CN102643284B - Preparation method and application of 4,9-bisalkylene indene thieno[3,2-b]thiophene derivative and conjugated polymer thereof - Google Patents
Preparation method and application of 4,9-bisalkylene indene thieno[3,2-b]thiophene derivative and conjugated polymer thereof Download PDFInfo
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Abstract
The invention relates to preparation of a 4,9-bis(alkylene) indene thieno[3,2-b]thiophene derivative which is applicable to organic optoelectronic materials. A 4,9-bis(alkylene) indene thieno[3,2-b]thiophene derivative has a chemical structure as shown in general formula (I). A preparation method of the 4,9-bis(alkylene) indene thieno[3,2-b]thiophene derivative comprises the following steps: reacting indene thieno[3,2-b]thiophene-4,9-diketone with a Grignard reagent prepared by brominated alkanes with a chain length of C1-C20 and magnesium, performing heating reflux for dehydroxylation of the obtained tertiary alcohol in the presence of hydrochloric acid or other mixed acids so as to obtain 4,9-bis(alkylene) indene thieno[3,2-b]thiophene. The preparation method of the invention can obtain the 4,9-bis(alkylene) indene thieno[3,2-b]thiophene derivative with good solution processability and a long carbon chain; the mother ring of indene thieno[3,2-b]thiophene and the alkylene have good coplanarity, and the alkylene has good flexibility.
Description
Technical field
The present invention relates to can be used for organic optoelectronic material 4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] preparation of two thiophene derivants; The invention still further relates to two (alkylidene group) indeno [1,2-b based on 4,9-; 5,6-b] preparation of two thiophene derivant conjugation copolymerization.
Background technology
1976, American scientist Alan J. Heeger, since Macdiarmid and Japanese scientist Hideki Shirakawa etc. find conjugated polymers, due to its electricity and optical property both with metal or inorganic semiconductor, retain again high molecular superior mechanical property and processing characteristics and get more and more people's extensive concerning.In recent years, scientist has synthesized many conjugated polymerss with photoelectric activity.Simultaneously, utilize these conjugated polymerss charge transfer or can luminous, prepared such as polymer electroluminescence diode (PLEDs), polymer solar battery (PPVCs), photodetector, biosensor and field-effect transistor.
OTFT as a kind of with respect to a kind of transistor outside the conventional thin film transistor with inorganic semiconductor material, more and more come into one's own, with respect to other organic semiconductors such as now widely used pentacene, thiophene oligomers, although the charge mobility based on these materials and OTFT has reached 10
-7-10
1cm
2/ Vs, ON/OFF current ratio reaches 10
5-10
8.The corresponding data of the performance of part material devices and amorphous silicon base device quite or more outstanding.But the thin film transistor based on organic electronic material is still low than traditional inorganic semiconductor thin film transistor aspect the over-all properties such as stability, tooling cost at present.
On the other hand, along with the increase year by year of global energy demand, the petering out of the disposable energy such as oil, people have invested the renewable energy source such as sun power, Hydrogen Energy eye, and sun power is one of following most promising energy.Utilizing the solar cell of photovoltaic effect carrying out raising the efficiency and reducing costs as energy conversion device is the research of target.At present, solar cell ripe on market is mainly the inorganic solar cell such as silicon single crystal, polysilicon, non-crystalline silicon, gallium arsenide, indium phosphide and polycrystalline film compound semiconductor, wherein, polysilicon and non-crystal silicon solar cell are occupied an leading position in civil solar Battery Market, and the highest energy efficiency of inorganic solar cell has reached 30% left and right now.Although countries in the world have given very large financial support and encouragement to solar electrical energy generation industry in recent years, many developed countries have also set up many demonstration centres power station (the maximum solar power station in the world building up as the Demonstration Station of Davis 400KW of about 64 KW of, French Order and California, USA and the Demonstration Station of 6.2 ten thousand kilowatts of Portugal Moura and Germany etc.).But compared with traditional energy, also there is too expensive unfavorable factor in solar electrical energy generation now.The high major cause of cost of the inorganic solar cell on open market is: 1. the price of raw material is higher, 2. complex manufacturing.Conjugated polymers solar photovoltaic device, owing to likely realizing big area, softness, solar cell cheaply, likely addresses this problem and is subject to extensive concern.
These 1992, N.S. Sariciftci etc. were at SCIENCE (Science
2581474 (1992)) on, reported the ultrafast Photoinduced Electron transfer phenomena between conjugated polymers and C60, the laminated film that can be used for preparing polymkeric substance/C60 and derivative thereof due to this physical phenomenon is optical activity layer, realize big area, softness, solar cell and light detecting device cheaply, and cause that academia and industrial community pay attention to greatly.1994, (the Science such as G. Yu
270, 1789 (1995)) and by a certain proportion of MEH-PPV and C
60make the polymer solar battery of the sandwich structure of MEH-PPV/C60 blend film, due to the mutually each self-forming co-continuous of electron donor(ED) and electron acceptor(EA) network phase (bi-continuousnetwork), the electronics that photoinduction produces and hole can be respectively separately mutually in transport and be collected on corresponding electrode, photo-generated carrier is greatly reduced by again compound probability reaching before corresponding electrode, and photo-quantum efficiency is greatly improved.Through effort in recent years, 8% present left and right is brought up in the existing 0.04% initial left and right of the photoelectric transformation efficiency of polymer solar battery.But want large-scale application, photoelectric transformation efficiency is still too low.And to make high performance polymer solar cell, except the further improvement of device architecture, it is a very important aspect that electron acceptor material and electron donor material are optimized.Present stage, concerning electron acceptor material, although people developed as, pyrene diamide, the phthalein mountain valley with clumps of trees and bamboo, inorganic nano material etc., but the performance of the device still making as electron acceptor material using C60 and its derivative etc. is now best, on the other hand, to with electron donor(ED) phase material, it is narrower that synthesizes energy bandwidth exactly, and spectral response is more mated with solar radiation, the conjugated polymers that charge carrier mobility is higher.In March, 2006, the D.C. Bradley study group of Britain's Imperial College at Nature Materials(with reference to people such as Kim, Nature Materials, 5,197 (2006)) regularity and the state of certainly organizing of upper report Polythiophene are electron donor material to Polythiophene, PCBM is the impact of the performance of the polymer solar battery of electron acceptor material, research is found, along with the raising of Polythiophene regularity, the opto-electronic conversion performance of the spectral response of device and device is all improved, simultaneously, in the time of thermal treatment, the formation of the orderly fine aggregation structure of Polythiophene, favourable to improving the spectral response of battery and the performance of battery, although the raising of Polythiophene regularity and orderly fine aggregation structure have improved the spectral response of battery, but analyze from spectral response data, the raising of cell photoelectric conversion performance, mainly the expansion due to the raising of Polythiophene regularity and orderly fine accumulation area, the raising of the mobility of Polythiophene phase causes, this explanation polymer charge mobility has great significance for the efficiency that improves polymer solar battery.In April, 2006.The researchist of Stanford university is at Nature Materials(Mcculloch etc., Nature Materials, 5,328 (2006)) upper report is found thiophene also [3,2-b] thiophene introduces in alkylthrophene polymer chain, be conducive to reduce the intermolecular and distance pi-conjugated unit of molecule Nei π –, thereby be conducive to form large orderly crystal phase structure in the crystallisation process of mesomorphic phase, they have obtained the polymer materials that mobility can match in excellence or beauty with the polysilicon of present commercialization.Illustrate and build the how parallel thiophene aromatic ring yl conjugated polymers with large conjugate planes, can effectively improve the charge mobility of this base polymer.2007, and Man-Kit Ng etc. (Zhao etc. J. Org. Chem., 72 (17), 6364 (2007)) synthesize a class indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone derivative, the research of XRD shows, utilizes the film of such material prepared by solution spin-coating method to have good ordered structure.Patent CN101798310 has announced a class 4, the derivative preparation of two (two itrile group methylene radical) the indenes 1,4-Dithiapentalenes of 9-, and the electronic mobility of such material has reached 0.33 cm2/Vs.Patent US 20090299029 has announced the preparation of the conjugated polymers of a class based on 4,4,9,9-tetra-(4-alkyl phenyl) indenes 1,4-Dithiapentalene.Obtain the conjugated polymers that a class has excellent charge mobility and solution processing and ultraviolet-ray visible absorbing performance.Although indeno [1,2-b; 5,6-b] two thiophene-4, two (two itrile group methylene radical) the indenes 1,4-Dithiapentalenes of 9-diketone and 4,9-have larger conjugate planes, are conducive to form large ordered phase structure, and the charge mobility based on these materials has reached 0.33 cm2/Vs.But because the solubleness of this bi-material is lower, be not easy to the conjugated polymers based on these monomers for preparation; Although patent US 20090299029 has announced a class based on 4,4,9,9-tetra-(4-alkyl phenyl) indeno [1,2-b; 5,6-b] preparation of conjugated polymers of two thiophene, introduce alkylbenzene or alkyl 4,9 of indenes 1,4-Dithiapentalene, although solved the problem of indenes 1,4-Dithiapentalene poor solubility, be unfavorable for reducing indeno [1,2-b; 5,6-b] distance of the intermolecular and pi-conjugated unit of molecule Nei π – of two thiophene, be unfavorable for forming large ordered phase structure, obtain the organic semiconductor material that mobility is higher.
summary of the invention:
The object of the invention is to avoid the deficiencies in the prior art, two (alkylidene group) indeno [1, the 2-b of a kind of 4,9-are provided; 5,6-b] preparation method of two thiophene derivants.The present invention uses indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone and 2,8-, bis-bromos or 2,8-diiodo-indeno [1,2-b; 5,6-b] two thiophene-4, alkyl bromide or magnesium iodide that 9-diketone is C1-C20 with chain length react, and then with hydrochloric acid or other nitration mixture deshydroxies, prepare two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] two thiophene derivants.
Another object is to provide a kind of based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] preparation method of two thiophene derivant conjugated copolymers.The present invention uses 4 of 2,8-, bis-bromos or 2,8 diiodo-s, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene, prepare two (alkylidene group) indeno [1,2-b based on 4,9-; 5,6-b] conjugated polymers of two thiophene.
The present invention is 4 of indenes 1,4-Dithiapentalene, and alkylidene group is introduced in 9-position, not only can obtain having 4 of good solution processing characteristics, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, and due to two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] two thiophene derivants have larger conjugate surface and the good kindliness of alkylidene group, thus can effectively reduce two (alkylidene group) indeno two thiophene derivants of 4,9-and based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] distance of the intermolecular and pi-conjugated unit of molecule Nei π – of the conjugated polymers of two thiophene derivants, be conducive to form large ordered phase structure, improve the charge mobility of material.Obtain having more commercial value for OTFT and polymer solar battery based on conjugated polymers and small molecule organic semiconductor material.
For achieving the above object, the technical scheme that the present invention takes is: two alkylidene group indeno [1, the 2-b of a kind of 4,9-; 5,6-b] two thiophene derivants, its principal character is that chemical structure of general formula is:
In described (I), R1, R2 are independently selected from the straight or branched alkyl of hydrogen atom or C1-C10.
The present invention originally relates to 2,8-dibromo (or diiodo-)-4, two alkylidene group indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, it is characterized in that: chemical structural formula is:
In described (II), X group is independently selected from bromine, iodine atom, and R1, R2 are independently selected from the straight or branched alkyl of hydrogen atom or C1-C10.
Then, the present invention relates to utilize 2,8-dibromo or two iodo-4, two alkylidene group indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, by Stille linked reaction, prepare the conjugated copolymer based on the two alkylidene group indenes 1,4-Dithiapentalenes of 4,9-with two tin trimethyl compounds of thiophene thiophthene, thiophene, bithiophene, its chemical structure of general formula is (III):
Again, the present invention relates to utilize 2,8-dibromo (or diiodo-)-4, two alkylidene group indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, by Suzuki linked reaction, prepare two alkylidene group indeno [1,2-b based on 4,9-with two (4,4,5,5-tetramethyl--1,3, the 2-dioxa borine-2-yl) diazosulfides of 4,7-; 5,6-b] conjugated copolymer of two thiophene, its chemical structure of general formula is (IV):
Finally, the present invention relates to a kind of solar cell, it is characterized in that including described in claim 3 or 4 based on two alkylidene group indeno [1, the 2-b of 4,9-; 5,6-b] conjugated polymers of two thiophene derivants is for the electron donor material of polymer solar battery.
Described 4, the preparation method of two alkylidene group indeno two thiophene derivants of 9-, is characterized in that general formula is that the step of (I) is: 2,5-dibromoterephthalic acid, under excess ethyl alcohol and sulfur oxychloride exist, refluxes, and prepares 2,5-dibromoterephthalic acid diethyl ester; 2; 5-dibromoterephthalic acid diethyl ester reacts the 2-thienyl zinc chloride preparing under tetrakis triphenylphosphine palladium catalysis with the grignard reagent of 2-bromothiophene with Zinc Chloride Anhydrous; obtain 2; 5-bis-(2-thienyl) diethyl terephthalate; saponification in potassium hydroxide aqueous solution (40%); then acidifying (PH=3); obtain 2; 5-bis-(2-thienyl) terephthalic acid is in excess chlorination sulfoxide back flow reaction; prepare 2; 5-bis-(2-thienyl) p-phthaloyl chloride under aluminum trichloride (anhydrous) effect, indeno [1, the 2-b obtaining; 5,6-b] two thiophene-4, the Grignard reagent that the brominated alkanes that 9-diketone is C1-C20 with chain length prepares with magnesium reacts, and the tertiary alcohol obtaining heats deshydroxy under hydrochloric acid or the existence of other nitration mixture, obtains 4,9-bis-(alkylidene group) indeno [1,2-b; 5,6-b] two thiophene.
Described 2,8-dibromo or two iodo-4, two alkylidene group indeno [1, the 2-b of 9-, 5,6-b] preparation method of two thiophene derivants, it is characterized in that general formula is that the step of (II) is: 2,5-dibromoterephthalic acid, under excess ethyl alcohol and sulfur oxychloride exist, refluxes, and prepares 2,5-dibromoterephthalic acid diethyl ester, 2, 5-dibromoterephthalic acid diethyl ester reacts preparation with 2-thiophene magnesium bromide 2-thienyl zinc chloride with Zinc Chloride Anhydrous is under tetrakis triphenylphosphine palladium catalysis, obtain 2, 5-bis-(2-thienyl) diethyl terephthalate, in trichloromethane, use N-bromo-succinimide or N-N-iodosuccinimide bromination, obtain 2, backflow saponification in 5-bis-(5-bromine or 5-iodothiophen-2-yl) potassium hydroxide for diethyl terephthalate (quality percentage composition ratio is 40%), then use concentrated hydrochloric acid acidifying (PH=3), obtain 2, 5-bis-(5-bromine or iodine thiophene-2-yl) terephthalic acid is in excess chlorination sulfoxide back flow reaction, prepare 2, 5-bis-(2-bromine or 5-iodothiophen base) p-phthaloyl chloride is under aluminum trichloride (anhydrous) effect, obtain 2, 8-dibromo or diiodo-indenes 1,4-Dithiapentalene-4, 9-diketone, by 2, 8-dibromo indenes 1,4-Dithiapentalene-4, 9-diketone or 2, 8-diiodo-indeno [1, 2-b, 5,6-b] two thiophene-4,9-diketone is added in there-necked flask, adds dry orthodichlorobenzene under anhydrous and oxygen-free state.After stirring at room temperature 20 min, the alkyl magnesium bromide preparing in advance (alkyl chain length is C1-C20) is at room temperature joined in reaction.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake is washed by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, decompression steams solvent.Obtain brown solid.Brown solid is dissolved in to heat (60-65
oc) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, heating reflux reaction spends the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.
Described 4, two alkylidene group indeno [1, the 2-b of 9-; 5; 6-b] and two thiophene derivant conjugated polymerss (preparation method of chemical structure of general formula (III), its characterization step is: by purified 2,8-dibromo or two iodo-4; two (alkylidene group) the indenes 1,4-Dithiapentalenes and 2 of 9-; two (trimethyl-tin-radical) thiophenes of 5-are [3,2-b] thiophene or two (trimethyl-tin-radical) thiophene or 5 of 2,5-also; 5 '-bis-(trimethyl-tin-radicals) 2; 2 '-bis-bithiophenes in molar ratio 1:1 are dissolved in THF, under nitrogen protection, add PdCl
2(PPh
3), after back flow reaction 36 h, add two (trimethyl-tin-radical) thiophene of 2,5-to react 6 h to remove bromine end group, then add 2-bromothiophene to remove tributyl tin end group; Then use methanol extraction, the polymkeric substance obtaining processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24 h under vacuum.
Described 4, two alkylidene group indeno [1, the 2-b of 9-; 5,6-b] preparation method of two thiophene derivant conjugated polymerss (IV), its characterization step is: will be after careful purifying 2,8-dibromo or two iodo-4, two alkylidene group indeno two thiophene derivants and 4 of 9-, 7-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-2-yl) diazosulfide is dissolved in toluene for 1:1 in molar ratio, then adds the aqueous solution and the Pd (PPh of 20% Tetrabutyl amonium bromide
3)
4after degassed, under nitrogen protection, reflux 36h, then uses phenylo boric acid and bromobenzene end-blocking, and the reaction solution obtaining precipitates in methyl alcohol, then processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24 h under vacuum.
The preparation method of described solar cell, is characterized in that including following steps: based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] two thiophene derivant conjugated polymerss (chemical structure is III or the IV simultaneously) preparation that is the polymer solar battery of electron donor material: mark and the cleaning of (1) ITO substrate; (2) spin coating of anode buffer layer; (3) preparation of polymkeric substance and acceptor material layer composite bed, includes two 4,9-(alkylidene group) indeno [1,2-b; 5,6-b] two thiophene derivant conjugated polymerss and [6,6]-C
61-benzoyl-1 methyl-butyrate (PC
61or [6,6]-C BM)
71-benzoyl-1 methyl-butyrate (PC
71bM) [6,6]-C
61phenyl-C
61butyric acid (PC
61bM) be placed in clean sample bottle and weigh, proceed in the glove box that is full of nitrogen protection, with toluene, chlorobenzene dissolves and is placed on mixing platform and stirs conjugated polymers is uniformly dissolved, the above-mentioned solution obtaining (1:1,1:2 in proportion; 1:4) mix, the mixing solutions obtaining filters with 0.45 micron of filtering head, with the oarse-grained insoluble impurities of filtering, plays the effect that improves film planarization.Then, the substrate that scribbles anode buffer layer good vacuum-drying is moved into the spin coating of carrying out polymkeric substance/PC61BM in glove box, spin coating process is identical with anode buffer layer; (4) (vacuum tightness is 3 × 10 to the evaporation of metal aluminium electrode
-4pa).
Beneficial effect of the present invention is; At indeno [1,2-b; 5,6-b] two thiophene 4, alkylidene group is introduced in 9-position, not only can obtain having 4 of good solution processing characteristics, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants.And due to two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] the middle alkylidene group of the two thiophene derivants bridge olefinic carbon atom by 4,9 is connected, thereby make to obtain 4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] female ring indeno [1,2-b in two thiophene derivants; 5,6-b] two thiophene and good coplanarity and the good kindliness of alkylidene group of alkylidene group, thus can effectively reduce two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] two thiophene derivants and based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5; 6-b] distance of the intermolecular and pi-conjugated unit of molecule Nei π – of the conjugated polymers of two thiophene derivants; be conducive to form large ordered phase structure; improve the charge mobility of material; obtain a series of organic electronic opto-electronic devices that are applicable to; particularly 4 of the material of OTFT and organic solar batteries, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene and the conjugated polymers based on two (alkylidene group) indenes 1,4-Dithiapentalenes of 4,9-.
Embodiment
Below principle of the present invention and feature are described; example, only for explaining the present invention, is not intended to limit scope of the present invention, within the spirit and principles in the present invention all; any amendment of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Indeno [1, the 2-b using in the present invention; 5,6-b] two thiophene-4,9-diketone comprises the steps: that 2,5-dibromoterephthalic acid, under excess ethyl alcohol and sulfur oxychloride existence, refluxes, and prepares 2,5-dibromoterephthalic acid diethyl ester; 2; 5-dibromoterephthalic acid diethyl ester reacts preparation with the Grignard reagent of 2-bromothiophene 2-thienyl zinc chloride with Zinc Chloride Anhydrous is under tetrakis triphenylphosphine palladium catalysis; obtain 2; the saponification in potassium hydroxide aqueous solution of 5-bis-(2-thienyl) diethyl terephthalate; then acidifying; obtain 2; 5-bis-(2-thienyl) terephthalic acid is in excess chlorination sulfoxide back flow reaction; prepare 2; 5-bis-(2-thienyl) p-phthaloyl chloride is under aluminum trichloride (anhydrous) effect; obtain indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone, can have following reaction scheme to represent:
Reaction scheme 1. indenes 1,4-Dithiapentalene-4, the preparation of 9-diketone
Above-mentioned indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone is according to Zhao et. al.(J. Org. Chem., 72 (17), 6364 (2007)) described in method preparation.
Embodiment 1:4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] preparation of two thiophene:
By indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone (1.0 g, 3.4 mmol) is added in the there-necked flask of 250 mL, adds dry orthodichlorobenzene 100 mL under anhydrous and oxygen-free state.After stirring at room temperature 20 min, under at room temperature being stirred, the Grignard reagent of bromo-1-preparing in advance 2-hexyl decane (preparing gained by the 1-bromo-2-hexyl decane of 6.4 g and the magnesium of 0.5g in anhydrous tetrahydro furan 60 mL) adds.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake washs by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, decompression steams solvent.Obtain brown solid.Brown solid is dissolved in to (the 60-65 of heat
oc) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, heating reflux reaction spends the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.Structure is as follows:
Productive rate: 28%;
1h NMR(CDCl
3, δ pmm); 7.52 (s, 2H), 7.34 (d, 2H), 7.16(s; 2H) 6.38 (m, 2H), 3.02 (bd, 2H), 2.10 (m; 2H), 1.62-1.09 (m, 46H), 0.84 (t, 12H); C48H70S2:Calcd. C 81.06, H 9.92, S 9.02; Found C 81.03, H 9.96, S 8.99; FAB-MS:m/z=711 (M+).
Embodiment 2:4, two (sub-decyl) indeno [1, the 2-b of 9-; 5,6-b] preparation of two thiophene
By indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone (1.0 g, 3.4 mmol) adds in the there-necked flask of 250 mL, adds dry orthodichlorobenzene 100 mL under anhydrous and oxygen-free state.After stirring at room temperature 20 min, during the Grignard reagent of the bromo-decane of 1-preparing in advance (being prepared in anhydrous tetrahydro furan 60 mL by the bromo-decane of 1-of 4.6 g and the magnesium of 0.5g) is at room temperature joined and reacted.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake washs by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, remove solvent under reduced pressure.Obtain brown solid.Brown solid is dissolved in to (the 60-65 of heat
oc) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, heating reflux reaction spends the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.Structure is as follows:
Productive rate: 26%;
1h NMR(CDCl
3, δ pmm); 7.62 (s, 2H), 7.44 (d, 2H), 7.14 (s; 2H), 6.41 (m, 2H), 3.07 (b, 2H); 1.62-1.11 (m, 28 H), 0.86 (t, 6H); C36H46S2:Calcd. C 79.65, H 8.54, S 11.81; Found C 79.62, H 8.57, S 11.79; FAB-MS:m/z=543 (M+).
Embodiment 3:4,9-two (the sub-heptadecyl of 9-) indeno [1,2-b; 5,6-b] preparation of two thiophene
By indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone (1.0 g, 3.4 mmol) is added in the there-necked flask of 250 mL, adds anhydrous orthodichlorobenzene 100 mL under anhydrous and oxygen-free state.After stirring at room temperature 20 min, the margaric Grignard reagent of 9-bromine preparing in advance (being prepared in anhydrous tetrahydro furan 60 mL by the 9-bromine heptadecane of 6.65 g and the magnesium of 0.5g) is at room temperature added.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake washs by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, decompression steams solvent.Obtain brown solid.Brown solid is dissolved in to (the 60-65 of heat
oc) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, heating reflux reaction spends the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.Structure is as follows:
Productive rate: 32%;
1h NMR(CDCl
3, δ pmm); 7.58 (s, 2H), 7.36 (d, 2H), 7.14 (s, 2H), 6.41 (d, 2H), 1.72-1.11 (m, 56 H), 0.86 (t, 12H); C50H74S2:Calcd. C 81.26, H 10.09, S 8.67; Found C 81.22, H 10.13, S 8.62; FAB-MS:m/z=739 (M+).
The structure in the organic field principle similar with homologue chemical property is widely cognitive, therefore above-mentioned other 4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants to be to be prepared by above-mentioned similar preparation method, as: 4,9-bis-(alkylidene group) indeno [1,2-b; 5,6-b] the alkyl halide magnesium that prepared by corresponding bromo uncle's alkane or the secondary alkane of bromo (alkyl chain length is C1-C20) and corresponding iodo uncle's alkane or the secondary alkane of iodo (alkyl chain length is C1-C20) and magnesium of two thiophene, alkyl halide magnesium and indeno [1,2-b; 5,6-b] two thiophene-4, the reaction of 9-diketone, obtains indenes 1,4-Dithiapentalene tertiary alcohol derivative, reflux (oil bath temperature, 110 of indenes 1,4-Dithiapentalene tertiary alcohol derivative under hydrochloric acid exists
0c) to prepare general formula be 4 shown in following formula I to deshydroxy, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, illustrated by reaction scheme below:
Reaction scheme 2. 4, the preparation of two (alkylidene group) indeno two thiophene derivants of 9-
The alkyl halide magnesium of the bromo uncle's alkane that is characterized as independent selection different chain length structure of above-mentioned reaction or the secondary alkane of bromo and corresponding iodo uncle's alkane or the iodo alkane second month in a season, with indeno [1,2-b; 5,6-b] two thiophene-4, the reaction of 9-diketone obtains two alkyl indeno [1, the 2-b of 4,9-; 5,6-b] two thiophene-4, the two alcohol derivate of 9-, the deshydroxy that then refluxes under hydrochloric acid or other nitration mixture exist, preparation have R1, R2 be independently selected from hydrogen atom or C1-C10 straight or branched alkyl 4,9-bis-(alkylidene group) indeno [1,2-b; 5,6-b] two thiophene derivants.
Prepared by aforesaid method 4, the representative example of two (alkylidene group) indeno two thiophene derivants of 9-is as following chemical structural formula:
Embodiment 4:2,8-bis-is bromo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] preparation of two thiophene
By 2,8-dibromo indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone (1.0g, 2.2 mmol) is added in the there-necked flask of 250 mL, adds dry orthodichlorobenzene 100 mL under anhydrous and oxygen-free state.After stirring at room temperature 20 min, during the Grignard reagent of bromo-1-preparing in advance 2-hexyl decane (the bromo-2-hexyl of the 1-decane by 4.1 g is prepared in anhydrous tetrahydro furan 60 mL with the magnesium of 0.32 g) is at room temperature joined and reacted.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake is washed by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, decompression steams solvent.Obtain brown solid.Brown solid is dissolved in to heat (60-65
0c) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, reflux (oil bath temperature, 110
0c) reaction is spent the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.Structure is as follows:
Productive rate: 25%;
1h NMR(CDCl
3, δ pmm); (7.55 s, 2H), 7.34 (d, 2H), 6.38 (d, 2H), 3.02 (bd, 2H), 1.66-1.11 (m, 48H), 0.84 (t, 12H); C48H68Br2S2:Calcd. C 66.34, H 7.89, Br, 18.39, S 7.38; Found C 66.31, H 7.92, S 7.33; FAB-MS:m/z=869 (M+).
Embodiment 5:2,8-bis-is iodo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] preparation of two thiophene
By 2,8-diiodo-indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone (1.0g, 1.8 mmol) is added in the there-necked flask of 250 mL, adds dry orthodichlorobenzene 100 mL under anhydrous and oxygen-free state.After stirring at room temperature 20 min, during the Grignard reagent of bromo-1-preparing in advance 2-hexyl decane (the bromo-2-hexyl of the 1-decane decane by 4.1 g is prepared in anhydrous tetrahydro furan 60 mL with the magnesium of 0.32 g) is at room temperature joined and reacted.Under argon shield, stirring reaction spends the night.Add water after cancellation, suction filtration, filter cake is washed by ethyl acetate, and filtrate is extracted with ethyl acetate after washing.Anhydrous Na SO
4dry, remove solvent under reduced pressure.Obtain brown solid.Brown solid is dissolved in to (the 60-65 of heat
0c) in 30 mL dehydrated alcohols.Be transferred in the there-necked flask of 100 mL, add the hydrochloric acid of 10 mL.The THF of 20 mL, heating reflux reaction spends the night.Be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.Structure is as follows:
Productive rate: 21%;
1h NMR(CDCl
3, δ pmm); (7.57 s, 2H), 7.36 (d, 2H), 6.35 (m, 2H), 3.01 (bd, 2H), 1.69-1.11 (m, 48H), 0.84 (t, 12H); C48H68I2S2:Calcd. C 59.87, H 7.12, I, 26.36, S 6.66; Found C 59.68, H7.16, S 6.61; FAB-MS:m/z=963 (M+)
Above-mentioned 2,8-dibromo or diiodo-indeno [1,2-b, 5, 6-b] two thiophene-4, 9-diketone comprises the steps: above described 2, N-bromo-succinimide or the reaction of N-N-iodosuccinimide for 5-bis-(2-thienyl) diethyl terephthalate, prepare 2, the saponification in potassium hydroxide aqueous solution of 5-bis-(5-bromine or iodine-thiophene-2-yl) diethyl terephthalate, then acidifying, obtain 2, 5-bis-(5-bromine or iodine-thiophene-2-yl) terephthalic acid is in excess chlorination sulfoxide back flow reaction, prepare 2, 5-bis-(5-thiophene-2-yl) p-phthaloyl chloride is under aluminum trichloride (anhydrous) effect, obtain 2, 8-bis-bromine or iodine indenos [1, 2-b, 5,6-b] two thiophene-4,9-diketone, can be expressed as following reaction scheme:
Reaction scheme 3. 2,8-dibromo or diiodo-indeno [1,2-b; 5,6-b] two thiophene-4, the preparation of 9-diketone
Above-mentioned 2,8-dibromo indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone is with reference to Zhao et. al.(Journal of Organic Chemistry, 2007,72 (17), 6364) described in method preparation.
The structure in the organic field principle similar with homologue chemical property is widely cognitive, utilize be same as above-mentioned 2,8-dibromo or two iodo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5; 6-b] preparation method of two thiophene; can prepare corresponding alkyl halide magnesium with magnesium by bromo uncle alkane or the secondary alkane of bromo (alkyl chain length is C1-C20) and corresponding iodo uncle's alkane or the secondary alkane of iodo (alkyl chain length is C1-C20); alkyl halide magnesium and 2; 8-dibromo or diiodo-indeno [1,2-b; 5,6-b] two thiophene-4,9-diketone reaction, obtains 2,8-dibromo or two iodo-4, two alkyl indeno [1, the 2-b of 9-; 5,6-b] two thiophene-4, the two alcohol derivate of 9-, then 2,8-dibromo or two iodo-4, two alkyl indeno [1, the 2-b of 9-; 5,6-b] two thiophene-4, the two alcohol derivate of 9-heat deshydroxy under hydrochloric acid exists, and to prepare general formula be 2 of Formula Il, 8-dibromo or two iodo-4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants, illustrated by reaction scheme below:
Reaction scheme four. 2,8-dibromo (iodine)-4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] preparation of two thiophene derivants
The alkyl halide magnesium of the bromo uncle's alkane that is characterized as independent selection different chain length (C1-C20) of above-mentioned reaction or the secondary alkane of bromo and corresponding iodo uncle's alkane or the iodo alkane second month in a season, with 2,8-dibromo or diiodo-indeno [1,2-b; 5; 6-b] two thiophene-4; 9-diketone reaction obtains 2,8-dibromo or two iodo-4, the two alkyl indenes of 9-1,4-Dithiapentalene-4; the two alcohol derivate of 9-; and then there is lower backflow deshydroxy in hydrochloric acid, preparation have R1 and R2 independently be selected from hydrogen atom or chain length long be 2 of C1-C10 alkyl chain, 8-dibromo or two iodo-4; two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants.
Prepared by aforesaid method 2,8-bis-is bromo-4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] representative example of two thiophene derivants comprises:
Embodiment 6: poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-thiophene is [3,2-b] thiophene-2 also, 5-) preparation (P1)
Will be through 2 of careful purifying, 8-bis-is bromo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5; 6-b] two thiophene (0.2607 g; 0.3 mmol) and 2; two (trimethyl-tin-radical) thiophenes of 5-also [3; 2-b] thiophene (0.1397 g; 0.3 mmol) be dissolved in the THF of 8-10 mL; under nitrogen protection; add PdCl2 (PPh3) 2 (0.014 g, 0.02 mmol), after back flow reaction 36 h; add a small amount of 2; 6 h are to remove bromine end group for two (trimethyl-tin-radical) thiophene (20mg is dissolved in the tetrahydrofuran (THF) of the 1mL) reaction of 5-, adding a small amount of 2-bromothiophene (0.1mL) to remove tributyl tin end group.Then use methanol extraction, the polymkeric substance obtaining processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24 h under vacuum, and productive rate is 70%, structure is as follows:
1h NMR(CDCl
3, δ pmm); 7.76-7.16 (m, 6H), 6.45 (m, 2H), 3.18 (m, 2H), 1.64-1.08 (m, 48 H), 0.88 (t, 12H); Mn=12100 g/mol (number-average molecular weight of polymkeric substance records with Waters GPC 2410, makes calibration curve by polystyrene standards, and tetrahydrofuran (THF) obtains as eluent, and PID is, 2.7).
Example 7: poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-thiophene-2,5-) (P2)
Will be through 2 of careful purifying, 8-bis-is bromo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two (trimethyl-tin-radical) thiophene (0.123 g, 0.3 mmol) of two thiophene (0.2607 g, 0.3 mmol) and 2,5-are dissolved in the THF of 8-10 mL, under nitrogen protection, add PdCl
2(PPh
3)
2(0.014 g, 0.02 mmol), after back flow reaction 36 h, add 2, two (trimethyl-tin-radical) thiophene (20mg of 5-, be dissolved in the tetrahydrofuran (THF) of 1mL) react 6 h to remove bromine end group, adding a small amount of 2-bromothiophene (0.1mL) to remove tributyl tin end group.Then use methanol extraction, the polymkeric substance obtaining processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24 h under vacuum, and productive rate is 45%, structure is as follows:
1h NMR(CDCl
3, δ pmm); 7.76-6.94 (m, 6H), 6.41 (m, 2H), 3.09 (m, 2H), 1.66-1.08 (m, 48 H), 0.88 (t, 12H); Mn=9400 g/mol (number-average molecular weight of polymkeric substance records with Waters GPC 2410, makes calibration curve by polystyrene standards, and tetrahydrofuran (THF) obtains as eluent, and PID is, 3.1).
Example 8: poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-5,5 '-bithiophene-2,2 '-) (P3)
Will be through 2 of careful purifying, 8-bis-is bromo-4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene (0.2607 g, 0.3 mmol) and two (trimethyl-tin-radical)-5 of 2,5-, 5 '-bithiophene (0.148 g, 0.3 mmol) is dissolved in the THF of 8-10 mL, under nitrogen protection, adds PdCl
2(PPh
3)
2(0.014 g, 0.02 mmol), after back flow reaction 36 h, add 2, two (trimethyl-tin-radical) thiophene (20mg of 5-, be dissolved in the tetrahydrofuran (THF) of 1mL) react 6 h to remove bromine end group, adding a small amount of 2-bromothiophene (0.1mL) to remove tributyl tin end group.Then use methanol extraction, the polymkeric substance obtaining processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24 h under vacuum, and productive rate is 66%, structure is as follows:
1h NMR(CDCl
3, δ pmm); 7.76-7.11 (m, 8H), 6.37 (m, 2H), 3.11 (m, 2H), 1.72-1.18 (m, 48 H), 0.88 (t, 12H); Mn=13400 g/mol (Waters GPC 2410 for the number-average molecular weight of polymkeric substance, makes calibration curve by polystyrene standards, and tetrahydrofuran (THF) obtains as eluent, and PID is, 1.9).
The Stille linked reaction that the preparation method of above-mentioned polymkeric substance is applied to, widely cognitive and be used widely in the synthetic field of organic chemistry filed and conjugated polymers, as Milstein etc., J. Am. Chem. Soc. 100 3636 (1978); Milstein etc., J. Am. Chem. Soc. 101 4992 (1979) and Nakamura etc., Angew. Chem., Int. Ed. 40 3208 (2001); With reference to patents such as Choudary, Patent No.:US20040192542.
Therefore utilize 2,8-dibromo (iodine)-4, two (alkylidene group) indeno [1, the 2-b of 9-; 5; 6-b] two thiophene derivants with as thiophene, thiophene also [3; 2-b] thiophene, 2; two tin trimethyls of 2 '-bis-bithiophenes or two tri-n-butyl tin compound are by Stille linked reaction; with above-mentioned identical method can prepare general formula be II based on 4; two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] conjugated polymers of two thiophene, can be represented by following reaction scheme:
The preparation of reaction scheme 5. III polymkeric substance
Above-mentioned based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] in the preparation method of polymkeric substance of two thiophene derivants, relate to 2, two (tin trimethyl) thiophene of 5-, or 2, two (tri-n-butyl tin) thiophene, 2 of 5-, two also [3, the 2-b] thiophene or 2 of (tin trimethyl) thiophene of 5-, two (tri-n-butyl tin) thiophenes of 5-also [3,2-b] thiophene, 5,5 '-bis-(tin trimethyl)-2,2 '-bithiophene, 5,5 '-bis-(tri-n-butyl tin)-2,2 '-bithiophene and Stille linked reaction are widely cognitive and described in detail in organic field, as:
Two (tin trimethyl) thiophene of (1) 2,5-(with reference to Seitz etc., Synth. Commun., 13,121 (1983); Kanbara etc., J. Polym. Sci., Part A:Polym. Chem., 33,999 (1995) and van Pham etc., J. Org. Chem., 49,5250 (1984)).
Two (tri-n-butyl tin) thiophene of (2) 2,5-(with reference to Saadeh etc., Macromolecules, 30,4608 (1997) and Hou etc., Macromolecules, 39,594 (2006)).
Two also [3, the 2-b] thiophene (with reference to people such as Tierney, Synth. Met. 148 195 (2005)) of (tin trimethyl) thiophene of (3) 2,5-.
Two (tri-n-butyl tin) thiophenes of (4) 2,5-also [3,2-b] thiophene (with reference to people such as Drew, Inorg. Synth. 13 47 (1972); The people such as Kotani, J. Organomet. Chem. 429 403 (1992); The people such as Tsuie, J. Mater. Chem. 9 2189 (1999), the people such as Morin, Synth. Met. 34 4680 (2001)).
(5) 5,5 '-bis-(tin trimethyl)-2,2 '-bithiophene (with reference to people such as Drew, Inorg. Synth. 13 47 (1972); Kotani etc., J. Organomet. Chem. 429 403 (1992).
(6) 5,5 '-bis-(tri-n-butyl tin)-2,2 '-bithiophene is (with reference to Miller etc., J. Org. Chem. 60 6813 (1995); Larhed etc., J. Org. Chem. 61 9852 (1996).
Example 9: poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-diazosulfide-4,7-) preparation (P4)
Will be through 4 of careful purifying, two (4,4,5,5-tetramethyl--1,3, the 2-dioxa borine-2-yl) diazosulfides (0.194 g, 0.5 mmol), 2 of 7-, 8-bis-is bromo-4,9-bis-(the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene (0.3693 g, 0.5 mmol) are dissolved in the tetrabutyl phosphonium bromide aqueous ammonium of toluene and 2 mL 20%, and then add (PPh
3)
4pd (0) (2.0mg), after return stirring 24 h, adds the phenylo boric acid of 0.1 g to react after 6 h under nitrogen atmosphere, then adds bromobenzene 0.1mL end-blocking.The object of end-blocking is to eliminate bromine end group and boric acid ester end group, then finishes reaction, pours in methyl alcohol and precipitates, filter, then with washing with acetone 3 h to remove oligopolymer and catalyst residue, products therefrom air drying spends the night, and follows vacuum-drying 24 h.Productive rate: 85%.Structure is as follows:
1h NMR(CDCl
3, δ pmm); 7.92-7.14 (m, 6H), 6.40 (m, 2H), 3.15 (m, 2H), 1.82-1.11 (m, 48 H), 0.88 (t, 12H); Mn=16100 g/mol (Waters GPC 2410 for the number-average molecular weight of polymkeric substance, makes calibration curve by polystyrene standards, and tetrahydrofuran (THF) obtains as eluent, and PID is 2.3).
Above-mentionedly be characterised in that and utilize with 2,8-dibromo (iodine)-4,9 two (alkylidene group) indeno [1,2-b by the preparation method that Suzuki reacts, general formula can be expressed as the conjugated copolymer of IV; 5,6-b] two (4,4,5,5-tetramethyl--1,3, the 2-dioxa borine-2-yl) diazosulfides of two thiophene derivants and 4,7-react by Suzuki, the alternating copolymer obtaining, the independent R that selects of preparation
1and R
2having chain length is C
2-C
204, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants are as the conjugated polymers of correlation unit.
Above-mentioned based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] the reacting in the preparation method of polymkeric substance of preparation by Suzuki of two thiophene derivants, relate to 4,7-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-2-yl) diazosulfide and Suzuki linked reaction be widely cognitive and described in detail in organic field, as:
Two (4,4,5,5-tetramethyl--1,3, the 2-dioxa borine-2-yl) diazosulfides of (1) 4,7-; (people such as Lim, Org. Electron., 11,1772 (2010)).
(2) Suzuki linked reaction, as: (with reference to Miyaura etc., Tetrahedron Lett. 20 3437 (1979); Wolfe etc., J. Am. Chem. Soc. 121 9950 (1999); Yamada etc., Chem. Commun. 68 7733 (2003); Leadbeater etc., Chem. Commun. 2881 (2005) and Kotha etc., Adv. Synth. Catal. 347 1215 (2005); With reference to Spivak patent, Patent No.:US6838585, (2005); Guram etc., Patent No.:US6265601, (2001) and Nolan etc., Patent No.:6583307, (2003).
Therefore utilize 2,8-dibromo or two iodo-4, two (alkylidene group) indeno [1, the 2-b of 9-; 5,6-b] two thiophene derivants and 4,7-two (4,4; 5,5-tetramethyl--1,3,2-dioxa borine-2-yl) diazosulfide is by Suzuki linked reaction; with above-mentioned identical method can prepare general formula be IV based on two (alkylidene group) indeno [1, the 2-b of 4,9-; 5,6-b] conjugated copolymer of two thiophene and diazosulfide, can be represented by following reaction scheme:
The preparation of reaction scheme 5. IV polymkeric substance.
Embodiment 10: based on poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-thiophene is [3,2-b] thiophene-2 also, 5-) be (P1) preparation of the polymer solar battery of electron donor material,
It comprises the following steps:
(1) mark of ITO substrate and cleaning
ITO conductive glass substrate is to buy from Shenzhen company of SAST, and precut becomes the regular square of 15mm × 15mm, and ITO layer is removed in the side photoetching that width is 5mm.The technical parameter of ito glass substrate is: square resistance is less than 20 Ω/, and transparency is greater than 85%, and roughness is within the scope of 5nm.
The conductive layer of ito glass substrate is water white, differentiates the face at its ITO layer place by mark, determines ito surface with the resistance grade of digital multimeter, then in nonconducting one side glass cutter marker number.
Because and even the pollutent of ITO substrate surface is all very large on the impact of the final device performance of the film forming of spin coating anode buffer layer and polymer light-emitting layer subsequently, therefore the cleaning of ITO substrate is a very crucial step, must carry out careful cleaning thoroughly to remove the pollutent of substrate surface.Conventionally these pollutents are divided into four classes: Micro-particles, as dust etc.; Organic substance, as grease and coating etc.; Inorganic substance, as alkali, salt etc.; Microorganism body.The method of removing substrate surface dirt has: chemical cleaning method, ultrasonic cleaning process, vacuum bakeout method and ion bombardment method etc.We mainly adopt ultrasonic cleaning process in laboratory, and the ITO substrate of marker number is placed on film hanger, follow these steps to carry out surface cleaning:
1, acetone cleans: with acetone soln ultrasonic cleaning 10 minutes, object was grease and other organism in order to remove ITO substrate surface.
2, washing composition cleans: the micro level semiconductor special purpose detergent ultrasonic cleaning with 1% 10 minutes, grease and the organism removed not yet completely to clean acetone solvent.
3, washed with de-ionized water: with deionized water ultrasonic cleaning twice, be 10 minutes, be mainly washing composition and some inorganicss of removing containing dirt at every turn.
4, Virahol cleans: with Virahol ultrasonic cleaning 10 minutes, object was to wash the remaining organic impurity of possibility.
After having cleaned through above four steps, ITO substrate is put into constant temperature oven and dry (100
0c).
(2) spin coating of anode buffer layer
Before spin coating anode buffer layer, ITO substrate surface will pass through oxygen Plasma(plasma) to process, the condition that Plasma processes is 2～3mPa, and oxygen flow is 4～5ml/s, and the treatment time is 4 minutes.The object that Plasma processes is the effect of further removing the residual organic dirt of ITO substrate surface, improving substrate surface contact angle and improving ITO work function.
According to experiment purpose difference, select PEDOT:PSS(to gather 3,4-ethylene dioxythiophene/poly styrene sulfonate) be anode buffer layer.PEDOT:PSS solution is to buy from German Bayer company, is numbered P4083, is dailyly placed in refrigerator storeroom in case degraded rises to room temperature and just can get rid of film before use.
(the KW-4A of sol evenning machine for buffer layer, the Microelectronics Center, Academia Sinica) high speed spin-coating film, thickness is generally determined by strength of solution and rotating speed, concrete surface profiler (the Alpha step-500 of Tencor company of the U.S.) mensuration for thickness, obtains needed buffer layer thickness by the rotating speed of adjusting sol evenning machine.The spin coating of buffer layer is preferably processed in latter 30 minutes and is completed at oxygen Plasma, otherwise airborne impurity is re-attached on ITO substrate, and the contact angle of ITO substrate surface is increased again, causes buffer layer to be difficult to adhere to.In addition, in order to obtain uniform buffer layer, spin coating ground speed should be too not low, and rule of thumb data is that 1000～3000rps is good.
By spin coating the ITO substrate of anode buffer layer be placed in vacuum drying oven and carry out vacuum-drying, constant temperature is at 80 DEG C, general vacuum-drying just can be removed remaining solvent for 3 hours.
(3) preparation of polymkeric substance and acceptor material layer composite bed
Conjugated polymers is placed in clean sample bottle and is weighed, proceed in the glove box (VAC company) that is full of nitrogen protection, dissolve and be placed on mixing platform (Cole-Pamer company of the U.S.) with suitable solvent (as toluene, chlorobenzene etc.) and stir conjugated polymers is uniformly dissolved; General formula is using [6, the 6]-C as electron acceptor material
61phenyl-C61 butyric acid (PC
61bM) be placed in clean sample bottle and weigh; proceed in the glove box (VAC company) that is full of nitrogen protection; with suitable solvent (as toluene; chlorobenzene etc.) dissolve and be placed on mixing platform (Cole-Pamer company of the U.S.) and stir conjugated polymers is uniformly dissolved; the above-mentioned solution obtaining by a certain percentage (in this example, ratio is 1:1) mixes; the mixing solutions obtaining filters with 0.45 micron of filtering head, with the oarse-grained insoluble impurities of filtering, plays the effect that improves film planarization.Then, the substrate that scribbles anode buffer layer good vacuum-drying is moved in glove box and carries out polymkeric substance/PC
61the spin coating of BM, spin coating process is identical with anode buffer layer.Before spin coating, carry out thickness measuring with surface profiler and observe surface topography to obtain the uniform film of desired thickness.
(4) evaporation of metal electrode
Spin coating has the diaphragm of luminescent layer to be transferred to electrode evaporation special gloves case through transitional storehouse by getting rid of film glove box.Electrode evaporation completes in DM-300B type vacuum plating unit (Beijing instrument plant), and F-160/450 type turbomolecular pump is main pump, and oil diffusion pump is forepump.
Open evaporation mask, selected electrode column also clips plating boat, puts into corresponding electrode materials.The ITO substrate of film forming is placed on special mask frame, notes the location of anode scraping article, then the mask frame that substrate is housed is moved into the top of evaporation chamber plating boat.The evaporation mask that closes, opens prime mechanical pump, opens the valve between evaporation chamber and mechanical pump, and prime mechanical pump is taken out in advance evaporation chamber vacuum to time below 4Pa and shut this valve.Then open the valve between mechanical pump and molecular pump, also take out in advance molecular pump vacuum to 4Pa, open subsequently the valve between molecular pump and evaporation chamber, open cooling water power source and molecular pump power source, after molecular pump shows normal operation, open high vacuum gauge power supply.When the reading of high vacuum gauge reaches 3 × 10
-4pa is following can electrode evaporation.
The thickness of evaporation speed and each electrode layer is monitored in real time by quartz resonator film thickness monitor (STM-100 type, Sycon company).Conventionally the empirical condition of evaporating Al layer is:
Al: Bulk Density: 2.73Gm/cm
3
The impedance factor (z-Factor): 1.08
Plating initial vacuum degree: 3 × 10
-4pa
Thickness is less than at 500 o'clock, speed: <10/s
After evaporation finishes, close successively the valve between high vacuum gauge, molecular pump, molecular pump and evaporation chamber, equimolecular pump cuts out the valve between mechanical pump and molecular pump after stopping completely.After approximately spending 10 minutes, evaporation cavity temperature is down to room temperature can, toward pouring nitrogen in it, open evaporation mask taking-up device.Close subsequently evaporation mask, then with mechanical pump by the forvacuum of evaporation chamber below 4Pa.Close valve, water coolant and each power supply between mechanical pump and evaporation chamber.So far electrode evaporation finishes.
(5) test of polymer solar battery:
This testing laboratory adds AM 0 spectral filter and AM 1 spectral filter is realized AM 1.5 simulated solar irradiations before the xenon source of 100W.Adopt 100mW/cm2 irradiance.Irradiance is to be determined by standard silicon solar cell.This standard light battery is calibrated through national defence 3004 calibration laboratories: under AM 1.5 standard spectrums, use 100mW/cm
2when the illumination of radiant illumination, standard light electric current is 0.125A.After determining radiant illumination, can carry out current voltage characteristic test, its effciency of energy transfer can be calculated by defining:
Wherein P
maxfor peak power output, unit is mW; P
infor radiant illumination, unit is mW/cm
2; S is the useful area of device, and unit is cm
2.
For example,, with poly-(4,9-two (the sub-decyl of 2-hexyl) indeno [1,2-b; 5,6-b] two thiophene-2,8-thiophene is [3,2-b] thiophene-2 also, 5-) and be electron donor material, PC
61bM is electron acceptor material, and the master data of the polymer solar battery of being prepared by the preparation process of above-mentioned polymer solar battery is as follows:
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. one kind 4, two alkylidene group indeno two thiophene derivants of 9-, is characterized in that, chemical structure of general formula is:
2. one kind 2,7-dibromo or two iodo-4, two alkylidene group indeno two thiophene derivants of 9-, is characterized in that, chemical structure of general formula is:
3. the conjugated copolymer based on two alkylidene group indeno two thiophene derivants of 4,9-, is characterized in that, general structure is:
Utilize 2 described in claim 2,7-dibromo or two iodo-4, two alkylidene group indeno two thiophene derivants and 2 of 9-, two (trimethyl-tin-radical) thiophenes of 5-also [3,2-b] thiophene or 2, two (trimethyl-tin-radical) thiophene or 2 of 5-, 2 '-bis-(trimethyl-tin-radical)-5,5 '-bis-bithiophenes are prepared by Stille linked reaction.
4. the conjugated copolymer based on two alkylidene group indeno two thiophene derivants of 4,9-and diazosulfide, is characterized in that, chemical structure of general formula is:
Utilize 2 described in claim 2,7-dibromo or two iodo-4, two alkylidene group indeno two thiophene derivants of 9-are prepared by Suzuki linked reaction with 4,7-pair of (4,4,5,5-tetramethyl--[1,3,2]-dioxa borine-2-yl) diazosulfides.
5. as claimed in claim 14, the preparation method of two alkylidene group indeno two thiophene derivants of 9-, it is characterized in that general formula is that the preparation process of (I) is: 2,5-dibromoterephthalic acid is under excess ethyl alcohol and sulfur oxychloride existence, reflux, prepare 2,5-dibromoterephthalic acid diethyl ester, 2, 5-dibromoterephthalic acid diethyl ester reacts with 2-thiophene magnesium bromide the 2-thienyl zinc chloride preparing and reacts under tetrakis triphenylphosphine palladium catalysis with Zinc Chloride Anhydrous, obtain 2, 5-bis-(thiophene-2-yl) diethyl terephthalate, be the saponification that refluxes in 30-48% in potassium hydroxide aqueous solution mass percent, then be acidified to pH=3 with concentrated hydrochloric acid, obtain 2, 5-bis-(thiophene-2-yl) terephthalic acid is in excess chlorination sulfoxide back flow reaction, prepare 2, 5-bis-(thiophene-2-yl) p-phthaloyl chloride is under aluminum trichloride (anhydrous) effect, indenes 1,4-Dithiapentalene-4 that reaction obtains, the Grignard reagent that the brominated alkanes that 9-diketone is C1-C20 with chain length again prepares with magnesium reacts, hydrochloric acid reflux dehydroxylation for the tertiary alcohol obtaining, obtain 4, 9-bis-(alkylidene group) indenes 1,4-Dithiapentalene.
6. as claimed in claim 22,7-dibromo or two iodo-4, the preparation method of two alkylidene group indeno two thiophene derivants of 9-, its feature preparation process is: 2,5-dibromoterephthalic acid, under excess ethyl alcohol and sulfur oxychloride existence, refluxes, prepare 2,5-dibromoterephthalic acid diethyl ester, 2, 5-dibromoterephthalic acid diethyl ester reacts preparation with 2-thiophene magnesium bromide 2-thienyl zinc chloride with Zinc Chloride Anhydrous is under tetrakis triphenylphosphine palladium catalysis, obtain 2, 5-bis-(thiophene-2-yl) diethyl terephthalate, in trichloromethane, use N-bromo-succinimide or N-N-iodosuccinimide bromination or iodate, obtain 2, 5-bis-(5-bromine or 5-iodothiophen-2-yl) diethyl terephthalate is the saponification that refluxes in 30-48% at potassium hydroxide quality percentage composition ratio, then be acidified to pH=3 with concentrated hydrochloric acid, obtain 2, 5-bis-(5-bromine or iodine thiophene-2-yl) terephthalic acid is in excess chlorination sulfoxide back flow reaction, prepare 2, 5-bis-(2-bromine or 5-iodothiophen base) p-phthaloyl chloride is under aluminum trichloride (anhydrous) effect, obtain 2, 7-dibromo or diiodo-indenes 1,4-Dithiapentalene-4, 9-diketone, by 2, 7-dibromo indenes 1,4-Dithiapentalene-4, 9-diketone or 2, 7-diiodo-indenes 1,4-Dithiapentalene-4, 9-diketone is added in there-necked flask, under anhydrous and oxygen-free state, add dry orthodichlorobenzene, after stirring at room temperature 20min, the alkyl magnesium bromide that is C1-C20 by the alkyl chain length preparing in advance at room temperature joins in reaction, under argon shield, stirring reaction spends the night, add water after cancellation, suction filtration, filter cake is washed by ethyl acetate, and filtrate is extracted with ethyl acetate after washing, anhydrous Na SO
4dry, decompression steams solvent, obtain brown solid, brown solid is dissolved in the hot dehydrated alcohol of 30mL60-65 DEG C, be transferred in the there-necked flask of 100mL, add the hydrochloric acid of 10mL, the THF of 20mL, heating reflux reaction spends the night, be cooled to room temperature, the cancellation that adds water, with petroleum ether extraction, removes solvent under reduced pressure, and sherwood oil is crossed the post yellow solid of purifying to obtain.
7. as claimed in claim 3 based on 4; the preparation method of the conjugated copolymer of two alkylidene group indeno two thiophene derivants of 9-; its characterization step comprises: by purified 2; 7-dibromo or two iodo-4; the two alkylidene group indenes 1,4-Dithiapentalenes and 2 of 9-; two (trimethyl-tin-radical) thiophenes of 5-also [3; 2-b] thiophene or 2; two (trimethyl-tin-radical) thiophene or 5 of 5-; 5 '-bis-(trimethyl-tin-radical)-2; 2 '-bis-bithiophenes are dissolved in THF for 1:1 in molar ratio, under nitrogen protection, add PdCl
2(PPh
3), after back flow reaction 36h, add two (trimethyl-tin-radical) thiophene reaction of 2,5-6h to remove bromine end group or iodine end group, then add 2-bromothiophene to remove tributyl tin end group; Then use methanol extraction, the polymkeric substance obtaining processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24h under vacuum.
8. as claimed in claim 4 based on 4, the preparation method of the conjugated copolymer of two alkylidene group indeno two thiophene derivants of 9-and diazosulfide, its characterization step comprises: will be after careful purifying 2,7-dibromo or two iodo-4, two alkylidene group indeno two thiophene derivants and corresponding 4 of 9-, 7-two (4,4,5,5-tetramethyl--[1,3,2]-dioxa borine-2-yl) diazosulfide is dissolved in toluene for 1:1 in molar ratio, then adds the aqueous solution and the Pd (PPh of 20% Tetrabutyl amonium bromide
3)
4after degassed, under nitrogen protection, reflux 36h, then uses phenylo boric acid and bromobenzene end-blocking, and the reaction solution obtaining precipitates in methyl alcohol, then processes to remove oligopolymer and catalyst residue with alchlor chromatography column, dry 24h under vacuum.
9. a solar cell, the photovoltaic material layer that it is characterized in that battery comprises claimed in claim 3 based on 4, the conjugated copolymer of two alkylidene group indeno two thiophene derivants of 9-or the conjugated copolymer based on two alkylidene group indeno two thiophene derivants of 4,9-and diazosulfide claimed in claim 4.
10. the preparation method of solar cell as claimed in claim 9, based on claimed in claim 34, the two alkylidene group indeno two thiophene derivant conjugated copolymers or claimed in claim 4 based on 4 of 9-, the conjugated copolymer of two alkylidene group indeno two thiophene derivants of 9-and diazosulfide is electron donor material, it is characterized in that including following steps: mark and the cleaning of (1) ITO substrate; (2) spin coating of anode buffer layer; (3) preparation of polymkeric substance and acceptor material layer composite bed, comprise claimed in claim 3 based on 4, two (alkylidene group) indeno two thiophene derivant conjugated copolymers or claimed in claim 4 based on 4 of 9-, after the conjugated copolymer of two alkylidene group indeno two thiophene derivants of 9-and diazosulfide weighs, in the glove box that is full of nitrogen, dissolve and stir with toluene or chlorobenzene; Equally, by [6,6]-phenyl-C
61-methyl-butyrate or [6,6]-phenyl-C
71-methyl-butyrate dissolves and stirs with toluene or chlorobenzene after weighing in the glove box that is full of nitrogen; Then, above-mentioned two kinds of solution are mixed in the ratio of 1:1-1:4, after filtering with the filtering head of 0.45 micron, carry out spin coating; (4) evaporation of metal aluminium electrode, vacuum tightness is 3 × 10
-4pa.
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