CN101671428B - Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof - Google Patents
Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof Download PDFInfo
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- CN101671428B CN101671428B CN 200810222098 CN200810222098A CN101671428B CN 101671428 B CN101671428 B CN 101671428B CN 200810222098 CN200810222098 CN 200810222098 CN 200810222098 A CN200810222098 A CN 200810222098A CN 101671428 B CN101671428 B CN 101671428B
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Abstract
The invention relates to a conjugated polymer based on thiophene-containing condensed ring and diazosulfide, a preparation method and an application of the conjugated polymer as an active layer material in organic optoelectronic devices, such as polymer solar energy cells, organic field effect transistors and organic light emitting diodes. The conjugated polymer based on the thiophene-containing condensed ring and diazosulfide has an excellent sunlight capture ability and a hole transmission ability, and the conjugated polymer solution has good processability, thermostability, charge transmission performance and lightadsorption and is an ideal organic semiconducting material in the organic electronic devices, such as solar energy cells, field effect transistors and light emitting diodes. A general formula of the conjugated polymer is shown as below.
Description
Technical field
The present invention relates to a class based on conjugated polymers of condensed ring that contains thiophene and diazosulfide and preparation method thereof, and this conjugated polymers is as the application of active layer material in organic optoelectronic device such as polymer solar battery, organic field effect tube and Organic Light Emitting Diode.
Background technology
The solar cell that uses mainly relies on the panel realization opto-electronic conversion that inorganic materials such as silicon or rare metal alloy are made at present, though inorganic solar cell has high-level efficiency, long-life advantage, but inorganic semiconductor material costliness, complicated process of preparation is because of the too high factor of cost but limits its large-scale application all the time.Make solar energy power generating obtain large-scale promotion, just must find more cheap solar cell material.Organic polymer solar cell is the novel solar battery that grows up the nineties in 20th century, it forms (G.Yu by the body heterojunction that organic polymer acceptor between the positive and negative electrode and donor material film heterojunction or blend form together, J.Gao, J.C.Hummelen, F.Wudl, A.J.Heeger, " Polymerphotovoltaic cells:enhanced efficiencies via a network of internal donor-acceptorheterojunctions ", Science, 1995,270,1789).Compare with inorganic solar cell, organic solar batteries have low cost, ultra-thin, in light weight, manufacture craft simple, can prepare outstanding advantage such as large area flexible device, have important development and application prospect, become current novel material and new energy field one of research forward position (S.Gunes, the H.Neugebauer of rich vigour and vitality, N.S.Sariciftci, " Conjugated polymer-based organic solar cells ", Chem.Rev., 2007,107,1324.).Although organic polymer solar cell has been obtained significant progress, also have very big distance from the marketization, the key issue that faces is efficient and life-span.2007, U.S. scientist Alan Heeger research group utilizes new device making technics, the efficient of organic solar batteries has been brought up to 6.5% (J.Y.Kim, K.Lee, N.E.Coates, D.Moses, T.-Q.Nguyen, M.Dante, A.J.Heeger, " Efficient tandem polymer solar cells fabricated by all-solution processing ", Science, 2007,317,222.), practical application then needs 10% efficiency of conversion at least, and gap is still very big.Analyze from the material angle, inefficient major cause has 2 points: it is not wide that (1) organic polymer semiconductor material absorbs the sunlight wave band, the most absorbed wave bands that comprise polymkeric substance photovoltaic star material P3HT and MEH-PPV are at 350～650nm, and sunlight maximum photon stream is at 600～800nm, therefore organic polymer semiconductor material absorption spectrum and sun emmission spectrum commonly used at present do not match, and the sunlight utilization ratio is low; (2) carrier mobility of organic polymer semiconductor material is low, material that the overwhelming majority is commonly used such as the mobility of P3HT, MEH-PPV and CN-PPV etc., and particularly electronic mobility is lower than 10
-4Cm
2V
-1s
-1, the current carrier that produces after charge separation of exciton can not fast and effeciently be transferred to electrode and form electric current like this.
The decision device efficiency and the key factor in life-span are material and device preparation technology, and wherein the material breakthrough is the most important thing.The polymkeric substance photovoltaic material of good combination property lacks very much at present.Orderly poly-(the 3-hexyl thiophene) in zone (P3HT) utilizes the supramolecule self-organization directly to prepare high order film by the solution working method, can also reduce the trap in textural defect and the device, thereby improves device stability.It has excellent comprehensive performances, as good stability, higher mobility and the absorption of broad, is widely used in polymer solar battery, is acknowledged as best polymer-electronics donor material.But blemish in an otherwise perfect thing is that this material exists still that hole mobility is on the low side, 650nm does not have problems such as absorption with exterior domain.The hole mobility of P3HT is 10
-3Cm
2V
-1s
-1About, and can only absorb 21% solar photon.
Over the past two years, several in the world research groups introduced main polymer chain (1.M.Heeney, C.Bailey to the condensed ring thiophene unit, K.Genevicius, M.Shkunov, D.Sparrowe, S.Tierney, I.McCulloch, " Stable polythiophene semiconductors incorporatingthieno[2,3-b] thiophene ", J.Am.Chem.Soc., 2005,127,1078; 2.I.McCulloch, M.Heeney, C.Bailey, K.Genevicius, I.MacDonald, M.Shkunov, D.Sparrowe, S.Tierney, R.Wagner, W.Zhang, M.L.Chabinyc, R.J.Kline, M.D.McGehee, M.F.Toney, " Liquid-crystalline semiconducting polymers with high charge-carriermobility ", Nature Mater., 2006,5,328; 3.H.Pan, Y.Li, Y.Wu, P.Liu, B.S.Ong, S.Zhu, G.Xu, " Low-temperature, solution-processed, high-mobility polymersemiconductors for thin-film transistors ", J.Am.Chem.Soc., 2007,129,4112; 4.M.Zhang, H.N.Tsao, W.Pisula, C.Yang, A.K.Mishra, K.M ü llen, " Field-effecttransistors based on a benzothiadiazole-cyclopentadithiophene copolymer ", J.Am.Chem.Soc., 2007,129,3472; 5.H.Ohkita, S.Cook, Y.Astuti, W.Duffy, S.Tierney, W.Zhang, M.Heeney, I.McCulloch, J.Nelson, D.D.C.Bradley, J.R.Durrant, " Charge carrier formation in polythiophene/fullerene blend films studied bytransient absorption spectroscopy ", J.Am.Chem.Soc., 2008,130,3030; 6.J.Li, F.Qin, C.M.Li, Q.Bao, M.B.Chan-Park, W.Zhang, J.Qin, B.S.Ong, " High-performance thin-film transistors from solution-processeddithienothiophene polymer semiconductor nanoparticles ", Chem.Mater., 2008,20,2507).Because the condensed ring that contains thiophene has bigger coplanar structure and more sulphur atom than thiophene, its molecular interaction and pi accumulation are stronger, and the mobility ratio P3HT of polymkeric substance that therefore can predict them theoretically is higher.Field-effect transistor (OFET) mobility of constructing with these polymkeric substance is up to 0.1～0.7cm
2V
-1s
-1, than high 2～3 orders of magnitude of P3HT.In addition, the condensed ring that contains thiophene has bigger conjugacy and electron delocalization than thiophene, compare with P3HT, based on the absorption meeting red shift of the polymkeric substance of the condensed ring that contains thiophene to infrared region, thereby mate with the sunlight emmission spectrum.The maximum absorption wavelength that bibliographical information contains the condensed ring polymkeric substance of thiophene is 720nm, than P3HT red shift 150nm, reaches 3.2% with the solar battery efficiency of it and PCBM blend preparation, than the P3HT height under the equal conditions (D.M ü hlbacher, M.Scharber, M.Morana, Z.Zhu, D.Waller, R.Gaudiana, C.Brabec, " High photovoltaicperformance of a low-bandgap polymer ", Adv.Mater., 2006,18,2884).
Summary of the invention
The object of the present invention is to provide the conjugated polymers of a class based on excellent sunlight capture ability of having of condensed ring that contains thiophene and diazosulfide and cavity transmission ability.
A further object of the present invention provides a kind of preparation method of the conjugated polymers based on condensed ring that contains thiophene and diazosulfide.
An also purpose of the present invention provides based on the conjugated polymers of condensed ring that contains thiophene and diazosulfide as the application of electron donor material in organic solar batteries etc.
The present invention prepared a series of brand-new, the solution processibility is good, order is good, to the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of air-stable, wide absorption, narrow band gap.The transfer transport that electron deficiency diazosulfide and electron rich contain between the condensed ring of thiophene can be extended near infrared region to photoabsorption, can obtain the polymkeric substance that narrow band gap, wide band absorb like this.Use ultimate analysis, nucleus magnetic resonance has characterized the chemical structure based on the conjugated polymers of condensed ring that contains thiophene and diazosulfide, with gel permeation chromatography based on the molecular weight of the conjugated polymers of condensed ring that contains thiophene and diazosulfide, tested thermostability with thermogravimetric analysis and differential thermal analysis based on the conjugated polymers of condensed ring that contains thiophene and diazosulfide, characterized electrochemical properties with cyclic voltammetric, studied photophysical property based on the conjugated polymers of condensed ring that contains thiophene and diazosulfide with ultra-violet absorption spectrum and fluorescence spectrum based on the conjugated polymers of condensed ring that contains thiophene and diazosulfide.
Conjugated polymers based on condensed ring that contains thiophene and diazosulfide of the present invention has following formula:
Wherein: m is 0,1,2,3,4,5 or 6, and m is preferably 0,1,2,3 or 6, and m most preferably is 1.
N is 5～200.
X is S, Si, C or N, and X is preferably S, C or Si, and X most preferably is S.
R is normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl, R is preferably n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl, and R most preferably is dodecyl.
R
1Be hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl, R
1Be preferably hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl, R
1Most preferably be hydrogen or positive certain herbaceous plants with big flowers base.
R
2Be hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base, dodecyl, 2-certain herbaceous plants with big flowers base tetradecyl, 2,6-two (sec.-propyl) phenyl, 3,4,5-three (dodecyloxy) phenyl, 3,4,5-three (dodecyloxy) benzyl or R
2The place does not have substituting group, R
2Be preferably hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base, dodecyl or do not have substituting group, R
2Most preferably be and do not have substituting group or positive certain herbaceous plants with big flowers base.
In the conjugated polymers structure based on condensed ring that contains thiophene and diazosulfide of the present invention, preferred version is that R is n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl; R
1Be hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl; R
2For hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base, dodecyl or there is not substituting group; X is S, C or Si; M is 0,1,2,3 or 6; N is 5～200.
In the conjugated polymers structure based on condensed ring that contains thiophene and diazosulfide of the present invention, preferred version is that R is a dodecyl; R
1Be hydrogen; R
2There is not substituting group; X is S (sulphur); M is 1; N is 10～200.
In the conjugated polymers structure based on condensed ring that contains thiophene and diazosulfide of the present invention, preferred version is R
1Be the n-decane base; R
2There is not substituting group; X is S (sulphur); M is 0; N is 5～100.
The preparation method of the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of the present invention may further comprise the steps:
1) with the R that has of equimolar amount, R
1, R
2Substituent pair of bromine thiophene-condensed ring-thiophene monomer that replaces and the diazosulfide monomer that two boric acid esters replace join in the reaction vessel logical protection of inert gas;
2) adding toluene solvant and wet chemical (wherein have R in salt of wormwood and the step 1), R in the reaction vessel of step 1)
1, R
2The monomeric ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 20: 1; (have R, R in preferred four triphenyl phosphorus palladiums and the step 1) with the four triphenyl phosphorus palladium catalysts that add catalytic amount behind the air in the rare gas element eliminating reaction vessel
1, R
2The monomeric ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 1: 15～1: 20); At 100～120 ℃ of following stirring reactions, after reaction is finished, be cooled to room temperature, use the chloroform extraction organic phase, the washing organic phase concentrates, and uses methanol extraction, can obtain having the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of said structure formula; Or
A) with the R that has of equimolar amount
1, R
2The monomer of substituent pair of organotin condensed ring monomer that replaces and the thiophene-diazosulfide-thiophene that has substituent pair of bromine replacement of R joins in the reaction vessel logical protection of inert gas;
B) in the reaction vessel of step a), add toluene solvant; (have R in preferred four triphenyl phosphorus palladiums and the step a) with the four triphenyl phosphorus palladium catalysts that add catalytic amount behind the air in the rare gas element eliminating reaction vessel
1, R
2Condensed ring thiophene monomer that the substituent pair of organotin replaces or the monomeric ratio that has thiophene-diazosulfide-thiophene that substituent pair of bromine of R replace are 1: 15～1: 20); At 100～120 ℃ of following stirring reactions, after reaction is finished, be cooled to room temperature, use the chloroform extraction organic phase, the washing organic phase concentrates, and uses methanol extraction, can obtain having the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of said structure formula.
Described rare gas element is nitrogen or argon gas etc.
A preferred embodiment of the present invention is: have R, R
1, R
2Thiophene-condensed ring-the thiophene monomer of substituent pair of bromine replacement is 0.2～1mmol, and the diazosulfide monomer that two boric acid esters replace is 0.2～1mmol; Wet chemical, salt of wormwood with have a R, R
1, R
2The monomeric mol ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 20: 1; Four triphenyl phosphorus palladiums with have a R, R
1, R
2The monomeric mol ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 1: 15～1: 20.
Of the present invention-kind of preferred version is: have R
1, R
2The condensed ring monomer of substituent pair of organotin replacement is 0.2～1mmol, and the thiophene-diazosulfide-thiophene monomer that has substituent pair of bromine replacement of R is 0.2～1mmol; Four triphenyl phosphorus palladiums with have a R
1, R
2Condensed ring monomer that the substituent pair of organotin replaces or the mol ratio that has thiophene-diazosulfide-thiophene monomer that substituent pair of bromine of R replace are 1: 15～1: 20.
Conjugated polymers based on condensed ring that contains thiophene and diazosulfide of the present invention can be used as light and catches with electron donor material and use in organic solar batteries.
Conjugated polymers based on condensed ring that contains thiophene and diazosulfide of the present invention can be used as hole mobile material and uses in organic field effect tube.
Conjugated polymers based on condensed ring that contains thiophene and diazosulfide of the present invention can be used as luminescent material and uses in Organic Light Emitting Diode.
Major advantage of the present invention is:
1. synthetic is good based on the conjugated polymers solution processibility of condensed ring that contains thiophene and diazosulfide, is soluble in organic solvents such as chloroform, tetrahydrofuran (THF) and chlorobenzene.
2. based on the Heat stability is good of the conjugated polymers of condensed ring that contains thiophene and diazosulfide, initial heat decomposition temperature is above 350 ℃.
3. the conjugated polymers based on condensed ring that contains thiophene and diazosulfide is a black, and light absorptive is good, and light abstraction width covers 300～1000nm, and band gap is narrower.
Description of drawings
Fig. 1 is the synthetic route based on the conjugated polymers P1 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 1.
Fig. 2 is the ultraviolet-visible-near-infrared absorption spectrum based on the conjugated polymers P1 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 1.
Fig. 3 is the cyclic voltammetry curve based on the conjugated polymers P1 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 1.
Fig. 4 is the thermogravimetric curve based on the conjugated polymers P1 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 1.
Fig. 5 is the differential scanning calorimetry curve based on the conjugated polymers P1 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 1.
Fig. 6 is the synthetic route based on the conjugated polymers P2 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 2.
Fig. 7 is the uv-visible absorption spectra based on the conjugated polymers P2 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 2.
Fig. 8 is the fluorescence spectrum based on the conjugated polymers P2 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 2.
Fig. 9 is the cyclic voltammetry curve based on the conjugated polymers P2 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 2.
Figure 10 is the thermogravimetric curve based on the conjugated polymers P2 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 2.
Figure 11 is the synthetic route based on the conjugated polymers P3 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 3.
Figure 12 is the synthetic route based on the conjugated polymers P4 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 4.
Figure 13 is the synthetic route based on the conjugated polymers P5 of condensed ring that contains thiophene and diazosulfide of the embodiment of the invention 5.
Embodiment
The synthetic route of polymer P 1 as shown in Figure 1.
(1) 2,6-two (3-dodecyl thiophene)-three thiophthenes
With 2-bromo-3-dodecyl thiophene (1.25mmol; 664mg) with 2; 6-two (tributyl tin) three thiophthene (0.41mmol; 320mg) add in the 50ml there-necked flask; logical nitrogen deoxygenation 30 minutes; the secluding air state injects 10ml exsiccant toluene down, adds catalyst P d (PPh under nitrogen protection
3)
4(26 μ mol 30mg), are heated to 110 ℃, stir reaction down and spend the night (four triphenyl phosphorus palladiums).Be cooled to room temperature, add 2 and a half hours precipitations of potassium fluoride aqueous solution 10ml (8g KF) stirring and remove organotin impurity.Use the chloroform extraction reaction solution, again organic phase collected and wash twice, anhydrous magnesium sulfate drying, remove behind toluene and the chloroform solvent column chromatography purify (silicagel column, sherwood oil drip washing) get final product orange solids (228mg, 79%).
1H NMR (400MHz, CDCl
3): δ 7.29 (s, 2H), 7.23 (d, J=8.0Hz, 2H), 6.97 (d, J=8.0Hz, 2H), 2.80 (t, J=7.0Hz, 4H), 1.70 (m, 4H), 1.5-1.25 (m, 36H), 0.87 (t, J=6.4Hz, 6H).
13C NMR (400MHz, CDCl
3): δ 140.9,140.3,136.9,130.6,130.0,124.3,119.2,31.9,30.7,29.7,29.6,29.5,29.4,29.2,22.7,14.1. ultimate analysis calculated value (C
40H
56S
5): C, 68.91; H, 8.10. experimental value: C, 68.90; H, 8.06%.
(2) 2,6-two (5,5 '-two bromo-3-dodecyl thiophene)-three thiophthenes
In 100mL single port bottle, add 2,6-two (3-dodecyl thiophene)-three thiophthene (600mg, 0.86mmol), the 15ml chloroform, the 15ml Glacial acetic acid is cooled to 0 ℃ with ice bath, add N-bromo-succinimide (NBS) (383mg, 2.15mmol), the lucifuge reaction rose to room temperature after 30 minutes, reacted 6 hours again.Suspension is poured in the sodium hydroxide solution of cold 150ml2M and stirred 10 minutes, separatory washes organic phase with water twice, anhydrous magnesium sulfate drying.Remove the rear pillar chromatography purification of desolvating and obtain buff powder (287mg, 41%).
1H NMR (400MHz, CDCl
3): δ 7.22 (s, 2H), 6.93 (s, 2H), 2.73 (m, 4H), 1.63 (m, 4H), 1.30 (m, 36H), 0.89 (m, 6H).
13C NMR (400MHz, CDCl
3): δ 141.13,141.05,135.6,132.7,131.9,130.8,119.7,111.3,39.4,31.9,30.6,30.0,29.7,29.6,29.4,29.2,28.0,22.7,14.1.MS (MALDI): 854 (M
+). ultimate analysis calculated value (C
40H
54Br
2S
5): C, 56.19; H, 6.37. experimental value: C, 56.11; H, 6.27%.(3) gather { [2,6-two (3-dodecyl thiophene)-three thiophthenes]-alternately-(2,1, the 3-diazosulfide) } (P1)
In the 25mL two-mouth bottle, add 2,6-two (5,5 '-two bromo-3-dodecyl thiophene)-three thiophthene (170mg, 0.2mmol) and the diazosulfide that replaces of two boric acid ester (diazosulfide that two boric acid esters replace can be synthetic according to following document: M.Zhang, H.N.Tsao, W.Pisula, C.Yang, A.K.Mishra, K.M ü illen, " Field-effect transistors based on abenzothiadiazole-cyclopentadithiophene copolymer ", J.Am.Chem.Soc., 2007,129,3472) (78mg, 0.2mmol), add toluene (2mL) and wet chemical (2ml, 550mg again, 4mmol), the inflated with nitrogen deoxygenation is 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(13.3 μ mol 15mg), are heated to 100 ℃.This is reflected at 100 ℃ and stirred 3 days down.Be cooled to room temperature,, wash organic phase again twice with the chloroform extraction organic phase of 100ml * 2.Organic phase is concentrated into 2.5ml, splashes in the 200ml methyl alcohol, filter and obtain lividity solid (128mg, 84%).
1H NMR (400MHz, CDCl
3): δ 7.90 (br, 2H), 7.60 (br, 2H), 7.16 (s, 1H), 6.88 (s, 1H), 2.80 (br, 4H), 1.20 (br, 40H), 0.82 (br, 6H). ultimate analysis calculated value (C
46H
56N
2S
6): C, 66.62; H, 6.81; N, 3.38. experimental value: C, 63.12; H, 6.69; N, 3.01%. number-average molecular weight: 39000g mol
-1, molecular weight distribution: 1.7.UV (CHCl
3), λ
Max: 434,596nm.391 ℃ of initial heat decomposition temperatures, 96 ℃ of fusing points.The film absorption of this polymkeric substance can cover 300～1000nm (see figure 2).Fig. 2 is the ultraviolet-visible absorption spectra based on the conjugated polymers P1 of condensed ring thiophene and diazosulfide; Fig. 3 is a cyclic voltammetry curve, and ferrocene is interior mark; Fig. 4 is a thermogravimetric curve; Fig. 5 is the differential scanning calorimetry curve.
The synthetic route of polymer P 2 as shown in Figure 6.
(1) 2,6-two bromo-3,5-two decyls three thiophthenes
With 3, (0.42g, 0.88mmol), 10ml chloroform, 10ml Glacial acetic acid join in the 100ml single port bottle 5-two decyls three thiophthenes.The single port bottle wraps up with tinfoil, is cooled to 0 ℃.(410mg 2.30mmol) is dissolved in the 3ml dimethyl formamide (DMF), dropwise is added drop-wise in the single port bottle again, stirs, and reacts to rise to room temperature after 1 hour, stirs 4 hours with NBS (N-bromo-succinimide).The xanchromatic mixture joins in the NaOH solution of 200ml (2M) ice, stirs 10 minutes.Use the dichloromethane extraction organic phase of 200ml * 2 then, collect organic phase and use anhydrous magnesium sulfate drying.Filter, after being spin-dried for, cross silicagel column with sherwood oil drip washing and separate, remove and desolvate, get faint yellow solid (385mg, 69%).
1HNMR (400MHz, CDCl
3): δ 2.73 (m, 4H), 1.71 (m, 4H), 1.26 (m, 28H), 0.88 (m, 6H).
13C NMR (100M, CDCl
3): δ 138.47,135.14,129.02,108.72,31.91,29.61,29.55,29.35,29.30,29.02,28.09,22.69,14.03. ultimate analysis calculated value (C
28H
42Br
2S
3): C, 52.99; H, 6.67. experimental value: C, 52.98; H, 6.63%.
(2) gather { [3,5-two decyls-three thiophthene]-alternately-(2,1, the 3-diazosulfide) } (P2)
In the 50ml there-necked flask, add monomer 2,6-two bromo-3,5-two decyls three thiophthenes (634.6mg, 1.0mmol), (388.1mg 1.0mmol) and 10ml toluene and 2.8g salt of wormwood (being dissolved in the 10ml water), stirs the diazosulfide that replaces of two boric acid ester.Feed nitrogen 30 minutes, and under nitrogen atmosphere, added Pd (PPh
3)
4(58mg, 0.05mmol).Be warming up to 100 ℃ after 20 minutes, reflux, stirring reaction is 72 hours under the nitrogen atmosphere.Then reactant is cooled to room temperature, uses filter paper filtering, with chloroform flushing filter paper repeatedly, wash organic phase again twice.Organic phase is concentrated into 2.5ml, splashes in the 200ml methyl alcohol, get dark red solid (274mg, 45%).
1H NMR (400MHz, CDCl
3): δ: 7.80-7.68 (br, 2H), 3.01-2.76 (br, 4H), 1.86-1.06 (br, 32H), 0.87 (br, 6H). ultimate analysis calculated value (C
34H
44N
2S
4): C, 67.06; H, 7.28, N, 4.60. experimental value: C, 67.76; H, 8.02; N, 3.38%. number-average molecular weight: 5500g mol
-1, molecular weight distribution: 1.7.UV (CHCl
3), λ
Max: 332,488nm.114 ℃ of initial heat decomposition temperatures.The film absorption of this polymkeric substance can cover 200～600nm (see figure 7).Fig. 7 is this ultraviolet-visible absorption spectra based on the conjugated polymers P2 of condensed ring thiophene and diazosulfide; Fig. 8 is a fluorescence spectrum; Fig. 9 is a cyclic voltammetry curve, and ferrocene is interior mark; Figure 10 is a thermogravimetric curve.
Embodiment 3
The synthetic route of polymer P 3 as shown in figure 11.
Poly-[4,4-two (decyl) two thieno-cyclopentadiene]-replace-(2,1, the 3-diazosulfide) (P3)
In 25 milliliters of three mouthfuls of round-bottomed flasks, add 2,7-two bromo-4,4-two decyls two thieno-cyclopentadiene (2,7-two bromo-4,4-two decyls two thieno-cyclopentadiene are synthetic according to following literature method: M.Zhang, H.N.Tsao, W.Pisula, C.Yang, A.K.Mishra, K.M ü llen, " Field-effecttransistors based on a benzothiadiazole-cyclopentadithiophene copolymer ", J.Am.Chem.Soc., 2007,129,3472) (123mg, 0.2mmol) and the diazosulfide (78mg that replaces of two boric acid ester, 0.2mmol), add toluene (2ml) and wet chemical (2ml, 550mg again, 4mmol), the inflated with nitrogen deoxygenation is 30 minutes.Under nitrogen protection, add catalyst P d (PPh
3)
4(10 μ mol 12mg), are heated to 100 ℃.This is reflected at 100 ℃ and stirred 3 days down.Be cooled to room temperature, with the chloroform extraction organic phase of 100ml * 2, collect organic phase, washing is collected the organic phase that obtains twice again.Organic phase is concentrated into 2.5ml, splashes in the 200ml methyl alcohol, filter and obtain black solid (47mg, 40%).1H NMR (400MHz, CDCl
3): δ 8.3-7.3 (br, 4H), 2.0-1.9 (br, 4H), 1.5～0.8 (br, 38H). number-average molecular weight: 10000g mol
-1, molecular weight distribution: 2.6.UV (CHCl
3), λ
Max: 418,718nm.420 ℃ of initial heat decomposition temperatures.The film absorption of this polymkeric substance can cover 300～800nm.
Embodiment 4
The synthetic route of polymer P 4 as shown in figure 12.
Poly-[4,4-two (decyl)-two thieno-cyclopentadiene]-replace-[4,7-two thiophene-(2,1, the 3-diazosulfide)] (P4)
In the 25ml two-mouth bottle, add 2,6-two (tin trimethyl)-4,4-two (decyl)-two thieno-cyclopentadiene (2,6-two (tin trimethyl)-4,4-two (decyl)-two thieno-cyclopentadiene is synthetic according to following document: A.J.Moul é, A.Tsami, T.W.B ü nnagel, M.Forster, N.M.Kronenberg, M.Scharber, M.Koppe, M.Morana, C.J.Brabec, K.Meerholz, U.Scherf, " Two novel cyclopentadithiophene-based alternating copolymers aspotential donor components for high-efficiency bulk-heterojunction-type solarcells ", Chem.Mater., 2008,20,4045) (0.2mmol, 157mg) and 4,7-two (5-bromothiophene)-2,1,3-diazosulfide (4,7-two (5-bromothiophene)-2,1, the 3-diazosulfide is synthetic according to following document: A.J.Moul é, A.Tsami, T.W.B ü nnagel, M.Forster, N.M.Kronenberg, M.Scharber, M.Koppe, M.Morana, C.J.Brabec, K.Meerholz, U.Scherf, " Twonovel cyclopentadithiophene-based altemating copolymers as potential donor components for high-efficiency bulk-heterojunction-type solar cells ", Chem.Mater., 2008,20,4045) (0.2mmol 92mg), feeds argon gas deoxygenation 30 minutes, under argon gas stream, add 10 milliliters of toluene and four triphenyl phosphorus palladiums (10 μ mol, 12mg), 10 minutes post-heating to 120 ℃ stirred three days.Be cooled to room temperature, with the chloroform extraction organic phase of 100ml * 2, collect organic phase, washing is collected the organic phase that obtains twice again.Organic phase is concentrated into 2.5ml, splashes in the 200ml methyl alcohol, filter and obtain solid, this solid again with 2 milliliters of chloroform dissolvings, is splashed in the methyl alcohol and precipitates, get faint blue solid (91mg, 60%) after the vacuum-drying.
1H NMR (400MHz, CDCl
3): 8.0-6.80 (br, 8H), 1.8 (4H), 1.5-0.9 (32H), 0.7-0.6 (6H). number-average molecular weight: 13200g mol
-1, molecular weight distribution: 1.5.UV (tetrahydrofuran (THF)), λ
Max: 435,615nm.
Embodiment 5
The synthetic route of polymer P 5 as shown in figure 13.
Poly-[7,7-two (decyl)-two thieno-sila cyclopentadiene]-replace-[4,7-two thiophene-(2,1, the 3-diazosulfide)] (P5)
In 25 milliliters of three mouthfuls of round-bottomed flasks, add 2,5-two (tin trimethyl)-7,7-two (decyl)-two thieno-sila cyclopentadiene (2,5-two (tin trimethyl)-7,7-two (decyl)-two thieno-sila cyclopentadiene is synthetic according to following document: L.Liao, L.Dai, A.Smith, M.Durstock, J.Lu, J.Ding, Y.Tao, " Photovoltaic-active dithienosilole-containing polymers ", Macromolecules, 2007,40,9406) (0.2mmol, 160mg) and 4,7-two (5-bromothiophene)-2,1, (0.2mmol 92mg), feeds argon gas deoxygenation 30 minutes to the 3-diazosulfide, under argon gas stream, add 10 milliliters of toluene and four triphenyl phosphorus palladiums (10 μ mol, 12mg), 10 minutes post-heating to 120 ℃ stirred three days.Be cooled to and add 10 ml waters after the room temperature, with the chloroform extraction organic phase of 100ml * 2, collect organic phase, washing is collected the organic phase that obtains twice again.Organic phase is concentrated into 2.5ml, splashes in the 200ml methyl alcohol, filter and obtain solid, this solid again with 2 milliliters of chloroform dissolvings, is splashed in the methyl alcohol and precipitates, get black solid (100mg, 65%) after the vacuum-drying.
1H NMR (400MHz, CDCl
3): 8.1-6.9 (br, 8H), 1.27 (br, 36H), 0.89 (br, 6H). number-average molecular weight: 29200g mol
-1, molecular weight distribution: 5.2.UV-vis (chloroform): λ
Max=593nm.Heat decomposition temperature is 324 ℃, and second-order transition temperature is 114 ℃.
Claims (10)
1. conjugated polymers based on condensed ring that contains thiophene and diazosulfide is characterized in that: should have following formula based on conjugated polymers of condensed ring that contains thiophene and diazosulfide:
Wherein: m is 0,1,2,3,4,5 or 6;
N is 5～200;
X is S, Si, C or N;
And X is C, and m is not 0;
R is normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl;
R
1Be hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base or dodecyl;
R
2Be hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive certain herbaceous plants with big flowers base, n-undecane base, dodecyl, 2-certain herbaceous plants with big flowers base tetradecyl, 2,6-two (sec.-propyl) phenyl, 3,4,5-three (dodecyloxy) phenyl, 3,4,5-three (dodecyloxy) benzyl or R
2The place does not have substituting group.
2. the conjugated polymers based on condensed ring that contains thiophene and diazosulfide according to claim 1 is characterized in that: R is n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl; M is 0,1,2,3 or 6; R
1Be hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base or dodecyl; R
2For hydrogen, n-hexyl, n-octyl, positive certain herbaceous plants with big flowers base, dodecyl or there is not substituting group; X is S, C or Si; N is 5～200;
And X is C, and m is not 0.
3. the conjugated polymers based on condensed ring that contains thiophene and diazosulfide according to claim 1 and 2 is characterized in that: R is a dodecyl; M is 1; R
1Be hydrogen; R
2There is not substituting group; X is S; N is 10～200.
4. the conjugated polymers based on condensed ring that contains thiophene and diazosulfide according to claim 1 is characterized in that: m is 0; R
1Be the n-decane base; R
2There is not substituting group; X is S; N is 5～100.
5. preparation method according to each described conjugated polymers based on condensed ring that contains thiophene and diazosulfide of claim 1～4 is characterized in that this method may further comprise the steps:
1) with the R that has of equimolar amount, R
1, R
2Substituent pair of bromine thiophene-condensed ring-thiophene monomer that replaces and the diazosulfide monomer that two boric acid esters replace join in the reaction vessel logical protection of inert gas;
2) in the reaction vessel of step 1), add toluene solvant and wet chemical, wherein have R in salt of wormwood and the step 1, R
1, R
2The monomeric mol ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 20: 1; The four triphenyl phosphorus palladium catalysts that add catalytic amount behind the air in the eliminating reaction vessel; Behind 100～120 ℃ of following stirring reactions, promptly obtain having the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of following structural formula; Or
A) with the R that has of equimolar amount
1, R
2The monomer of substituent pair of organotin condensed ring monomer that replaces and the thiophene-diazosulfide-thiophene that has substituent pair of bromine replacement of R joins in the reaction vessel logical protection of inert gas;
B) in the reaction vessel of step a), add toluene solvant; The four triphenyl phosphorus palladium catalysts that add catalytic amount behind the air in the eliminating reaction vessel; Behind 100～120 ℃ of following stirring reactions, promptly obtain having the conjugated polymers based on condensed ring that contains thiophene and diazosulfide of following structural formula;
M in the formula, n, X, R, R
1And R
2Definition each is described with claim 1～4.
6. method according to claim 5 is characterized in that: four triphenyl phosphorus palladiums with have a R, R
1, R
2The monomeric mol ratio of diazosulfide that the thiophene-condensed ring-thiophene monomer of substituent pair of bromine replacement or two boric acid ester replace is 1: 15～1: 20; Four triphenyl phosphorus palladiums with have a R
1, R
2Condensed ring monomer that the substituent pair of organotin replaces or the mol ratio that has thiophene-diazosulfide-thiophene monomer that substituent pair of bromine of R replace are 1: 15～1: 20.
7. according to claim 5 or 6 described methods, it is characterized in that: have R, R
1, R
2Thiophene-condensed ring-the thiophene monomer of substituent pair of bromine replacement is 0.2～1mmol, and the diazosulfide monomer that two boric acid esters replace is 0.2～1mmol; Have R
1, R
2The condensed ring monomer of substituent pair of organotin replacement is 0.2～1mmol, and the thiophene-diazosulfide-thiophene monomer that has substituent pair of bromine replacement of R is 0.2～1mmol.
8. application according to each described conjugated polymers based on condensed ring that contains thiophene and diazosulfide of claim 1～4, it is characterized in that: this conjugated polymers is caught with electron donor material as light and is used in organic solar batteries.
9. application according to each described conjugated polymers based on condensed ring that contains thiophene and diazosulfide of claim 1～4, it is characterized in that: this conjugated polymers is used in organic field effect tube as hole mobile material.
10. application according to each described conjugated polymers based on condensed ring that contains thiophene and diazosulfide of claim 1～4, it is characterized in that: this conjugated polymers is used in Organic Light Emitting Diode as luminescent material.
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