CN106928255A - Furans organic micromolecule photovoltaic material of a kind of benzo two and its preparation method and application - Google Patents

Furans organic micromolecule photovoltaic material of a kind of benzo two and its preparation method and application Download PDF

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CN106928255A
CN106928255A CN201710197021.0A CN201710197021A CN106928255A CN 106928255 A CN106928255 A CN 106928255A CN 201710197021 A CN201710197021 A CN 201710197021A CN 106928255 A CN106928255 A CN 106928255A
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benzo
furans
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photovoltaic material
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CN106928255B (en
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刘波
陈远道
王晓波
王钢
刘骏
周诗彪
胡霞
何敏
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Hunan University of Arts and Science
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    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract

The invention discloses furans organic micromolecule photovoltaic material of a kind of benzo two and its preparation method and application.The present invention has synthesized a kind of benzo [1,2 b containing different alkyloxy side chains；3,4 b] two furans (BDF) organic electronic donor unit, the method being coupled by Stille, BDF units are connected by carbon-carbon single bond with another electron acceptor unit pyrrolo-pyrrole-dione (DPP), BDF organic micromolecule photovoltaic materials are obtained, shown in structure such as formula (I).There is these organic molecule photovoltaic materials visible region wide to absorb, the band gap of suitable HOMO and lumo energy and relative narrower.With such organic molecule as electron donor, PC61BM or organic matter electron acceptor are prepared for organic solar batteries for electron acceptor, and its highest energy conversion efficiency can reach 5.0%, with good photoelectric transformation efficiency.

Description

Furans organic micromolecule photovoltaic material of a kind of benzo two and its preparation method and application
Technical field
The present invention relates to photovoltaic material technical field, and in particular to a kind of furans organic micromolecule photovoltaic material of benzo two And its preparation method and application.
Background technology
Benzo [1,2-b；3,4-b] two furans (BDF) have obtained very as electron donor in polymer solar battery Good application, is the very excellent electron donor unit of a class performance [Bo Liu, Xuewen Chen, Yingping Zou, Lu Xiao,Xinjun Xu,Yuehui He,Lidong Li,and Yongfang Li.Macromolecules,2012,45, 6896-6905.], but it is applied to the organic molecule sun after being coupled as electron donor and other electron acceptor units Energy field of batteries is seldom reported in the literature.BDF has and benzo [1,2-b；3,4-b] the similar condensed hetero ring of Dithiophene (BDT) Structure, BDT is applied in organic molecule solar cell as electron donor, obtains up to 5.8% energy conversion effect Rate [Yuze Lin, Lanchao Ma, Yongfang Li, Yunqi Liu, Daoben Zhu, and Xiaowei Zhan.Advanced Energy Materials, 2013,3,1166-1170.], old Yongsheng seminar of Nankai University uses 4,8- Two different octyloxies-benzo [1,2-b；3,4-b] Dithiophene is connected the thiophene coupling of company three of strong electron-withdrawing group group with end, obtains A kind of BDT organic micromolecules photovoltaic material (DR3TSBDT), DR3TSBDT has in the range of 300~730nm to sunshine Absorb well, the energy conversion efficiency of the solar cell of preparation is up to 9.6%, be organic solar batteries conversion at that time World record [Bin Kan, Qian Zhang, Miaomiao Li, Xiangjian Wan, the Wang Ni, Guankui of efficiency Long,Yunchuang Wang,Xuan Yang,Huanran Feng,Yongsheng Chen.J.Am.Chem.Soc.2014, 136,15529-15532].Therefore, the DBF units for being obtained by the use of oxygen atom substitution sulphur atom are applied to organic as electron donor In small molecule solar cell, it is contemplated that efficient photovoltaic performance can be obtained.Reason is mainly oxygen atom with smaller than sulphur atom Atomic radius, so BDF has planar structure more more preferable than BDT, after BDF is coupled from different electron acceptor, obtain BDF organic micromolecules are expected to possess the carrier mobility of broader absorption spectrum and Geng Gao.
The present invention has synthesized the BDF monomers containing different flexible side-chains, and the method being coupled with Stille obtains a kind of BDF They have been carried out optics and electrochemistry etc. and characterized by organic micromolecule solar cell material, and to it in solar cell On application studied.
The content of the invention
In view of this, it is an object of the invention to propose a kind of furans organic micromolecule photovoltaic material of benzo two and its system Preparation Method and application, the organic molecule photovoltaic material are the BDF organic micromolecule photovoltaic materials of carbon-to-carbon singly-bound connection, and Solar cell can be applied to as electron donor material.
Based on the furans organic micromolecule photovoltaic material of a kind of benzo two that above-mentioned purpose, the present invention are provided, this is organic small Shown in the structure of molecule photovoltaic material such as formula (I)：
Wherein, R is alkyl.
Compound shown in formula (I) is 4,8- dialkoxies-benzo (1,2-b；4,5-b ') (2,5- of-two furans -2,6- two Diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones).
In the present invention, it is preferred to, R is 8~12 straight or branched alkane of carbon atom.
In the present invention, it is further preferred that the R is selected from the one kind in following group：
In the present invention, whenWhen, the target compound of synthesis is the different octyloxy-benzene of 4,8- bis- And (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) (M1)；
WhenWhen, the target compound of synthesis is 4,8-, bis- octyloxies-benzo (1,2-b； 4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) (M2)；
WhenWhen, the target compound of synthesis for 4,8- docosane epoxide- Benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) (M3)。
A kind of BDF organic micromolecules material that the present invention is provided has good machinability, and by tentatively tasting Examination proves there is preferable light transfer characteristic, has wide application as the working media of organic molecule solar cell Prospect.
Further, present invention also offers a kind of preparation of the described furans organic micromolecule photovoltaic material of benzo two Method, comprises the following steps：
1) furans -4 of benzo two, 8- diketone overnight, is cooled to room temperature with brominated alkanes back flow reaction in water, by mixture It is poured into water, extracts, dry, be spin-dried for solvent, cross silicagel column, obtains 4,8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans Mutter；
2) under nitrogen protection, by 4 at -78 DEG C, 8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans and positive fourth Base lithium mixes in anhydrous tetrahydro furan, reacts 1~3 hour, continuously adds excessive trimethyltin chloride, reacts at room temperature At night, pour the mixture into water, extraction is dried, and is spin-dried for solvent, is recrystallized to give 2,6- bis- (tin trimethyl)-(2- second of 4,8- bis- Base hexyloxy)-benzo [1,2-b；3,4-b '] two furans；
3) under nitrogen protection, by 2,6- bis- (tin trimethyl) -4,8- bis- (2- ethyl hexyl oxies)-benzo [1,2-b；3,4- B '] two furans and 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) are added to dry toluene In, add Pd (PPh3)4(tetrakis triphenylphosphine palladium), reacts 40~50 hours at 110~120 DEG C, is cooled to room temperature, precipitating, Filtering, crosses silicagel column, obtains compound (I)；
Wherein, 4,8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans structural formula such as following formula (1) shown in：
(the 2- ethyl hexyl oxies)-benzo [1,2-b of 2,6- bis- (tin trimethyl) -4,8- two；3,4-b '] two furans structure Shown in formula such as following formula (2)：
The structural formula of 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) is shown below：
The synthetic route of target compound (I) of the present invention is as follows：
i)NaOH,Zn,H2O,RBr,reflux,overnight；ii)n-BuLi,THF,Sn(CH3)3Cl,-78℃, overnight；iii)Pd(PPh3)4,toluene,115℃,48h.
In the present invention, it is preferred to, step 1) described in brominated alkanes be n-octane bromide, bromo-iso-octane or bromo ten Dioxane；Furans -4,8- the diketone of benzo two is 1 with the mol ratio of brominated alkanes:2~3.
In the present invention, it is preferred to, step 2) in 4,8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans, positive fourth Base lithium is 1 with the mol ratio of trimethyltin chloride:3~4:3~5；Recrystallize to recrystallize in methyl alcohol.
In the present invention, it is preferred to, step 3) in 2,6- bis- (tin trimethyl) -4,8- bis- (2- ethyl hexyl oxies)-benzo [1,2-b；3,4-b '] two furans rub with 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) You are than being 1:1~3；Pd(PPh3)4With the matter of 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) Amount is than being 5~10：100.
In the present invention, it is preferred to, step 3) in precipitating be precipitating in methyl alcohol；The leacheate for crossing silicagel column is volume ratio 1:1 petroleum ether/dichloromethane mixed liquor.
A series of BDF organic molecules photovoltaic material preparation methods that the present invention is provided are the sides using Stille couplings Method, by BDF electron donors unit, directly coupling is formed with another kind of aromatic heterocycle electron acceptor unit.
The present invention has synthesized a kind of benzo [1,2-b containing different alkyloxy side chains；3,4-b] two furans (BDF) are organic Electron donor unit, the method being coupled by Stille, by BDF units by carbon-to-carbon singly-bound and another electron acceptor unit Pyrrolo-pyrrole-dione (DPP) is connected, and obtains BDF organic micromolecule photovoltaic materials.They common are machine solvent (such as Dichloromethane, chloroform, tetrahydrofuran etc.) in have good dissolubility, high-quality film can be prepared with solution methods. Meanwhile, there is these organic molecule photovoltaic materials visible region wide to absorb, suitable HOMO and lumo energy and relative Narrower band gap.With such organic molecule as electron donor, PC61BM or organic matter electron acceptor for electron acceptor be prepared for it is organic Solar cell, its highest energy conversion efficiency can reach 5.0%, with good photoelectric transformation efficiency.
Therefore, further, exist present invention also offers the described furans organic micromolecule photovoltaic material of benzo two Application in solar cell.
In the present invention, it is preferred to, the furans organic micromolecule photovoltaic material of the benzo two is used as solar cell electricity Sub- donor material.
The present invention is electron donor material with the furans organic micromolecule photovoltaic material of above-mentioned benzo two, is applied to organic small Molecular solar cells, its preparation method is as follows：
By BDF organic micromolecules electron donor material of the invention and electron acceptor (PC61BM or organic matter electronics are received Body) material blending, chloroform is added, mixture is fully dissolved, it is spin-coated on electro-conductive glass ITO and prepares conductive film, Then the evaporation metal aluminium electrode on film.
The BDF organic micromolecule photovoltaic materials that the present invention is provided have absorption spectrum and suitable electrochemical energy wide Level, and the molecular structure of each step synthetic product is characterized with the method for nuclear magnetic resoance spectrum, mass spectrum and elementary analysis.With it is ultraviolet-can See the optical property of Absorption Spectrum Research BDF organic micromolecule photovoltaic materials.It is organic BDF classes to be have studied with cyclic voltammetry The chemical property of small molecule photovoltaic material.And solar cell device has been made as electron donor using it, obtain good Photoelectric transformation efficiency.
Compared with prior art, the invention has the advantages that：
(1) route of present invention synthesis is simple, low cost, and synthetic method has universality, and can preferably promote should Use the synthesis of other BDF classes materials.
(2) BDF organic micromolecules photovoltaic material of the invention has the conjugated structure of big π planes, and the BDT classes that compare have Machine molecular material, is expected to obtain broader uv-visible absorption spectra.
(3) BDT class organic molecule materials are compared to, BDF organic micromolecules photovoltaic material of the invention has relatively low HOMO energy levels, the stability to oxygen is high, is conducive to the solar cell device that processability is more stable.
(4) the furans organic micromolecule photovoltaic material of present invention benzo two is electron donor material, is applied to organic small Molecular solar cells obtain energy conversion efficiency (PCE=5.0%) higher, have a good application prospect.
Brief description of the drawings
Fig. 1 is the absorption spectrum of BDF organic micromolecules photovoltaic material of the present invention；
Fig. 2 is the electrochemical analysis figure of BDF organic micromolecules photovoltaic material of the present invention；
Fig. 3 is the photoelectric transformation efficiency figure of BDF organic micromolecules photovoltaic material of the present invention；
Fig. 4 is the outer conversion quantum efficiency figure of BDF organic micromolecules photovoltaic material of the present invention；
Fig. 5 is the morphology analysis figure of BDF organic micromolecules photovoltaic material active layer of the present invention；Wherein a figures are height map, B figures are phasor.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and reference Accompanying drawing, the present invention is described in more detail.
The synthetic route of BDF organic micromolecules photovoltaic material of the present invention is as follows：
i)NaOH,Zn,H2O,RBr,reflux,overnight；ii)n-BuLi,THF,Sn(CH3)3Cl,-78℃, overnight；iii)Pd(PPh3)4,toluene,115℃,48h.
The different octyloxies of 1 4,8- of embodiment bis--benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyls - 3,6- furyl -2- pyrrolo-pyrrole-diones) (M1) preparation
Comprise the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds bromo-iso-octane (3.86g, 20mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (2.19g, yield 53%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,16H),0.86(t,12H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3mL, 7.0mmol), then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (8mL, 8.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.74g, yield 50%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 16H),0.97(m,12H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M1
Nitrogen protection under, by bromo- 2, the 6- bis- of the compound 2 and 2- of equimolar amounts (2,5- diisooctyl -3,6- furyls - 2- pyrrolo-pyrrole-diones) (0.2mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then Add Pd (PPh3)4(10mg), stirring reaction is cooled to room temperature after 48 hours at 115 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (237mg is produced to obtain blue solid M1 Rate 85%)；R group is as follows in wherein compound M1：
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 48H),0.97-0.85(m,36H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.02； H,8.21；N,4.03.
The different octyloxies of 2 4,8- of embodiment bis--benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyls - 3,6- furyl -2- pyrrolo-pyrrole-diones) (M1) preparation
Comprise the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds bromo-iso-octane (4.83g, 25mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (1.95g, yield 47%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,16H),0.86(t,12H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (2.6mL, 6.0mmol), then proceedes to Stirring 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (6mL, 6.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.70g, yield 47%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 16H),0.97(m,12H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M1
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.4mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(26mg), stirring reaction is cooled to room temperature after 50 hours at 110 DEG C, pours into precipitating in 100mL methyl alcohol, filtering, Crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), obtain blue solid M1 (230mg, yield 82%)；R group is as follows in wherein compound M1：
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 48H),0.97-0.85(m,36H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.02； H,8.21；N,4.03.
The different octyloxies of 3 4,8- of embodiment bis--benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyls - 3,6- furyl -2- pyrrolo-pyrrole-diones) (M1) preparation
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds bromo-iso-octane (5.79g, 30mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (2.10g, yield 51%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,16H),0.86(t,12H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3.4mL, 8.0mmol), then proceedes to 1.5 hours of stirring, move to room temperature lithiumation 1.5 hours, be cooled at -78 DEG C, disposably add trimethyltin chloride (10mL, 10.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow and consolidates Body, faint yellow acicular crystal compound 2 (0.68g, yield 46%) is obtained with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 16H),0.97(m,12H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M1
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.6mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(19.5mg), stirring reaction is cooled to room temperature after 40 hours at 120 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (232mg is produced to obtain blue solid M1 Rate 83%)；R group is as follows in wherein compound M1：
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 48H),0.97-0.85(m,36H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.02； H,8.21；N,4.03.
Bis- octyloxies of 4,8- of embodiment 4-benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3, 6- furyl -2- pyrrolo-pyrrole-diones) (M2) preparation
The synthetic method of compound M2 is identical with the synthetic method of compound M1 in embodiment 1, and brominated alkanes use bromo Normal octane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds n-octane bromide (3.86g, 20mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (2.19g, yield 53%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,22H),0.86(t,6H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3mL, 7.0mmol), then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (8mL, 8.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.74g, yield 50%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 22H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M2
Nitrogen protection under, by bromo- 2, the 6- bis- of the compound 2 and 2- of equimolar amounts (2,5- diisooctyl -3,6- furyls - 2- pyrrolo-pyrrole-diones) (0.2mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then Add Pd (PPh3)4(10mg), stirring reaction is cooled to room temperature after 48 hours at 115 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (220mg is produced to obtain blue solid M2 Rate 79%)；R group is as follows in wherein compound M2：
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 54H),0.97-0.85(m,30H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.01； H,8.22；N,4.05.
Bis- octyloxies of 4,8- of embodiment 5-benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3, 6- furyl -2- pyrrolo-pyrrole-diones) (M2) preparation
The synthetic method of compound M2 is identical with the synthetic method of compound M1 in embodiment 2, and brominated alkanes use bromo Normal octane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds n-octane bromide (4.83g, 25mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (1.95g, yield 47%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,22H),0.86(t,6H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (2.6mL, 6.0mmol), then proceedes to Stirring 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (6mL, 6.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.70g, yield 47%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 22H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M2
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.4mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(26mg), stirring reaction is cooled to room temperature after 50 hours at 110 DEG C, pours into precipitating in 100mL methyl alcohol, filtering, Crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), obtain blue solid M2 (210mg, yield 75%)；R group is as follows in wherein compound M2：
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 54H),0.97-0.85(m,30H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.01； H,8.22；N,4.05.
Bis- octyloxies of 4,8- of embodiment 6-benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3, 6- furyl -2- pyrrolo-pyrrole-diones) (M2) preparation
The synthetic method of compound M2 is identical with the synthetic method of compound M1 in embodiment 3, and brominated alkanes use bromo Normal octane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds n-octane bromide (5.79g, 30mmol), backflow is anti- Answer 2 hours, then add zinc powder (0.2g, 3mmol), after finishing, continue to react overnight.Room temperature is cooled to, water is poured the mixture into In, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column, and (petroleum ether is Leacheate), obtain colourless oil liquid compound 1 (2.10g, yield 51%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,22H),0.86(t,6H).
TOF-MS:M/z=414.
Anal.Calcd for C26H38O4(%):C,75.32；H,9.24；O, 15.44.Found (%):C,75.89；H, 9.19；O,15.47.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3.4mL, 8.0mmol), then proceedes to 1.5 hours of stirring, move to room temperature lithiumation 1.5 hours, be cooled at -78 DEG C, disposably add trimethyltin chloride (10mL, 10.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow and consolidates Body, faint yellow acicular crystal compound 2 (0.68g, yield 46%) is obtained with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 22H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=740.
Anal.Calcd for C32H54O4Sn2(%):C,51.92；H,7.35；O, 8.65.Found (%):C,51.93； H,7.38；O,8.67.
3. the synthesis of compound M2
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.6mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(19.5mg), stirring reaction is cooled to room temperature after 40 hours at 120 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (215mg is produced to obtain blue solid M2 Rate 77%)；R group is as follows in wherein compound M2：
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 54H),0.97-0.85(m,30H).
TOF-MS:M/z=1396.
Anal.Calcd for C86H114N4O12(%):C,74.00；H,8.23；N, 4.01.Found (%):C,74.01； H,8.22；N,4.05.
The 4,8- docosane epoxide of embodiment 7-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent for-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-diones) (M3) preparation
The synthetic method of compound M3 is identical with the synthetic method of compound M1 in embodiment 1, and brominated alkanes use bromo N-dodecane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds N-dodeeyl bromide (4.98g, 20mmol), backflow Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after finishing, continue to react overnight.Room temperature is cooled to, is poured the mixture into In water, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column (petroleum ether It is leacheate), obtain colourless oil liquid compound 1 (2.19g, yield 53%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,38H),0.86(t,6H).
TOF-MS:M/z=526.
Anal.Calcd for C34H54O4(%):C,77.52；H,10.33；O, 12.15.Found (%):C,77.53； H,10.36；O,12.17.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3mL, 7.0mmol), then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (8mL, 8.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.74g, yield 50%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 38H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=852.
Anal.Calcd for C40H70O4Sn2(%):C,56.36；H,8.28；O, 7.51.Found (%):C,56.33； H,8.30；O,7.52.
3. the synthesis of compound M3
Nitrogen protection under, by bromo- 2, the 6- bis- of the compound 2 and 2- of equimolar amounts (2,5- diisooctyl -3,6- furyls - 2- pyrrolo-pyrrole-diones) (0.2mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then Add Pd (PPh3)4(10mg), stirring reaction is cooled to room temperature after 48 hours at 115 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (268mg is produced to obtain blue solid M3 Rate 89%)；R group is as follows in wherein compound M3：
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 70H),0.97-0.85(m,30H).
TOF-MS:M/z=1508.
Anal.Calcd for C94H130N4O12(%):C,74.86；H,8.69；N, 3.72.Found (%):C,74.87； H,8.68；N,3.73.
The 4,8- docosane epoxide of embodiment 8-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent for-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-diones) (M3) preparation
The synthetic method of compound M3 is identical with the synthetic method of compound M2 in embodiment 2, and brominated alkanes use bromo N-dodecane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds N-dodeeyl bromide (6.23g, 25mmol), backflow Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after finishing, continue to react overnight.Room temperature is cooled to, is poured the mixture into In water, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column (petroleum ether It is leacheate), obtain colourless oil liquid compound 1 (1.95g, yield 47%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,38H),0.86(t,6H).
TOF-MS:M/z=526.
Anal.Calcd for C34H54O4(%):C,77.52；H,10.33；O, 12.15.Found (%):C,77.53； H,10.36；O,12.17.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (2.6mL, 6.0mmol), then proceedes to Stirring 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, disposably add trimethyltin chloride (6mL, 6.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, and organic phase is washed 2 times, anhydrous Magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow solid, uses methyl alcohol It is recrystallized to give faint yellow acicular crystal compound 2 (0.70g, yield 47%).
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 38H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=852.
Anal.Calcd for C40H70O4Sn2(%):C,56.36；H,8.28；O, 7.51.Found (%):C,56.33； H,8.30；O,7.52.
3. the synthesis of compound M3
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.4mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(26mg), stirring reaction is cooled to room temperature after 50 hours at 110 DEG C, pours into precipitating in 100mL methyl alcohol, filtering, Crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), obtain blue solid M3 (256mg, yield 85%)；R group is as follows in wherein compound M3：
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 70H),0.97-0.85(m,30H).
TOF-MS:M/z=1508.
Anal.Calcd for C94H130N4O12(%):C,74.86；H,8.69；N, 3.72.Found (%):C,74.87； H,8.68；N,3.73.
The 4,8- docosane epoxide of embodiment 9-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent for-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-diones) (M3) preparation
The synthetic method of compound M3 is identical with the synthetic method of compound M1 in embodiment 3, and brominated alkanes use bromo N-dodecane, comprises the following steps that：
1. the synthesis of compound 1
By furans -4 of benzo two, 8- diketone (1.88g, 10mmol), NaOH (6.0g, 150mmol) and zinc powder (1.43g, 22mmol) it is blended in 30mL water, after being stirred at reflux reaction 1 hour, adds N-dodeeyl bromide (7.48g, 30mmol), backflow Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after finishing, continue to react overnight.Room temperature is cooled to, is poured the mixture into In water, dichloromethane extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product crosses silicagel column (petroleum ether It is leacheate), obtain colourless oil liquid compound 1 (2.10g, yield 51%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.87(m,2H),7.37(m,2H),4.72(t,4H),2.12(m,2H), 1.34-1.22(m,38H),0.86(t,6H).
TOF-MS:M/z=526.
Anal.Calcd for C34H54O4(%):C,77.52；H,10.33；O, 12.15.Found (%):C,77.53； H,10.36；O,12.17.
2. the synthesis of compound 2
Compound 1 (0.83g, 2.0mmol) is placed in the flask with three necks,round bottom of 100mL, under nitrogen protection, with injection Device adds anhydrous tetrahydro furan 30mL, is cooled to -78 DEG C, then is slowly added dropwise n-BuLi (3.4mL, 8.0mmol), then proceedes to 1.5 hours of stirring, move to room temperature lithiumation 1.5 hours, be cooled at -78 DEG C, disposably add trimethyltin chloride (10mL, 10.0mmol), after finishing, room temperature reaction is overnight.Reactant mixture is poured into frozen water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dried, and is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product is changed into yellow and consolidates Body, faint yellow acicular crystal compound 2 (0.68g, yield 46%) is obtained with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):7.04(s,2H),4.32(d,4H),1.75(m,2H),1.55-1.34(m, 38H),0.97(m,6H),0.41(s,18H).
TOF-MS:M/z=852.
Anal.Calcd for C40H70O4Sn2(%):C,56.36；H,8.28；O, 7.51.Found (%):C,56.33； H,8.30；O,7.52.
3. the synthesis of compound M3
Under nitrogen protection, by compound 2 (0.2mmol) and bromo- 2, the 6- bis- of 2- (2,5- diisooctyl -3,6- furyls -2- Pyrrolo-pyrrole-dione) (0.6mmol is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou) is added in 10mL dry toluenes, then add Enter Pd (PPh3)4(19.5mg), stirring reaction is cooled to room temperature after 40 hours at 120 DEG C, pours into precipitating in 100mL methyl alcohol, mistake Filter, crude product crosses silicagel column, and (leacheate is petroleum ether：Dichloromethane=1:1 (v/v)), (265mg is produced to obtain blue solid M3 Rate 88%)；R group is as follows in wherein compound M3：
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elementary analysis are as follows：
1H NMR(400MHz,CDCl3,ppm):8.92(s,2H),8.64(s,2H),7.63(s,2H),7.31(s,2H), 7.26(s,2H),7.08(s,2H),4.34(d,4H),4.02-3.95(d,8H),1.84-1.77(m,6H),1.53-1.27(m, 70H),0.97-0.85(m,30H).
TOF-MS:M/z=1508.
Anal.Calcd for C94H130N4O12(%):C,74.86；H,8.69；N, 3.72.Found (%):C,74.87； H,8.68；N,3.73.
The preparation of the organic molecule solar cell of embodiment 10
Using BDF organic micromolecules material as working media, prepare the method for solar cell is the present invention：Will be above-mentioned BDF organic micromolecules material and appropriate PC61BM (fullerene) and its derivative or it is other can be as electron acceptor Material mixing, adds appropriate solvent dissolving, by conventional spin coating or other modes on ITO (tin indium oxide) electro-conductive glass One layer of translucent film is prepared, metal electrode is then prepared on photovoltaic active layers by way of vacuum evaporation.
Concretely comprise the following steps：The PC of the compound M1 and 2mg of 2mg61BM mixes, and the dissolving of 0.2mL chloroforms is added, by rotation Painting mode is through PEDOT:The thick films of one layer of about 100nm are prepared on the electro-conductive glass of PSS modifieds, by heat at 120 DEG C Annealing 20 minutes, then prepares metal electrode with aluminium/lithium fluoride by way of vacuum evaporation on photovoltaic active layers.Its is organic Small molecule solar cell device performance is：
Short circuit current=11.1mA/cm2；Open-circuit voltage=0.82V；Fill factor, curve factor=55.5%；
Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.0%.
The preparation of the organic molecule solar cell of embodiment 11
The PC of the compound M2 and 2mg of 2mg61BM mixes, and the dissolving of 0.2mL chloroforms is added, by spin coating mode in warp PEDOT:The thick film of one layer of about 100nm is prepared on the electro-conductive glass of PSS modifieds, by thermal annealing at 120 DEG C 20 minutes, Then metal electrode is prepared on photovoltaic active layers with aluminium/lithium fluoride by way of vacuum evaporation.Its organic molecule sun Can battery device performance be：
Short circuit current=0.81；Open-circuit voltage=10.4；Fill factor, curve factor=36.0%；
Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=3.1%.
The preparation of the organic molecule solar cell of embodiment 12
The PC of the compound M3 and 2mg of 2mg61BM mixes, and the dissolving of 0.2mL chloroforms is added, by spin coating mode in warp PEDOT:The thick film of one layer of about 100nm is prepared on the electro-conductive glass of PSS modifieds, by thermal annealing at 120 DEG C 20 minutes, Then metal electrode is prepared on photovoltaic active layers with aluminium/lithium fluoride by way of vacuum evaporation.Its organic molecule sun Can battery device performance be：
Short circuit current=0.81；Open-circuit voltage=11.1；Fill factor, curve factor=47.0%；
Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=4.2%.
Embodiment 13
By taking compound M1 as an example, spectrum analysis, chemical property analysis, photovoltaic performance analysis and pattern point are carried out to it Analysis.
1. the spectrum analysis of compound M1
Absorption spectrums of the compound M1 under chloroform soln and film-forming state is as shown in figure 1, made in embodiment 10 Under standby filminess, compound M1 has substantially absorption in 300~750nm scope interior focusings, and optics with gaps are 1.65eV, explanation Compound M1 is narrow with gaps photovoltaic material, can absorb more sunshines, obtains short circuit current high.Narrower energy gap is main It is attributed to the furans of benzo two to be incorporated into A- π-D- π-A molecules, forms charge transfer state, so as to reduce band gap, reaches wider Light absorption range.This kind of BDF organic micromolecules photovoltaic material has broad application prospects in the preparation of solar cell.
2. the chemical property of compound M1
In electrochemistry, cyclic voltammetry is usually used to the electrochemistry energy level for determining material, and Fig. 2 is that compound M1 exists The Bu of 0.1mol/L4NBF4/CH2Cl2The cyclic voltammetry curve measured in solution, we can be from oxidation finding out of curved portion Compound M1 has relatively low HOMO energy levels (5.76eV), and the lumo energy that can obtain compound M1 from reduction curved portion is 3.51eV, electrochemistry energy gap is 2.25eV, referring to table 1.Low HOMO energy levels show that compound M1 has good air stability, It is especially suitable for preparing the solar cell device of long life.
The optics and electrochemical results of the compound M1 of table 1
3. the photovoltaic performance analysis of compound M1
As a result the photovoltaic performance of compound M1 as shown in figure 3, show that compound M1 has good photovoltaic performance.Such as chemical combination Thing M1 and PC61When BM is blended, short circuit current=11.1mA/cm2；Open-circuit voltage=0.82V；Fill factor, curve factor=55.5%；Simulation Sunshine (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.0%, referring to table 2.It is believed that solar cell Conversion efficiency can further be lifted by the optimization of device conditions.The EQE curves of compound M1 are as shown in figure 4, from Fig. 4 In we can see that compound M1 have spectral response and EQE efficiency values higher wider.
The photovoltaic performance result of the compound M1 of table 2
4. morphology analysis of compound M1
The pattern of photovoltaic active layers is the key factor for determining energy conversion efficiency height.Tested using AFM Compound M1 and PC61The pattern of BM blend films, as shown in figure 5, as a result showing that photovoltaic active layers have good nanoscale phase Separate, compound M1 and PC61Inierpeneirating network structure is formd between BM acceptors, is conducive to the separation of electric charge and is collected, obtained higher Photoelectric current and fill factor, curve factor.
From embodiment 1-13, the route of present invention synthesis is simple, low cost, and synthetic method has universality, can Preferably to promote the use of the synthesis of other BDF classes materials；BDF organic micromolecules photovoltaic material of the invention has big The conjugated structure of π planes, compare BDT class organic molecule materials, is expected to obtain broader uv-visible absorption spectra；Compare Compared with BDT class organic molecule materials, BDF organic micromolecules photovoltaic material of the invention has relatively low HOMO energy levels, to oxygen Stability it is high, be conducive to the solar cell device that processability is more stable；The present invention is organic small with the furans of benzo two Molecule photovoltaic material is electron donor material, is applied to organic molecule solar cell and obtains energy conversion efficiency higher (PCE=5.0%), have a good application prospect.
In sum, the present invention has synthesized a kind of benzo [1,2-b containing different alkyloxy side chains；3,4-b] two furans (BDF) organic electronic donor unit, the method being coupled by Stille, by BDF units by carbon-to-carbon singly-bound and another electronics Receptor unit pyrrolo-pyrrole-dione (DPP) is connected, and obtains BDF organic micromolecule photovoltaic materials.They common are There is good dissolubility in machine solvent (such as dichloromethane, chloroform, tetrahydrofuran), can be prepared with solution methods high-quality The film of amount.Meanwhile, there is these organic molecule photovoltaic materials visible region wide to absorb, suitable HOMO and LUMO energy The band gap of level and relative narrower.With such organic molecule as electron donor, PC61BM or organic matter electron acceptor are electron acceptor system For organic solar batteries, its highest energy conversion efficiency can reach 5.0%, with good photoelectric transformation efficiency.
Those of ordinary skill in the art should be understood：The discussion of any of the above embodiment is exemplary only, not It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under thinking of the invention, above example Or can also be combined between the technical characteristic in different embodiments, and there is different aspect of the invention as described above Many other changes, in order to it is concise they provided not in details.Therefore, it is all within the spirit and principles in the present invention, Any omission, modification, equivalent, improvement for being made etc., should be included within the scope of the present invention.

Claims (10)

1. a kind of furans organic micromolecule photovoltaic material of benzo two, it is characterised in that the knot of the organic molecule photovoltaic material Shown in structure such as formula (I)：
Wherein, R is alkyl.
2. the furans organic micromolecule photovoltaic material of benzo according to claim 1 two, it is characterised in that R is 8~12 The straight or branched alkane of carbon atom.
3. the furans organic micromolecule photovoltaic material of benzo according to claim 2 two, it is characterised in that the R is selected from One kind in following group：
4. the preparation method of a kind of furans organic micromolecule photovoltaic material of benzo two as described in claim any one of 1-3, It is characterised in that it includes following steps：
1) furans -4 of benzo two, 8- diketone overnight, is cooled to room temperature with brominated alkanes back flow reaction in water, pours the mixture into In water, extraction is dried, and is spin-dried for solvent, crosses silicagel column, obtains 4,8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans；
2) under nitrogen protection, -- by 4,8- dialkoxies-benzo (1,2-b at 78 DEG C；4,5-b ')-two furans and n-BuLi Mix in anhydrous tetrahydro furan, react 1~3 hour, continuously add excessive trimethyltin chloride, react at room temperature overnight, Pour the mixture into water, extraction is dried, and is spin-dried for solvent, is recrystallized to give 2,6- bis- (tin trimethyl)-(2- ethyls of 4,8- bis- Hexyloxy)-benzo [1,2-b；3,4-b '] two furans；
3) under nitrogen protection, by 2,6- bis- (tin trimethyl) -4,8- bis- (2- ethyl hexyl oxies)-benzo [1,2-b；3,4-b '] two Furans and 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) are added in dry toluene, then are added Enter Pd (PPh3)4, reacted 40~50 hours at 110~120 DEG C, room temperature is cooled to, precipitating, filtering is crossed silicagel column, obtains chemical combination Thing (I).
5. the preparation method of the furans organic micromolecule photovoltaic material of benzo according to claim 4 two, it is characterised in that Step 1) described in brominated alkanes be n-octane bromide, bromo-iso-octane or bromododecane；Furans -4,8- the diketone of benzo two with The mol ratio of brominated alkanes is 1:2~3.
6. the preparation method of the furans organic micromolecule photovoltaic material of benzo according to claim 4 two, it is characterised in that Step 2) in 4,8- dialkoxies-benzo (1,2-b；4,5-b ')-two furans, n-BuLi and trimethyltin chloride mol ratio It is 1:3~4:3~5；Recrystallize to recrystallize in methyl alcohol.
7. the preparation method of the furans organic micromolecule photovoltaic material of benzo according to claim 4 two, it is characterised in that Step 3) in (the 2- ethyl hexyl oxies)-benzo [1,2-b of 2,6- bis- (tin trimethyl) -4,8- two；3,4-b '] two furans and 2 '- The mol ratio of bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) is 1:1~3；Pd(PPh3)4With 2 '- The mass ratio of bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) is 5~10：100.
8. the preparation method of the furans organic micromolecule photovoltaic material of benzo according to claim 4 two, it is characterised in that Step 3) in precipitating be precipitating in methyl alcohol；The leacheate for crossing silicagel column is volume ratio 1:1 petroleum ether/dichloromethane mixing Liquid.
9. the furans organic micromolecule photovoltaic material of benzo two described in any one of claim 1-3 in solar cells should With.
10. application in solar cells according to claim 9, it is characterised in that the furans of benzo two have Machine small molecule photovoltaic material is used as solar cell electron donor material.
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