymer Field-Effect Transistors ", Adv.Mater., 2008; 20,2217; M.M.Durban, P.D.Kazarinoff, C.K.Luscombe; " Synthesis and Characterization of Thiophene-Conataing Naphthalene Diimide n-Type Copolymers for OFET Applications ", Macromolecules, 2010; 43,6348.), wherein reason comprises: 1) exist moment of dipole-moment of dipole to interact in the D-A type molecule; It can promote that molecule is tightly packed, thereby helps current carrier jump transmission; 2) D-A type molecular energy is regulated its HOMO/LUMO energy level effectively, thereby makes device have good stability and low contact resistance.
Diazosulfide is a good acceptor groups, and it can reduce the lumo energy of molecule, increases molecular interaction and forms the intramolecular charge transfer; Therefore be commonly used to synthetic Organic Light Emitting Diode, organic solar batteries and organic field effect tube material (T.Kono, D.Kumaki, J.Nishida; T.Sakanoue, M.Kakita, H.Tada; S.Tokito, Y.Yamashita, " High-Performance and Light-Emitting n-Type Organic Field-Effect Transistors Based on Dithienylbenzothiadiazole and Related Heterocycles "; Chem.Mater.; 2007,19,1218; J.Liu, Y.Cheng, Z.Xie; Y.Geng, L.Wang, X.Jing; F.Wang, " White Electroluninescence from a Star-like Polymer with an Orange Emissive Core and Four Blue Emissive Arms ", Adv.Mater.; 2008,20,1357; X.Guo, C.Qin, Y.Cheng, Z.Xie; Y.Geng, X.Jing, F.Wang; L.Wang, " White Electroluminescence from a Phosphonate-Functionalized Single-Polymer System with Electron-Trapping Effect ", Adv.Mater.; 2009,19,1; J.Hou, M-H.Park, S.Zhang; Y.Yao, L-M.Chen, J-H.Li; Y.Yang, " Bandgap and Molecular Energy Level Control of Conjugated Polymer Photovoltaic Materials Based on Benzo [1,2-b; 4,5-b '] dithiophene ", Macromolecules., 2008,41,6012; P.M.Beaujuge, S.Ellinger, J.R.Reynolds; " The donor-acceptor approach allows a black-to-transmissive switching polymer electrochrome ", Nature Materials., 2008; 7,795; M.Velusamy, K.R.J.Thomas, J.T.Lin, Y-C.Hsu, K-C.Ho, " Organic Dyes Incorporating Low-Band-Gap Chromophores for Dye-Sensitized Solar Cells ", Org.Lett, 2005,7,1899.).
Biphenyl that the present invention designed and thiadiazoles structure are connected together two diazosulfides exactly through 5 singly-bounds; This structure had both had the premium properties of single diazosulfide; Simultaneously because single bonded turning effort; Two diazosulfides not in one plane, so it is fit to be used for synthetic nonplanar D-A type structuring polymer very much, is applied in non-doping OLED and the organic solar batteries device.Singly-bound on biphenyl and the thiadiazoles can be regarded as a bridge in addition; Through introducing suitable modification group, synthesize bridging conjugated molecule based on biphenyl and thiadiazoles, this quasi-molecule helps the transmission of electric charge; Improve mobility, be suitable for doing organic field effect tube (OFET).
Summary of the invention
One of the object of the invention provides one type of polymer materials based on biphenyl and thiadiazoles with good sunshine capture ability, cavity transmission ability and luminous efficiency.
Two of the object of the invention provides a kind of preparation method of the polymer materials based on biphenyl and thiadiazoles.
Three of the object of the invention provides polymkeric substance based on biphenyl and thiadiazoles as the application of active layer material in organic electronic devices such as solar cell, field-effect transistor and photodiode.
The present invention prepared a series of brand-new, solvability is good, the polymer materials based on biphenyl and thiadiazoles of good stability, they have showed excellent properties in devices such as organic solar batteries and organic field effect tube.Characterized chemical structure with ultimate analysis, nucleus magnetic resonance, gel permeation chromatography based on the polymkeric substance of biphenyl and thiadiazoles; Characterized thermostability with thermogravimetric analysis based on the polymkeric substance of biphenyl and thiadiazoles; Characterized electrochemical properties with cyclic voltammetric, studied photophysical property based on the polymkeric substance of biphenyl and thiadiazoles with uv absorption spectrum and fluorescence spectrum based on the polymkeric substance of biphenyl and thiadiazoles.
Polymkeric substance based on biphenyl and thiadiazoles of the present invention has following formula:
Wherein: D is any one structural unit among the formula II;
M is 0～6;
N is 1～5000;
R
1～R
4Independently be hydrogen, C
1-C
30Alkyl or C
1-C
30Alkoxyl group.
In the polymer architecture based on biphenyl and thiadiazoles of the present invention, preferred version is: D is any one structural unit among the formula II; M is 0～3; N is 5～1000; R
1～R
2Independently be hydrogen or C
1-C
12Alkyl, R
3～R
4Independently be hydrogen, C
1-C
30Alkyl or C
1-C
30Alkoxyl group.
In the polymer architecture based on biphenyl and thiadiazoles of the present invention, preferred version is: D is any one structural unit among the formula II; M is 0～1; N is 5～1000; R
1～R
2Independently be hydrogen or C
6-C
12Alkyl, R
3～R
4Independently be hydrogen, C
6-C
30Alkyl or C
6-C
30Alkoxyl group.
The preparation method of the polymkeric substance based on biphenyl and thiadiazoles of the present invention is: with mol ratio is 1: 1 ratio, will have R
1, R
2The distannic compound of substituent thiophene-D-thiophene and biphenyl and thiadiazoles dibromo compound join in the reaction vessel; With toluene as solvent; The tetrakis triphenylphosphine palladium catalyzer (the preferable tetrakis triphenylphosphine palladium catalyzer that is added and the mol ratio of biphenyl and thiadiazoles dibromo compound are 1: 10～100) that adds catalytic amount behind the air in logical rare gas element (like nitrogen) the eliminating reaction vessel is 100～120 ℃ of following stirring reactions (time of general stirring reaction is 12～72 hours) in temperature; After reaction finishes, add with respect to having R
1, R
2The excessive potassium fluoride solution of molar weight of the distannic compound of substituent thiophene-D-thiophene stirs extracted organic phase (preferably using chloroform); The washing organic phase, extracted organic phase (preferably using chloroform) again, the organic phase that dry extraction obtains; Organic phase is splashed in the methyl alcohol; Filtration obtains solid, and chromatography column (the preferential polystyrene microsphere chromatography column of crossing is crossed in extracting (described extracting is preferably carried out extracting with methyl alcohol, acetone and chloroform successively successively); Use the chloroform give eluent), the polymkeric substance that obtains having above-mentioned formula I structure based on biphenyl and thiadiazoles; Wherein: described R
1, R
2, D definition with the above.
Described washing organic phase is to use hydrochloric acid soln respectively, sodium hydrogen carbonate solution washing organic phase.
Described organic phase being splashed in the methyl alcohol, is after the organic phase that earlier extraction obtained is filtered, the organic phase that obtains after filtering to be concentrated again, and then spissated organic phase is splashed in the methyl alcohol.
Polymkeric substance based on biphenyl and thiadiazoles of the present invention can be used as light and catches with electron donor material and in organic solar batteries, use.
Polymkeric substance based on biphenyl and thiadiazoles of the present invention can be used as hole mobile material and in organic field effect tube, uses.
Polymkeric substance based on biphenyl and thiadiazoles of the present invention can be used as luminescent material and in Organic Light Emitting Diode, uses.
Major advantage of the present invention is:
1. but synthetic of the present invention is soluble in organic solvents such as chloroform, THF and chlorobenzene based on the polymkeric substance solution method processing of biphenyl and thiadiazoles.
2. the polymer thermostable property based on biphenyl and thiadiazoles of the present invention is good, and initial heat decomposition temperature is above 390 ℃.
3. the polymkeric substance absorptive based on biphenyl and thiadiazoles of the present invention is good, and low HOMO energy level is arranged, and is fit to do organic solar battery material.
4. the polymkeric substance based on biphenyl and thiadiazoles of the present invention has appropriate H OMO/LUMO energy level and high hole mobility, is fit to do the organic field effect tube material.
5. the polymkeric substance based on biphenyl and thiadiazoles of the present invention fluoresces, and is fit to do the Organic Light Emitting Diode material.
Description of drawings
Fig. 1 is the uv-visible absorption spectra based on the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.
Fig. 2 is the cyclic voltammetry curve based on the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.
Fig. 3 is the thermogravimetric curve based on the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.
Fig. 4 is the curve of output based on the organic field effect tube of the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.
Fig. 5 is the transition curve based on the organic field effect tube of the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.Mobility: 2 * 10
-3Cm
2V
-1s
-1, on-off ratio: 10
4, threshold voltage :-18V.
Fig. 6 is the I-V curve based on the organic solar batteries of the polymer P 1 of biphenyl and thiadiazoles of the embodiment of the invention 1.Short-circuit current J
ScBe 9.2mA cm
-2, open circuit voltage V
OcBe 0.98V, packing factor FF is 41%, and effciency of energy transfer PCE is 3.7%.
Fig. 7 is the uv-visible absorption spectra based on the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.
Fig. 8 is the cyclic voltammetry curve based on the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.
Fig. 9 is the thermogravimetric curve based on the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.
Figure 10 is the curve of output based on the organic field effect tube of the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.
Figure 11 is the transition curve based on the organic field effect tube of the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.Mobility: 3 * 10
-3Cm
2V
-1s
-1, on-off ratio: 1.7 * 10
3, threshold voltage :-5V.
Figure 12 is the I-V curve based on the organic solar batteries of the polymer P 2 of biphenyl and thiadiazoles of the embodiment of the invention 2.Short-circuit current J
ScBe 4.27mA cm
-2, open circuit voltage V
OcBe 0.82V, packing factor FF is 34%, and effciency of energy transfer PCE is 1.2%.
Embodiment
The synthetic route of polymer P 1 is following:
(1) N-(2-n-decane base tetradecyl)-2,7-two thiophene carbazoles (structural formula 2 in the above-mentioned reaction scheme)
In the 25ml bottle with two necks, add 660mg (1mmol) N-(2-n-decane base tetradecyl)-2; 7-dibromo carbazole (structural formula 1 in the above-mentioned reaction scheme); 1.12g (3mmol) 2-(tributyl tin) thiophene and 10ml exsiccant toluene solution; Drum nitrogen 15min adds 115mg (0.1mmol) four (triphenyl phosphine) palladium.Reaction solution is at 110 ℃ of refluxed 48h.After reacting liquid temperature is got back to room temperature, in reaction flask, add 10ml KF (5g) solution, continue to stir 2h, use the dichloromethane extraction organic phase, and successively to use mass concentration be 10% hydrochloric acid soln, saturated sodium bicarbonate solution washs organic phase.The dried over mgso organic phase, rotary evaporation removes and desolvates, and use sherwood oil and methylene chloride volume ratio are that 5: 1 mixture is done eluent, and silica gel (200～300 order) column chromatography is separated purification, obtains light yellow solid 330mg, productive rate 50%.
1H NMR (400MHz, CDCl
3): δ 8.04 (d, J=8.1Hz, 2H), 7.59 (s, 2H), 7.52 (dd, J=8.1Hz, J=1.1Hz; 2H), 7.41 (d, J=3.4Hz, 2H), 7.32 (d, J=5.1Hz, 2H); 7.15 (dd, J=4.8Hz, J=3.7Hz, 2H), 4.19 (d, J=7.2Hz, 2H); 2.19 (m, 1H), 1.31-1.22 (m, 40H), 0.91 (t, J=6.3Hz, 6H).
13C NMR (75MHz, CDCl
3): δ 145.75,141.91, and 132.06,128.09,124.47,122.92,122.17; 120.59,117.70,106.22,47.34,37.88,32.02,30.05; 29.80,29.75,29.48,29.46,26.69,22.80,14.24.MS (MALDI): m/z 667 (M
+). ultimate analysis calculated value (C
44H
61NS
2): C, 79.10; H, 9.10; N, 2.10. measured value: C, 79.22; H, 9.22; N, 2.10%.
(2) N-(2-n-decane base tetradecyl)-2,7-two (5-(tin trimethyl) thiophene) carbazole (structural formula 3 in the above-mentioned reaction scheme)
In the 25ml there-necked flask, add the N-(2-n-decane base tetradecyl)-2 that 233.5mg (0.35mmol) step (1) obtains, 7-two thiophene carbazoles and 8ml exsiccant tetrahydrofuran solution, drum nitrogen 15min; Temperature drops to-78 ℃, in solution, drips 0.31ml (0.77mmol) n-Butyl Lithium, and-78 ℃ were stirred after one hour; Add 153.2mg (0.77mmol) trimethyltin chloride; After ten minutes, temperature of reaction system is raised to room temperature, continues reaction and spends the night.In bottle, add several quenchers reactions of dripping, use the extracted with diethyl ether organic phase, washing organic phase twice, dry organic phase obtains light yellow oily solid after revolving dried organic phase.
1H?NMR(400MHz，CDCl
3)：δ8.03(d，J＝8.1Hz，2H)，7.59(s，2H)，7.52(d，J＝8.0Hz，2H)，7.51(d，J＝3.4Hz，2H)，7.22(d，J＝3.3Hz，2H)，4.20(d，J＝6.4Hz，2H)，2.17(m，1H)，1.43-1.22(m，40H)，0.89(t，J＝6.3Hz，6H)，0.49(t，J＝56.4，18H)。
(3) 4,7-'-dibromobiphenyls and thiadiazoles (structural formula 4 in the above-mentioned reaction scheme)
Add in the 50ml single port bottle biphenyl and thiazole (540mg, 2mmol), the 8ml Hydrogen bromide at room temperature slowly adds liquid bromine (1.92g; 12mmol is dissolved in the 6ml Hydrogen bromide), after adding, 110 ℃ were refluxed one day; Wash suspension-s to remove excessive bromine with saturated sodium sulfite solution after being chilled to room temperature, filter, solid is with a large amount of water flushings, and silica gel column chromatography is crossed in dry back; Using sherwood oil and methylene chloride volume ratio is that 1: 3 mixture is done eluent, purify light yellow solid 256mg, productive rate 30%.
1H NMR (400MHz, CDCl
3): δ 8.15 (s, 1H), 8.13 (d, J=9.2Hz, 1H), 7.97 (s, 1H), 7.76 (d, J=9.2Hz, 1H) .EI-MS:425.8251, calculated values: 425.8244.Ultimate analysis calculated value (C
12H
4N
4S
2Br
2): C, 33.67; H, 0.94; N, 13.09. measured value: C, 33.84; H, 0.95; N, 13.06%.
(4) gather [N-(2-n-decane base tetradecyl)-carbazole-2, the 7-support-alternately-(4,7-dithienyl-biphenyl and thiadiazoles)-5,5 '-support-] (the structural formula P1 in the above-mentioned reaction scheme)
In the 25ml bottle with two necks, add 4 of 64.2mg (0.15mmol) that step (3) obtains; 7-'-dibromobiphenyl and thiadiazoles; The N-of the 138.3mg (0.15mmol) that step (2) obtains (2-n-decane base tetradecyl)-2,7-two (5-(tin trimethyl) thiophene) carbazole, and 4ml toluene; Drum nitrogen 15min gets rid of the air in the bottle with two necks, adds 12mg (0.01mmol) tetrakis triphenylphosphine palladium, is 100～120 ℃ of following stirring reaction 72h in temperature.To be cooled after room temperature, in reaction flask, add 10ml KF (5g) solution, continue to stir 2h, use the chloroform extraction organic phase; Use hydrochloric acid soln respectively, sodium hydrogen carbonate solution washing organic phase is used the chloroform extraction organic phase again, and is washed organic phase twice; The dried over mgso organic phase is filtered, and concentrated filtrate is to 5ml; Splash in the 200ml methyl alcohol, filter and obtain solid, with methyl alcohol, acetone and chloroform extracting successively; Cross polystyrene microsphere chromatography column (preferentially using chloroform drip washing) more in batches, obtain sorrel solid 70mg, productive rate 88%.
1H NMR (400MHz, CDCl
3): δ 8.32 (br, 6H), 7.62 (br, 4H), 7.10 (br, 4H), 3.96 (br, 2H), 1.91 (br, 1H), 1.17 (br, 40H), 0.83 (br, 6H) .M
n, 11513, M
w/ M
n, 2.53. heat decomposition temperature: 421 ℃.Maximum absorption: 531nm (solution), 565nm (film).HOMO：-5.68eV，LUMO：-3.58eV。
Uv-visible absorption spectra based on the polymer P 1 of biphenyl and thiadiazoles is as shown in Figure 1; Cyclic voltammetry curve is as shown in Figure 2; Thermogravimetric curve is as shown in Figure 3.
The synthetic route of polymer P 2 is following:
(1) 4,8-two (5-n-decane base tetradecyl thiophene)-2,6-two (thienyl) benzo two thiophene (structural formula 6 in the above-mentioned reaction scheme)
In the 25ml bottle with two necks, add 853mg (0.63mmol) 4; 8-two (5-n-decane base tetradecyl thiophene)-2; 6-two (tin trimethyl) benzo two thiophene (structural formula 5 in the above-mentioned reaction scheme); 250mg (1.5mmol) 2-bromothiophene and 10ml exsiccant toluene solution behind the drum nitrogen 15min, add 60mg (0.05mmol) tetrakis triphenylphosphine palladium.Reaction solution is at 110 ℃ of refluxed 48h.After reacting liquid temperature is got back to room temperature, in reaction flask, add 10ml KF (5g) solution, continue to stir 2h, use the dichloromethane extraction organic phase, and successively to use mass concentration be 10% hydrochloric acid soln, saturated sodium bicarbonate solution washs organic phase.The dried over mgso organic phase, rotary evaporation removes and desolvates, and sherwood oil is done eluent, and silica gel (200～300 order) column chromatography is separated purification, obtains light yellow solid 230mg, productive rate 31%.
1H NMR (400MHz, CDCl
3): δ 7.65 (s, 2H), 7.31 (d, J=3.3Hz, 2H), 7.28 (d, J=3.4Hz; 2H), 7.26 (d, J=4.8Hz, 2H), 7.04 (dd, J=4.8Hz, J=3.4Hz; 2H), 6.91 (d, J=3.3Hz, 2H), 2.88 (d, J=6.5Hz, 4H); 1.75 (m, 2H), 1.30-1.22 (m, 80H), 0.87 (t, J=5.2Hz, 12H).
13C NMR (75MHz, CDCl
3): δ 145.93,138.69, and 137.96,137.65,137.32,136.99,127.93,127.82; 125.59,125.54,125.22,123.47,119.17,40.16,34.81,33.55; 32.06,30.18,29.87,29.52,26.85,22.82,14.23.MS (MALDI): m/z 1191 (M
+). ultimate analysis calculated value (C
74H
110S
6): C, 74.56; H, 9.30. measured value: C, 74.42; H, 9.42%.
(2) 4,8-two (5-n-decane base tetradecyl thiophene)-2,6-two (2-tin trimethyl thiophene) benzo two thiophene (structural formula 7 in the above-mentioned reaction scheme)
Add in the 25ml there-necked flask that 170mg (0.14mmol) step (1) obtains 4,8-two (5-n-decane base tetradecyl thiophene)-2,6-two (thienyl) benzo two thiophene and 4ml exsiccant tetrahydrofuran solution; Drum nitrogen 15min, temperature drops to-78 ℃, in solution, drips 0.13ml (0.33mmol) n-Butyl Lithium;-78 ℃ are stirred after one hour, add 62.6mg (0.31mmol) trimethyltin chloride, after ten minutes; Temperature of reaction system is raised to room temperature, continues reaction and spends the night.In bottle, add several quenchers reactions of dripping, use the extracted with diethyl ether organic phase, washing organic phase twice, dry organic phase obtains light yellow oily solid after revolving dried organic phase.
1H?NMR(400MHz，CDCl
3)：δ7.65(s，2H)，7.38(d，J＝3.2Hz，2H)，7.31(d，J＝3.3Hz，2H)，7.11(d，J＝3.3Hz，2H)，6.91(d，J＝3.2Hz，2H)，2.88(d，J＝6.5Hz，4H)，1.75(m，2H)，1.38-1.24(m，80H)，0.89(t，J＝4.7Hz，12H)，0.39(t，J＝28.3Hz，18H)。
(3) gather [4,8-two (5-n-decane base tetradecyl thiophene) benzo two thiophene-2, the 6-support-alternately-(4,7-dithienyl-biphenyl and thiadiazoles)-5,5 '-support-] (structural formula P2 in the above-mentioned reaction scheme)
In the 25ml bottle with two necks, add the 52mg (0.12mmol) 4 that embodiment 1 prepares, 7-'-dibromobiphenyl and thiadiazoles (structural formula 4), the 200mg (0.132mmol) 4 that step (2) obtains; 8-two (5-n-decane base tetradecyl thiophene)-2; 6-two (2-tin trimethyl thiophene) benzo two thiophene, and 4ml toluene, drum nitrogen 15min gets rid of the air in the bottle with two necks; Adding 12mg (0.01mmol) tetrakis triphenylphosphine palladium, is 100～120 ℃ of following stirring reaction 72h in temperature.To be cooled after room temperature, in reaction flask, add 10ml KF (5g) solution, continue to stir 2h, use the chloroform extraction organic phase; Use hydrochloric acid soln respectively, sodium hydrogen carbonate solution washing organic phase is used the chloroform extraction organic phase again, and is washed organic phase twice; The dried over mgso organic phase is filtered, and concentrated filtrate is to 5ml; Splash in the 200ml methyl alcohol, filter and obtain solid, with methyl alcohol, acetone and chloroform extracting successively; Cross polystyrene microsphere chromatography column (preferentially using chloroform drip washing) more in batches, obtain sorrel solid 80mg, productive rate 47%.
1H NMR (400MHz, CDCl
3): δ 8.10-7.31 (br, 10H), 7.08 (br, 2H), 6.91 (br, 2H), 2.96 (br, 4H), 1.74 (br, 2H), 1.38-1.22 (br, 80H), 0.83 (br, 12H) .M
n, 16576, M
w/ M
n, 4.69. heat decomposition temperature: 395 ℃.Maximum absorption wavelength: 563nm (solution), 591nm (film).HOMO：-5.7eV，LUMO：-3.7eV。
Uv-visible absorption spectra based on the polymer P 2 of biphenyl and thiadiazoles is as shown in Figure 7; Cyclic voltammetry curve is as shown in Figure 8; Thermogravimetric curve is as shown in Figure 9.
Organic field effect tube (OFET) preparation of devices and test:
Adopt the top contact electrode structure; The adulterated silicon of high n-type is used for doing gate electrode and gate insulation layer respectively with the silicon-dioxide (300nm) of heat growth; Substrate uses pure water respectively, and the vitriol oil/hydrogen peroxide (mass ratio 2: 1) mixing solutions cleans, and is clean with purified rinse water then; Wash once with Virahol, trichlorine 18 silane (OTS) are used for modifying the dielectric layer surface again.The chloroformic solution of the P2 that P1 that embodiment 1 obtains or embodiment 2 obtain (about 5mg/mL) is through getting rid of the film mode at the OTS surface filming.Baking removed and desolvates in 30 minutes under 60 ℃ of vacuum environments.The thick gold of vacuum deposition method vapor deposition 25nm is as source electrode and drain electrode, and channel length and width are respectively 50 μ m and 1mm.The sign of OFET is accomplished through the Keithley 4200SCS of band micromanipulator test platform.
Based on the curve of output of the organic field effect tube of the polymer P 1 (embodiment 1) of biphenyl and thiadiazoles and P2 (embodiment 2) shown in Fig. 4 and 10; Transition curve is shown in Fig. 5 and 11.
The preparation of solar photovoltaic device and performance test:
Tin indium oxide (ITO) glass that commerce is bought cleans with cleaning agent earlier; Water, deionized water, acetone, Virahol ultrasonic cleaning successively then; Dry back spin coating one deck 30nm is thick gathers the enedioxy thiophene: poly styrene sulfonate PEDOT: PSS (mass ratio 1: 1) (4083) anode modification layer; Drying is 20 minutes under 120 ℃, and is subsequent use.With the above-mentioned polymer P 1 that obtains (embodiment 1) or P2 (embodiment 2) and solubility fullerene derivate PC based on biphenyl and thiadiazoles
71The blend solution (20mg/ml) of BM (weight ratio is 1: 1～4) is spun on PEDOT: the active coating that forms device on the PSS anode modification layer.All thickness are all measured through Ambios Tech.XP-2 film thickness gauge.Photovoltaic device active coating useful area is 4mm
2Vacuum evaporation (3 * 10 on active coating at last
-5Pa) thickness is that metallic aluminium about 100nm is as the negative electrode of photovoltaic device.
Use the Newport 500W xenon lamp of being furnished with the AM1.5 spectral filter as the simulated solar light source, at 100mW/cm
2Under the light intensity device is carried out the photovoltaic performance test, light intensity is through the calibration of standard monocrystaline silicon solar cell; The J-V curve uses Keithley 236 to measure, and is controlled by computingmachine through Labview software.
Based on the I-V curve of the organic solar batteries of the polymer P 1 (embodiment 1) of biphenyl and thiadiazoles and P2 (embodiment 2) shown in Fig. 6 and 12.
Claims (10)
1. the polymkeric substance based on biphenyl and thiadiazoles is characterized in that, described polymkeric substance based on biphenyl and thiadiazoles has following formula:
Wherein: D is any one structural unit among the formula II;
M is 0～6;
N is 1～5000;
R
1～R
4Independently be hydrogen, C
1-C
30Alkyl or C
1-C
30Alkoxyl group.
2. the polymkeric substance based on biphenyl and thiadiazoles according to claim 1 is characterized in that: D is any one structural unit among the formula II; M is 0～3; N is 5～1000; R
1～R
2Independently be hydrogen or C
1-C
12Alkyl, R
3～R
4Independently be hydrogen, C
1-C
30Alkyl or C
1-C
30Alkoxyl group.
3. the polymkeric substance based on biphenyl and thiadiazoles according to claim 2 is characterized in that: D is any one structural unit among the formula II; M is 0～1; N is 5～1000; R
1～R
2Independently be hydrogen or C
6-C
12Alkyl, R
3～R
4Independently be hydrogen, C
6-C
30Alkyl or C
6-C
30Alkoxyl group.
4. preparation method according to any described polymkeric substance based on biphenyl and thiadiazoles of claim 1～3 is characterized in that: with mol ratio is 1: 1 ratio, will have R
1, R
2The distannic compound of substituent thiophene-D-thiophene and biphenyl and thiadiazoles dibromo compound join in the reaction vessel; As solvent, adding the tetrakis triphenylphosphine palladium catalyzer of catalytic amount with toluene behind the air in the logical rare gas element eliminating reaction vessel, is 100～120 ℃ of following stirring reactions in temperature; After reaction finishes, add with respect to having R
1, R
2The excessive potassium fluoride solution of molar weight of the distannic compound of substituent thiophene-D-thiophene stirs extracted organic phase; The organic phase that washing, dry extraction obtain; Organic phase is splashed in the methyl alcohol, filter and obtain solid, extracting; Cross chromatography column, obtain the polymkeric substance based on biphenyl and thiadiazoles of structure shown in the claim 1 formula I;
Wherein: described R
1, R
2, D definition each is said with claim 1～3.
5. preparation method according to claim 4 is characterized in that: the mol ratio of described tetrakis triphenylphosphine palladium catalyzer and biphenyl and thiadiazoles dibromo compound is 1: 10～100.
6. preparation method according to claim 4 is characterized in that: the time of described stirring reaction is 12～72 hours.
7. preparation method according to claim 4 is characterized in that: described extracting is to carry out extracting with methyl alcohol, acetone and chloroform successively.
8. preparation method according to claim 4 is characterized in that: described washing organic phase is to use hydrochloric acid soln respectively, sodium hydrogen carbonate solution washing organic phase.
9. preparation method according to claim 4 is characterized in that: described organic phase being splashed in the methyl alcohol, is after the organic phase that earlier extraction obtained is filtered, the organic phase that obtains after filtering to be concentrated again, and then spissated organic phase is splashed in the methyl alcohol.
10. application according to any described polymkeric substance based on biphenyl and thiadiazoles of claim 1～3, it is characterized in that: described polymkeric substance based on biphenyl and thiadiazoles is caught with electron donor material as light and in organic solar batteries, is used; Or in organic field effect tube, use as hole mobile material; Or in Organic Light Emitting Diode, use as luminescent material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013159567A1 (en) * | 2012-04-24 | 2013-10-31 | 南开大学 | Photoelectric material preparation |
| CN103606631A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市东大技术转移中心有限公司 | Polymer light emitting diode having hole transport layer |
| CN103606632A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市东大技术转移中心有限公司 | Polymer light-emitting diode |
| CN104119355A (en) * | 2014-06-27 | 2014-10-29 | 南开大学 | Organic photoelectric compounds, preparing method thereof and applications of the compounds |
| CN108767111A (en) * | 2018-06-26 | 2018-11-06 | 东莞理工学院 | Sandwich structure memory device containing polymer nanocomposite film and preparation method |
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|---|---|---|---|---|
| CN101993440A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院化学研究所 | Benzothiadiazole-based multi-arm conjugated molecules as well as preparation method and application thereof |
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2011
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| CN101993440A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院化学研究所 | Benzothiadiazole-based multi-arm conjugated molecules as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013159567A1 (en) * | 2012-04-24 | 2013-10-31 | 南开大学 | Photoelectric material preparation |
| CN104428303A (en) * | 2012-04-24 | 2015-03-18 | 南开大学 | Photoelectric material preparation |
| CN104428303B (en) * | 2012-04-24 | 2016-09-14 | 南开大学 | Prepared by photoelectric material |
| CN103606631A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市东大技术转移中心有限公司 | Polymer light emitting diode having hole transport layer |
| CN103606632A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市东大技术转移中心有限公司 | Polymer light-emitting diode |
| CN104119355A (en) * | 2014-06-27 | 2014-10-29 | 南开大学 | Organic photoelectric compounds, preparing method thereof and applications of the compounds |
| CN104119355B (en) * | 2014-06-27 | 2016-05-18 | 南开大学 | Organic photoelectric compound and its preparation method and application |
| CN108767111A (en) * | 2018-06-26 | 2018-11-06 | 东莞理工学院 | Sandwich structure memory device containing polymer nanocomposite film and preparation method |
| CN108767111B (en) * | 2018-06-26 | 2022-07-05 | 东莞理工学院 | Sandwich structure memory device containing polymer nano-film and preparation method thereof |
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