CN106928255B - A kind of two furans organic micromolecule photovoltaic material of benzo and its preparation method and application - Google Patents

A kind of two furans organic micromolecule photovoltaic material of benzo and its preparation method and application Download PDF

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CN106928255B
CN106928255B CN201710197021.0A CN201710197021A CN106928255B CN 106928255 B CN106928255 B CN 106928255B CN 201710197021 A CN201710197021 A CN 201710197021A CN 106928255 B CN106928255 B CN 106928255B
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benzo
furans
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CN106928255A (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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Abstract

The invention discloses a kind of two furans organic micromolecule photovoltaic materials of benzo 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 unit is connected by carbon-to-carbon singly-bound with another electron acceptor unit pyrrolo-pyrrole-dione (DPP), BDF organic micromolecule photovoltaic material is obtained, shown in structure such as formula (I).These small organic molecule photovoltaic materials have wide visible region absorption, suitable HOMO and lumo energy and relatively narrow band gap.Using such organic molecule as electron donor, PC61BM or organic matter electron acceptor are that electron acceptor is prepared for organic solar batteries, and highest energy transfer efficiency can reach 5.0%, have good photoelectric conversion efficiency.

Description

A kind of two furans organic micromolecule photovoltaic material of benzo and its preparation method and application
Technical field
The present invention relates to photovoltaic material technical fields, and in particular to a kind of two furans organic micromolecule photovoltaic material of benzo And its preparation method and application.
Background technique
Benzo [1,2-b；3,4-b] two furans (BDF) have obtained very in polymer solar battery as electron donor Good application, is the very excellent electron donor unit of a kind of 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 small 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 are applied in organic molecule solar cell as electron donor, obtain 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, Nankai University is with 4,8- Two different octyloxies-benzo [1,2-b；3,4-b] Dithiophene connect three thiophene of the company coupling of strong electron-withdrawing group group with end, obtains A kind of BDT organic micromolecule photovoltaic material (DR3TSBDT), DR3TSBDT has sunlight within the scope of 300~730nm The energy conversion efficiency of good absorption, the solar battery of preparation is up to 9.6%, is being 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 unit for replacing sulphur atom to obtain using oxygen atom is applied to organic as electron donor In small molecule solar battery, it is contemplated that efficient photovoltaic performance can be obtained.Reason is mainly oxygen atom with smaller than sulphur atom Atomic radius after BDF is with different electron acceptor coupling, obtained so BDF has planar structure more better than BDT BDF organic micromolecule is estimated to possess broader absorption spectrum and higher carrier mobility.
The present invention has synthesized the BDF monomer containing different flexible side-chains, obtains a kind of BDF with the method that Stille is coupled Organic micromolecule solar cell material has carried out the characterization such as optics and electrochemistry to them, and to it in solar battery On application studied.
Summary of the invention
In view of this, it is an object of the invention to propose a kind of two furans organic micromolecule photovoltaic material of benzo and its system Preparation Method and application, the small organic molecule photovoltaic material are the BDF organic micromolecule photovoltaic material of carbon-to-carbon singly-bound connection, and Electron donor material be can be used as applied to solar battery.
Based on above-mentioned purpose, a kind of two furans organic micromolecule photovoltaic material of benzo provided by the invention, this is organic small Shown in the structure of molecule photovoltaic material such as formula (I):
Wherein, R is alkyl.
Formula (I) compound represented is 4,8- dialkoxy-benzo (1,2-b；4,5-b ') two (2,5- of-two furans -2,6- Diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-dione).
In the present invention, it is preferred to, R is the linear chain or branched chain alkane of 8~12 carbon atoms.
In the present invention, it is further preferred that the R is selected from one of 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-dione) (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-dione) (M2)；
WhenWhen, the target compound of synthesis is 4,8- docosane oxygroup- Benzo (1,2-b；4,5-b ')-two furans -2,6- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-dione) (M3)。
A kind of BDF organic micromolecule material provided by the invention has good machinability, and by tentatively tasting Examination proves there is preferable light transfer characteristic, and the working media as organic molecule solar cell has wide application Prospect.
Further, the present invention also provides the preparations of the two furans organic micromolecule photovoltaic material of benzo described in one kind Method, comprising the following steps:
1) back flow reaction is stayed overnight in water for two furans -4,8- diketone of benzo and brominated alkanes, is cooled to room temperature, by mixture It is poured into water, extracts, it is dry, it is spin-dried for solvent, silicagel column is crossed, obtains 4,8- dialkoxy-benzo (1,2-b；4,5-b ')-two furans It mutters；
2) under nitrogen protection, by 4,8- dialkoxy-benzo (1,2-b at -78 DEG C；4,5-b ')-two furans and positive fourth Base lithium mixes in anhydrous tetrahydro furan, reacts 1~3 hour, continuously adds excessive trimethyltin chloride, reacted at room temperature Night pours the mixture into water, extracts, dry, 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 oxy)-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) is reacted 40~50 hours at 110~120 DEG C, is cooled to room temperature, precipitating, Filtering crosses silicagel column, obtains compound (I)；
Wherein, 4,8- dialkoxy-benzo (1,2-b；4,5-b ')-two furans structural formula such as following formula (1) shown in:
Two (2- ethyl hexyl oxy)-benzo [1,2-b of 2,6- bis- (tin trimethyl) -4,8-；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, brominated alkanes described in step 1) are n-octane bromide, bromo-iso-octane or bromo ten Dioxane；The molar ratio of two furans -4,8- diketone of benzo and brominated alkanes is 1:2~3.
In the present invention, it is preferred to, 4,8- dialkoxy-benzo (1,2-b in step 2)；4,5-b ')-two furans, positive fourth The molar ratio of base lithium and trimethyltin chloride is 1:3~4:3~5；Recrystallization is to recrystallize in methyl alcohol.
In the present invention, it is preferred to, 2,6- bis- (tin trimethyl) -4,8- bis- (2- ethyl hexyl oxy)-benzo in step 3) [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, precipitating is precipitating in methyl alcohol in step 3)；The leacheate for crossing silicagel column is volume ratio The petroleum ether of 1:1/methylene chloride mixed liquor.
A series of BDF small organic molecule photovoltaic material preparation methods provided by the invention are the sides using Stille coupling BDF electron donor unit and another kind of aromatic heterocycle electron acceptor unit are directly coupled by method.
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 BDF unit is passed through carbon-to-carbon singly-bound and another electron acceptor unit by electron donor unit, the method being coupled by Stille Pyrrolo-pyrrole-dione (DPP) is connected, and obtains BDF organic micromolecule photovoltaic material.They common organic solvent (such as Methylene chloride, chloroform, tetrahydrofuran etc.) in have good dissolubility, can use solution methods preparation high quality film. Meanwhile these small organic molecule photovoltaic materials are with wide visible region absorption, suitable HOMO and lumo energy and relatively Relatively narrow band gap.Using such organic molecule as electron donor, PC61BM or organic matter electron acceptor are prepared for organic for electron acceptor Solar battery, highest energy transfer efficiency can reach 5.0%, have good photoelectric conversion efficiency.
Therefore, further, the present invention also provides the two furans organic micromolecule photovoltaic materials of benzo to exist Application in solar battery.
In the present invention, it is preferred to, the two furans organic micromolecule photovoltaic material of benzo is used as solar battery electricity Sub- donor material.
The present invention is electron donor material with above-mentioned two furans organic micromolecule photovoltaic material of benzo, is applied to organic small Molecular solar cells, preparation method are as follows:
By BDF organic micromolecule electron donor material and electron acceptor (PC of the invention61BM or organic matter electronics by Body) substance blending, chloroform is added, dissolves mixture sufficiently, is spin-coated on electro-conductive glass ITO and prepares conductive film, Then the evaporation metal aluminium electrode on film.
BDF organic micromolecule photovoltaic material provided by the invention has wide absorption spectrum and suitable electrochemical energy Grade, and characterize with nuclear magnetic resoance spectrum, mass spectrum and the method for elemental analysis the molecular structure of each step synthetic product.With it is ultraviolet-can See the optical property of Absorption Spectrum Research BDF organic micromolecule photovoltaic material.It is organic that BDF class is had studied with cyclic voltammetry The chemical property of small molecule photovoltaic material.And it has been made into solar cell device using it as electron donor, it obtains good Photoelectric conversion efficiency.
Compared with prior art, the invention has the following advantages:
(1) route that the present invention synthesizes is simple, at low cost, and synthetic method has universality, can preferably promote and answer Use the synthesis of other BDF class materials.
(2) BDF organic micromolecule photovoltaic material of the invention has the conjugated structure of big π plane, and the BDT class that compares has Machine molecular material is expected to obtain broader uv-visible absorption spectra.
(3) it is compared to BDT class organic molecule material, BDF organic micromolecule photovoltaic material of the invention has lower HOMO energy level, it is high to the stability of oxygen, be conducive to the more stable solar cell device of processability.
(4) present invention is electron donor material with two furans organic micromolecule photovoltaic material of benzo, is applied to organic small Molecular solar cells obtain higher energy conversion efficiency (PCE=5.0%), have a good application prospect.
Detailed description of the invention
Fig. 1 is the absorption spectrum of BDF organic micromolecule photovoltaic material of the present invention；
Fig. 2 is the electrochemical analysis figure of BDF organic micromolecule photovoltaic material of the present invention；
Fig. 3 is the photoelectric conversion efficiency figure of BDF organic micromolecule photovoltaic material of the present invention；
Fig. 4 is the outer conversion quantum efficiency figure of BDF organic micromolecule photovoltaic material of the present invention；
Fig. 5 is the morphology analysis figure of BDF organic micromolecule photovoltaic material active layer of the present invention；Wherein a figure is height map, B figure is phasor.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference Attached drawing, the present invention is described in more detail.
The synthetic route of BDF organic micromolecule 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 octyloxy of 1 4,8- of embodiment bis--benzo (1,2-b；4,5-b ') two (2,5- diisooctyl-of-two furans -2,6- 3,6- furyl -2- pyrrolo-pyrrole-dione) (M1) preparation
Specific step is as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added bromo-iso-octane (3.86g, 20mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3mL, 7.0mmol) is slowly added dropwise, then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (8mL, 8.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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 bromo- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyls-of the compound 2 and 2- of equimolar amounts 2- pyrrolo-pyrrole-dione) (0.2mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 115 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M1, (237mg is produced Rate 85%)；Wherein R group is as follows in compound M1:
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elemental 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 octyloxy of 2 4,8- of embodiment bis--benzo (1,2-b；4,5-b ') two (2,5- diisooctyl-of-two furans -2,6- 3,6- furyl -2- pyrrolo-pyrrole-dione) (M1) preparation
Specific step is as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added bromo-iso-octane (4.83g, 25mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (2.6mL, 6.0mmol) is slowly added dropwise, then proceedes to Stir 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (6mL, 6.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.4mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(26mg) is cooled to room temperature after being stirred to react 50 hours at 110 DEG C, pours into precipitating in 100mL methanol, filters, Crude product crosses silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), obtains blue solid M1 (230mg, yield 82%)；Wherein R group is as follows in compound M1:
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elemental 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 octyloxy of 3 4,8- of embodiment bis--benzo (1,2-b；4,5-b ') two (2,5- diisooctyl-of-two furans -2,6- 3,6- furyl -2- pyrrolo-pyrrole-dione) (M1) preparation
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added bromo-iso-octane (5.79g, 30mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3.4mL, 8.0mmol) is slowly added dropwise, then proceedes to 1.5 hours are stirred, move to room temperature lithiumation 1.5 hours, is cooled at -78 DEG C, is added at one time trimethyltin chloride (10mL, 10.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, it is solid that crude product becomes yellow Body obtains faint yellow acicular crystal compound 2 (0.68g, yield 46%) with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.6mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(19.5mg) is cooled to room temperature after being stirred to react 40 hours at 120 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M1, (232mg is produced Rate 83%)；Wherein R group is as follows in compound M1:
The nuclear magnetic resoance spectrum of compound M1, mass spectrum and elemental 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.
4 bis- octyloxies of 4,8- of embodiment-benzo (1,2-b；4,5-b ')-two furans -2,6- two (diisooctyl -3 2,5-, 6- furyl -2- pyrrolo-pyrrole-dione) (M2) preparation
The synthetic method of compound M2 is identical as the synthetic method of compound M1 in embodiment 1, and brominated alkanes use bromo Normal octane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added n-octane bromide (3.86g, 20mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3mL, 7.0mmol) is slowly added dropwise, then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (8mL, 8.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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 bromo- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyls-of the compound 2 and 2- of equimolar amounts 2- pyrrolo-pyrrole-dione) (0.2mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 115 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M2, (220mg is produced Rate 79%)；Wherein R group is as follows in compound M2:
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elemental 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.
5 bis- octyloxies of 4,8- of embodiment-benzo (1,2-b；4,5-b ')-two furans -2,6- two (diisooctyl -3 2,5-, 6- furyl -2- pyrrolo-pyrrole-dione) (M2) preparation
The synthetic method of compound M2 is identical as the synthetic method of compound M1 in embodiment 2, and brominated alkanes use bromo Normal octane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added n-octane bromide (4.83g, 25mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (2.6mL, 6.0mmol) is slowly added dropwise, then proceedes to Stir 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (6mL, 6.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.4mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(26mg) is cooled to room temperature after being stirred to react 50 hours at 110 DEG C, pours into precipitating in 100mL methanol, filters, Crude product crosses silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), obtains blue solid M2 (210mg, yield 75%)；Wherein R group is as follows in compound M2:
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elemental 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.
6 bis- octyloxies of 4,8- of embodiment-benzo (1,2-b；4,5-b ')-two furans -2,6- two (diisooctyl -3 2,5-, 6- furyl -2- pyrrolo-pyrrole-dione) (M2) preparation
The synthetic method of compound M2 is identical as the synthetic method of compound M1 in embodiment 3, and brominated alkanes use bromo Normal octane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added n-octane bromide (5.79g, 30mmol), reflux is anti- It answers 2 hours, then adds zinc powder (0.2g, 3mmol), after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into water In, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, 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 elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3.4mL, 8.0mmol) is slowly added dropwise, then proceedes to 1.5 hours are stirred, move to room temperature lithiumation 1.5 hours, is cooled at -78 DEG C, is added at one time trimethyltin chloride (10mL, 10.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, it is solid that crude product becomes yellow Body obtains faint yellow acicular crystal compound 2 (0.68g, yield 46%) with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.6mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(19.5mg) is cooled to room temperature after being stirred to react 40 hours at 120 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M2, (215mg is produced Rate 77%)；Wherein R group is as follows in compound M2:
The nuclear magnetic resoance spectrum of compound M2, mass spectrum and elemental 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.
7 4,8- docosane oxygroup of embodiment-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent by-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-dione) (M3) preparation
The synthetic method of compound M3 is identical as the synthetic method of compound M1 in embodiment 1, and brominated alkanes use bromo N-dodecane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added N-dodeeyl bromide (4.98g, 20mmol), reflux Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into In water, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, is spin-dried for solvent, crude product crosses silicagel column (petroleum ether For leacheate), obtain colourless oil liquid compound 1 (2.19g, yield 53%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3mL, 7.0mmol) is slowly added dropwise, then proceedes to stir Mix 1 hour, move to room temperature lithiumation 1 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (8mL, 8.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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 bromo- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyls-of the compound 2 and 2- of equimolar amounts 2- pyrrolo-pyrrole-dione) (0.2mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then Pd (PPh is added3)4(10mg) is cooled to room temperature after being stirred to react 48 hours at 115 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M3, (268mg is produced Rate 89%)；Wherein R group is as follows in compound M3:
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elemental 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.
8 4,8- docosane oxygroup of embodiment-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent by-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-dione) (M3) preparation
The synthetic method of compound M3 is identical as the synthetic method of compound M2 in embodiment 2, and brominated alkanes use bromo N-dodecane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added N-dodeeyl bromide (6.23g, 25mmol), reflux Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into In water, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, is spin-dried for solvent, crude product crosses silicagel column (petroleum ether For leacheate), obtain colourless oil liquid compound 1 (1.95g, yield 47%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (2.6mL, 6.0mmol) is slowly added dropwise, then proceedes to Stir 0.5 hour, move to room temperature lithiumation 0.5 hour, be cooled at -78 DEG C, be added at one time trimethyltin chloride (6mL, 6.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, and ether extraction, organic phase is washed 2 times, anhydrous Magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, crude product becomes yellow solid, uses methanol 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 elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.4mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(26mg) is cooled to room temperature after being stirred to react 50 hours at 110 DEG C, pours into precipitating in 100mL methanol, filters, Crude product crosses silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), obtains blue solid M3 (256mg, yield 85%)；Wherein R group is as follows in compound M3:
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elemental 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.
9 4,8- docosane oxygroup of embodiment-benzo (1,2-b；4,5-b ') (2,5- bis- is different pungent by-two furans -2,6- two Base -3,6- furyl -2- pyrrolo-pyrrole-dione) (M3) preparation
The synthetic method of compound M3 is identical as the synthetic method of compound M1 in embodiment 3, and brominated alkanes use bromo N-dodecane, the specific steps are as follows:
1. the synthesis of compound 1
By two furans -4,8- diketone (1.88g, 10mmol) of benzo, NaOH (6.0g, 150mmol) and zinc powder (1.43g, It 22mmol) is blended in 30mL water, after being stirred at reflux reaction 1 hour, is added N-dodeeyl bromide (7.48g, 30mmol), reflux Reaction 2 hours, then zinc powder (0.2g, 3mmol) is added, after, the reaction was continued overnight.It is cooled to room temperature, pours the mixture into In water, methylene chloride extraction, organic phase is washed 2 times, and anhydrous magnesium sulfate is dry, is spin-dried for solvent, crude product crosses silicagel column (petroleum ether For leacheate), obtain colourless oil liquid compound 1 (2.10g, yield 51%).
The nuclear magnetic resoance spectrum of compound 1, mass spectrum and elemental 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 Anhydrous tetrahydro furan 30mL is added in device, is cooled to -78 DEG C, then n-BuLi (3.4mL, 8.0mmol) is slowly added dropwise, then proceedes to 1.5 hours are stirred, move to room temperature lithiumation 1.5 hours, is cooled at -78 DEG C, is added at one time trimethyltin chloride (10mL, 10.0mmol), after, room temperature reaction is overnight.Reaction mixture pours into ice water, ether extraction, organic phase washing 2 Secondary, anhydrous magnesium sulfate is dry, is spin-dried for solvent, and crude product is yellow oily liquid, and after cryogenic freezing, it is solid that crude product becomes yellow Body obtains faint yellow acicular crystal compound 2 (0.68g, yield 46%) with recrystallizing methanol.
The nuclear magnetic resoance spectrum of compound 2, mass spectrum and elemental 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- 2,6-, bis- (2,5- diisooctyl -3, the 6- furyl -2- of 2- Pyrrolo-pyrrole-dione) (0.6mmol, buy in Receive triumphant scientific and technological Co., Ltd. in Suzhou) be added in 10mL dry toluene, then plus Enter Pd (PPh3)4(19.5mg) is cooled to room temperature after being stirred to react 40 hours at 120 DEG C, pours into precipitating in 100mL methanol, mistake Filter, crude product cross silicagel column (leacheate is petroleum ether: methylene chloride=1:1 (v/v)), and obtaining blue solid M3, (265mg is produced Rate 88%)；Wherein R group is as follows in compound M3:
The nuclear magnetic resoance spectrum of compound M3, mass spectrum and elemental 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 10 organic molecule solar cell of embodiment
Using BDF organic micromolecule material as working media, the method for preparing solar battery is the present invention: will be above-mentioned BDF organic micromolecule material and suitable PC61BM (fullerene) and its derivative or others can be used as electron acceptor Suitable solvent dissolution is added, through conventional spin coating or other modes on ITO (tin indium oxide) electro-conductive glass in material mixing One layer of translucent film is prepared, then prepares metal electrode on photovoltaic active layers by way of vacuum evaporation.
Specific steps are as follows: the PC of the compound M1 and 2mg of 2mg61BM mixing is added the dissolution of 0.2mL chloroform, passes through rotation Painting mode prepares the film of one layer of about 100nm thickness on the electro-conductive glass through PEDOT:PSS modified, by hot 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 are as follows:
Short circuit current=11.1mA/cm2；Open-circuit voltage=0.82V；Fill factor=55.5%；
Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.0%.
The preparation of 11 organic molecule solar cell of embodiment
The PC of the compound M2 and 2mg of 2mg61BM mixing is added the dissolution of 0.2mL chloroform, is being passed through by spin coating mode The film that one layer of about 100nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, by thermal annealing 20 minutes at 120 DEG C, Then metal electrode is prepared on photovoltaic active layers with aluminium/lithium fluoride by way of vacuum evaporation.Its small organic molecule sun Energy battery device performance are as follows:
Short circuit current=0.81；Open-circuit voltage=10.4；Fill factor=36.0%；
Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=3.1%.
The preparation of 12 organic molecule solar cell of embodiment
The PC of the compound M3 and 2mg of 2mg61BM mixing is added the dissolution of 0.2mL chloroform, is being passed through by spin coating mode The film that one layer of about 100nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, by thermal annealing 20 minutes at 120 DEG C, Then metal electrode is prepared on photovoltaic active layers with aluminium/lithium fluoride by way of vacuum evaporation.Its small organic molecule sun Energy battery device performance are as follows:
Short circuit current=0.81；Open-circuit voltage=11.1；Fill 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 spectrum 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 obvious absorption in 300~750nm range interior focusing, and optics with gap is 1.65eV, explanation Compound M1 is narrow with gap photovoltaic material, and more sunlights can be absorbed, and obtains high short circuit current.Relatively narrow energy gap is main Due to two furans of benzo is introduced into A- π-D- π-A molecule, charge transfer state is formd, to reduce band gap, reaches wider Light absorption range.This kind of BDF organic micromolecule photovoltaic material has broad application prospects in the preparation of solar battery.
2. the chemical property of compound M1
In electrochemistry, cyclic voltammetry is usually used to the electrochemistry energy level of measurement substance, 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 Closing object M1 has lower HOMO energy level (5.76eV), and the lumo energy from the reduction available compound M1 of curved portion is 3.51eV, electrochemistry energy gap is 2.25eV, referring to table 1.Low HOMO energy level shows that compound M1 has good air stability, It is very suitable to the solar cell device of preparation long life.
The optics and electrochemical results of 1 compound M1 of table
3. the photovoltaic performance of compound M1 is analyzed
The photovoltaic performance of compound M1 is as shown in Figure 3, the results showed that compound M1 has good photovoltaic performance.Such as chemical combination Object M1 and PC61When BM is blended, short circuit current=11.1mA/cm2；Open-circuit voltage=0.82V；Fill factor=55.5%；Simulation Sunlight (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.0%, referring to table 2.It is believed that solar battery Transfer efficiency can further be promoted by the optimization of device conditions.The EQE curve of compound M1 is as shown in figure 4, from Fig. 4 In we can see that compound M1 have wider spectral response and higher EQE efficiency value.
The photovoltaic performance result of 2 compound M1 of table
4. the morphology analysis of compound M1
The pattern of photovoltaic active layers is the key factor for determining energy conversion efficiency height.It is tested using atomic force microscope Compound M1 and PC61The pattern of BM blend film, as shown in Figure 5, the results showed that photovoltaic active layers have good nanoscale phase Separation, compound M1 and PC61Inierpeneirating network structure is formd between BM receptor, is conducive to the separation and collection of charge, is obtained higher Photoelectric current and fill factor.
It is at low cost by embodiment 1-13 it is found that the route that synthesizes of the present invention is simple, and synthetic method has universality, it can Preferably to promote the use of the synthesis of other BDF class materials；BDF organic micromolecule photovoltaic material of the invention has big The conjugated structure of π plane, compare BDT class organic molecule material, is expected to obtain broader uv-visible absorption spectra；It compares Compared with BDT class organic molecule material, BDF organic micromolecule photovoltaic material of the invention has lower HOMO energy level, to oxygen Stability it is high, be conducive to the more stable solar cell device of processability；The present invention is organic small with two furans of benzo Molecule photovoltaic material is electron donor material, obtains higher energy conversion efficiency applied to organic molecule solar cell (PCE=5.0%), it has a good application prospect.
In conclusion the present invention has synthesized a kind of benzo [1,2-b containing different alkyloxy side chains；3,4-b] two furans (BDF) BDF unit is passed through carbon-to-carbon singly-bound and another electronics by organic electronic donor unit, the method being coupled by Stille Receptor unit pyrrolo-pyrrole-dione (DPP) is connected, and obtains BDF organic micromolecule photovoltaic material.They common are There is good dissolubility in solvent (such as methylene chloride, chloroform, tetrahydrofuran), can be prepared with solution methods high-quality The film of amount.Meanwhile there is these small organic molecule photovoltaic materials wide visible region to absorb, suitable HOMO and LUMO energy Grade and relatively narrow band gap.Using such organic molecule as electron donor, PC61BM or organic matter electron acceptor are electron acceptor system It can reach 5.0% for organic solar batteries, highest energy transfer efficiency, there is good photoelectric conversion efficiency.
It should be understood by those ordinary skilled in the art that: 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 embodiments Or it can also be combined between the technical characteristic in different embodiments, and there are different aspects present invention as described above Many other variations, in order to it is concise they do not provided in details.Therefore, all within the spirits and principles of the present invention, Any omission, modification, equivalent replacement, improvement for being made etc., should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of preparation method of two furans organic micromolecule photovoltaic material of benzo, which comprises the following steps:
1) back flow reaction is stayed overnight in water for two furans -4,8- diketone of benzo and brominated alkanes, is cooled to room temperature, is poured the mixture into In water, extract, it is dry, it is spin-dried for solvent, silicagel column is crossed, obtains 4,8- dialkoxy-benzo (1,2-b；4,5-b ')-two furans；
2) under nitrogen protection, by 4,8- dialkoxy-benzo (1,2-b at -78 DEG C；4,5-b ')-two furans and n-BuLi It mixing in anhydrous tetrahydro furan, reacts 1~3 hour, continuously add excessive trimethyltin chloride, reaction is stayed overnight at room temperature, It pours the mixture into water, extracts, it is dry, it is spin-dried for solvent, is recrystallized to give 2,6- bis- (tin trimethyl) -4,8- dialkoxy - Benzo [1,2-b；3,4-b '] two furans；
3) under nitrogen protection, by 2,6- bis- (tin trimethyl) -4,8- dialkoxy-benzo [1,2-b；3,4-b '] two furans with 2 '-bromo- two (2,5- diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-diones) are added in dry toluene, add Pd (PPh3)4, react 40~50 hours at 110~120 DEG C, be cooled to room temperature, precipitating, filter, cross silicagel column；
Wherein, the structure of the two furans organic micromolecule photovoltaic material of benzo such as (I) is shown:
Wherein, R is the linear or branched alkyl group of 8~12 carbon atoms.
2. a kind of preparation method of two furans organic micromolecule photovoltaic material of benzo according to claim 1, feature It is, the R is selected from one of following group:
3. a kind of preparation method of two furans organic micromolecule photovoltaic material of benzo according to claim 1, feature It is, brominated alkanes described in step 1) are n-octane bromide, bromo-iso-octane or bromododecane；Two furans -4,8- of benzo The molar ratio of diketone and brominated alkanes is 1:2~3.
4. the preparation method of two furans organic micromolecule photovoltaic material of benzo according to claim 1, which is characterized in that 4,8- dialkoxy-benzo (1,2-b in step 2)；4,5-b ')-two furans, n-BuLi and trimethyltin chloride molar ratio For 1:3~4:3~5；Recrystallization is to recrystallize in methyl alcohol.
5. the preparation method of two furans organic micromolecule photovoltaic material of benzo according to claim 1, which is characterized in that 2,6- bis- (tin trimethyl) -4,8- dialkoxy-benzo [1,2-b in step 3)；3,4-b '] two furans and 2 '-bromo- two (2,5- Diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-dione) molar ratio be 1:1~3；Pd(PPh3)4With 2 '-bromo- two (2,5- Diisooctyl -3,6- furyl -2- pyrrolo-pyrrole-dione) mass ratio be 5~10:100.
6. the preparation method of two furans organic micromolecule photovoltaic material of benzo according to claim 1, which is characterized in that Precipitating is precipitating in methyl alcohol in step 3)；The leacheate for crossing silicagel column is the petroleum ether of volume ratio 1:1/methylene chloride mixing Liquid.
7. existing according to the two furans organic micromolecule photovoltaic material of benzo of any one of the claim 1-6 preparation method preparation Application in solar battery.
8. application in solar cells according to claim 7, which is characterized in that two furans of benzo are organic Small molecule photovoltaic material is used as solar battery electron donor material.
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