CN107200747B - One kind [2.1.3] benzoxadiazole class photovoltaic material and its preparation method and application - Google Patents

One kind [2.1.3] benzoxadiazole class photovoltaic material and its preparation method and application Download PDF

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CN107200747B
CN107200747B CN201710398879.3A CN201710398879A CN107200747B CN 107200747 B CN107200747 B CN 107200747B CN 201710398879 A CN201710398879 A CN 201710398879A CN 107200747 B CN107200747 B CN 107200747B
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benzoxadiazole
photovoltaic material
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CN107200747A (en
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刘波
陈远道
王晓波
王钢
刘骏
胡霞
何敏
周诗彪
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Yuewang Agricultural Group Co ltd
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Hunan University of Arts and Science
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • H—ELECTRICITY
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    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a kind of [2.1.3] benzoxadiazole class photovoltaic materials and its preparation method and application, belong to photovoltaic material technical field.Its structure is indicated by formula (I).The present invention also provides the preparation method and application of [2.1.3] benzoxadiazole class photovoltaic material.The method being mainly coupled by stille when prepared by such photovoltaic material, [2.1.3] benzoxadiazole (BO) organic electronic donor unit that a kind of terminal groups are trifluoromethyl is synthesized, changes different side chain units to regulate and control optics, the chemical property of organic molecule.The synthetic route is simple, and at low cost and synthetic method has universality, can preferably be applied to the synthesis of other [2.1.3] benzoxadiazole class materials；[2.1.3] benzoxadiazole class photovoltaic material has bigger conjugated structure, is expected to obtain broader uv-visible absorption spectra and carrier mobility；And [2.1.3] benzoxadiazole class photovoltaic material has lower HOMO energy level, and it is high to the stability of oxygen, be conducive to the more stable solar cell device of processability.

Description

One kind [2.1.3] benzoxadiazole class photovoltaic material and its preparation method and application
Technical field
The present invention relates to photovoltaic material technical field, particularly relate to a kind of [2.1.3] benzoxadiazole class photovoltaic material and Preparation method and application.
Background technique
With increasingly sharpening for global energy crisis, sight has been turned to reproducible clean energy resource by countries in the world.Therefore, It is directed to the concern of technology that solar energy highly effective utilizes increasingly by scientific circles and industrial circle.Organic molecule solar cell Quick development was obtained at nearly 5 years as the device for converting the solar into electric energy, energy conversion efficiency has been over 10% [Bin Kan, Qian Zhang, Miaomiao Li, Xiangjian Wan, Wang Ni, Guankui Long, Yunchuang Wang,Xuan Yang,Huanran Feng,Yongsheng Chen.Journal of the American Chemical Society,2014,136,15529].But performance efficiency and stable small molecule photovoltaic material category are less, So need to design and synthesize a greater variety of small organic molecule photovoltaic materials, by the modification of structure and the optimization of device come into The photovoltaic performance of one step raising organic solar batteries.
[2.1.3] benzoxadiazole (BO) is an important electron acceptor unit, using BO as the polymerization of electron acceptor Object in recent years electrochromism, sensor, light emitting diode and in terms of obtained extensive research [(1) Bo Liu,Xuewen Chen,Yuehui He,Yongfang Li,Xinjun Xu,Lu Xiao,Lidong Li,Yingping Zou.Journal of Materials Chemistry A,2013,1,570.(2)Ping Ding,Chengmei Zhong, Yingping Zou,Chunyue Pan,Kelong Huang,Hongbin Wu,Yong Cao.Journal of Physics Chemistry,2011,115,16211.].But after BO is coupled as receptor unit and other aromatic heterocycle donor monomers Applied to the rare report of organic molecule solar cell.In fact, BO and diazosulfide (BT) and benzotriazole (BTz) Chemical structure is similar, and the atomic radius of O atom is smaller than S atom, has the molecular structure of more plane, thus is expected to obtain Obtain higher carrier mobility.BT is widely used in organic solar batteries as classical electron acceptor. For example, Guillermo C.Bazan seminar applies to BT as electron acceptor in organic molecule solar cell, synthesis Organic small point of p-DTS (FBTTh2)2, as p-DTS (FBTTh2)2With PC71When BM is blended, the organic solar batteries of preparation are obtained Obtained up to 8.2% energy conversion efficiency [Ye Huang, Wen Wen, Subhrangsu Mukherjee, Harald Ade, Edward J.Kramer,Guillermo C.Bazan.Advanced Materials,2014,26,4168.].In conclusion BO organic micromolecule has extensive prospect in the application of solar battery.
In view of photovoltaic material in area of solar cell broad application prospect, develop new [2.1.3] benzo and dislike Diazoles photovoltaic material is of great significance.
Summary of the invention
In view of this, it is an object of the invention to propose one kind [2.1.3] benzoxadiazole class photovoltaic material and its preparation Methods and applications, being somebody's turn to do [2.1.3] benzoxadiazole class photovoltaic material has more regular planar conjugate structure, is expected to obtain more High carrier mobility；And its synthetic route is simple, and synthetic method has universality, is used to prepare solar cell device With preferable energy conversion efficiency.
Based on a kind of above-mentioned purpose [2.1.3] benzoxadiazole class photovoltaic material provided by the invention, structure such as formula (I) It is shown:
Wherein, R is alkyl in the formula (I).
Preferably, R is selected from one of flowering structure in the formula (I):
Based on identical inventive concept, the present invention also provides a kind of systems of [2.1.3] benzoxadiazole class photovoltaic material Preparation Method includes the following steps: that step 1) compound 1 and 2- (three normal-butyls) furans react to obtain 2 crude product of compound, crosses silicagel column Elute to obtain compound 2；Step 2) compound 2 and N- bromo-succinimide react to obtain 3 crude product of compound, cross silicagel column and elute Compound 3；Step 3) compound 3 and 4- trifluoromethyl -2- phenyl boric acid react to obtain 4 crude product of compound, cross silicagel column and elute to change Close object 4；Step 4) compound 4 and compound 5 react described [2.1.3] benzoxadiazole class photovoltaic material crude product, cross silica gel Column elutes described [2.1.3] benzoxadiazole class photovoltaic material；
Wherein, the R in the compound 1 is selected from one of flowering structure:
When the structural formula of R isWhen, the compound being prepared is n-octyloxy-[2.1.3] Benzoxadiazole-thiophene benzofuran (M1)；
When the structural formula of R isWhen, the compound being prepared is different octyloxy-[2.1.3] benzo Oxadiazoles-thiophene benzofuran (M2)；
When the structural formula of R isWhen, the compound being prepared is n-dodecane Oxygroup-[2.1.3] benzoxadiazole-thiophene benzofuran (M3).
The preparation route of heretofore described [2.1.3] benzoxadiazole class photovoltaic material is as follows:
Preferably, the molar ratio of compound 1 and 2- (three normal-butyls) furans is 1:(2~3.5 in the step 1))；Reaction Temperature is 85~95 DEG C, and the reaction time is 20~30 hours；The leacheate used that elutes is liquid A: liquid B=(4~ 7): 1 (V/V), the liquid A are n-hexane or petroleum ether, and the liquid B is dichloromethane or chloroform.
Preferably, the molar ratio of compound 2 and N- bromo-succinimide is 1:(2.5~4 in the step 2))；Room temperature Reaction 12~24 hours；The leacheate used that elutes is liquid A: liquid B=(4~6): 1 (V/V), the liquid A are positive Hexane or petroleum ether, the liquid B are dichloromethane or chloroform.
Preferably, the molar ratio of compound 3 and 4- trifluoromethyl -2- phenyl boric acid is 1:(1~3 in the step 3))；Instead Answering temperature is 90~95 DEG C, and the reaction time is 24~48 hours；The leacheate used that elutes is liquid A: liquid B=(1~ 4): 1 (V/V), the liquid A are n-hexane or petroleum ether, and the liquid B is dichloromethane or chloroform.
Preferably, the molar ratio of compound 4 and compound 5 is (2~4) in the step 4): 1；Reaction temperature be 110~ 120 DEG C, the reaction time is 24~48 hours；The leacheate used that elutes is liquid A: liquid B=1:(2~5) (V/V), The liquid A is n-hexane or petroleum ether, and the liquid B is dichloromethane or chloroform.
Based on identical inventive concept, the present invention also provides a kind of answering for [2.1.3] benzoxadiazole class photovoltaic material With [2.1.3] the benzoxadiazole class photovoltaic material is preparing the application in solar battery.
Preferably, after described [2.1.3] the benzoxadiazole class photovoltaic material and electron acceptor mixed dissolution, conductive thin is prepared Then film prepares metal electrode on film.
It is highly preferred that the mass ratio of [2.1.3] the benzoxadiazole class photovoltaic material and electron acceptor is 1:(1~3)； The electron acceptor is PC61BM or derivatives thereof.
From the above it can be seen that the advantages of the present invention are:
(1) present invention in [2.1.3] benzoxadiazole class photovoltaic material relative to diazosulfide organic micromolecule light For lying prostrate material, there is more smooth planar conjugate structure, be expected to obtain higher carrier mobility.
(2) present invention in [2.1.3] benzoxadiazole class photovoltaic material relative to diazosulfide organic micromolecule light For lying prostrate material, there is lower HOMO energy level, it is high to the stability of oxygen, be conducive to the more stable solar-electricity of processability Pond device.
(3) synthetic route of [2.1.3] benzoxadiazole class photovoltaic material is simple in the present invention, at low cost and synthetic method With universality, it can preferably be applied to the synthesis of other benzoxadiazole class photovoltaic materials.
(4) it utilizes [2.1.3] benzoxadiazole class photovoltaic material to prepare solar battery in the present invention, obtains preferable Energy conversion efficiency (PCE=5.3%), has a good application prospect.
Detailed description of the invention
Fig. 1 is the thermogravimetic analysis (TGA) result of M1 in the embodiment of the present invention；
Fig. 2 is the absorption spectrum of M1 in the embodiment of the present invention；
Fig. 3 is the cyclic voltammetry curve of M1 in the embodiment of the present invention；
Fig. 4 is the photovoltaic performance of M1, M2 and M3 in the embodiment of the present invention.
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.
Used compound 5 and the purchase of 2- (three normal-butyls) furans are received triumphant science and technology in Suzhou and are had in following example 1~9 Limit company；
In Examples 1 to 3, when R structure isWhen the purchase of compound 1 receive triumphant science and technology in Suzhou Co., Ltd；
In embodiment 4~6, when R structure isWhen the purchase of compound 1 in Suzhou to receive triumphant science and technology limited Company；
In embodiment 7~9, when R structure isWhen compound 1 buy in Soviet Union Zhou Nakai Science and Technology Ltd..
Embodiment 1
The preparation of n-octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M1), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (4.64g, 13.00mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.74g, 0.64mmol), after, 90 DEG C back flow reaction 24 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, is changed 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the petroleum ether and two that the leacheate used is 4:1 for volume ratio The mixed liquor of chloromethanes obtains 2.49g orange solids compound 2, reaction yield 94%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (25mL) and chloroform (60mL) is added in 150mL single port bottle, then divides three for N- bromo-succinimide (1.16g, 6.50mmol) in 1 hour It is secondary to be added in reaction system, after, continue to be protected from light and react 18 hours at room temperature.After reaction, mixture is poured into water, Methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by 3 crude product of compound Silicagel column elution is crossed, the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 5:1 for volume ratio is eluted, obtains 1.39g Orange solids compound 3, reaction yield 81%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,20H),0.92-0.88(m,6H)；Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H, 5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.38g, It 2.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (2.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (208mg, 0.18mmol) be cooled to room temperature after reacting 24 hours at 95 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 1:1 for volume ratio, it is red to obtain 0.89g Color solid chemical compound 4, reaction yield 61%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)； Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H, 5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.32g, 0.44mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 15mg3)4), it is stirred to react 48 hours at 115 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M1 crude product, M1 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and chloroform that volume ratio is 1:2 mixed solution, obtain 332mg black solid M1, reaction produces Rate is 89%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M1's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,50H),0.92-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 2
The preparation of n-octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M1), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (3.74g, 10.48mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.92g, 0.8mmol), after, 85 DEG C back flow reaction 30 hours.After reaction, it is cooled to room temperature, will react Mixture is poured into water, and is extracted with dichloromethane 3 times, and organic phase is dry, filters, removes extra organic solvent, obtained change 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the n-hexane and two that the leacheate used is 7:1 for volume ratio The mixed liquor of chloromethanes obtains 2.37g orange solids compound 2, reaction yield 89%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (35mL) and chloroform (50mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.86g, 10.40mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 24 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, obtains 1.35g orange solids compound 3, reaction yield 78%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,20H),0.92-0.88(m,6H)；Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H, 5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (1.14g, It 6.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (3.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (289mg, 0.25mmol) be cooled to room temperature after reacting 48 hours at 90 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, obtains 1.1g red Solid chemical compound 4, reaction yield 75%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)； Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H, 5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.59g, 0.80mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 18mg3)4), it is stirred to react 48 hours at 110 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M1 crude product, M1 crude product is crossed into silicagel column elution, elution uses Leacheate be petroleum ether and chloroform that volume ratio is 1:5 mixed solution, obtain 343mg black solid M1, reaction produces Rate is 92%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M1's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,50H),0.92-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 3
The preparation of n-octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M1), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (6.55g, 18.34mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.58g, 0.50mmol), after, 95 DEG C back flow reaction 20 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, obtains 2 crude product of compound is crossed silicagel column elution by 2 crude product of compound, elute the leacheate that uses for volume ratio be 6:1 petroleum ether and The mixed liquor of chloroform obtains 2.13g orange solids compound 2, reaction yield 80%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (20mL) and chloroform (65mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.392g, 7.80mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 12 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 6:1 for volume ratio, obtains 1.45g orange solids compound 3, reaction yield 84%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,20H),0.92-0.88(m,6H)；Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H, 5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.76g, It 4.0mmol) is dissolved in 40mL toluene, adds 10mL sodium carbonate (2.5mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (347mg, 0.3mmol) be cooled to room temperature, mixture is poured into water, dichloro after reacting 36 hours at 92 DEG C Methane extraction, organic phase is dry, filters, removes extra organic solvent, obtains 4 crude product of compound, 4 crude product of compound is crossed silicon Rubber column gel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 3:1 for volume ratio, obtains 0.92g red Solid chemical compound 4, reaction yield 63%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,20H),0.92-0.88(m,6H)； Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H, 5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.29g, 0.40mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 12mg3)4), it is stirred to react 24 hours at 120 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M1 crude product, M1 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and methylene chloride that volume ratio is 1:3 mixed solution, obtain 306mg black solid M1, reaction produces Rate is 82%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M1's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,50H),0.92-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 4
The preparation of different octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M2), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (4.64g, 13.00mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.74g, 0.64mmol), after, 90 DEG C back flow reaction 24 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, is changed 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the petroleum ether and two that the leacheate used is 4:1 for volume ratio The mixed liquor of chloromethanes obtains 2.59g orange solids compound 2, reaction yield 97%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.94 (d, 2H), 7.27 (d, 2H), 6.99 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (25mL) and chloroform (60mL) is added in 150mL single port bottle, then divides three for N- bromo-succinimide (1.16g, 6.50mmol) in 1 hour It is secondary to be added in reaction system, after, continue to be protected from light and react 18 hours at room temperature.After reaction, mixture is poured into water, Methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by 3 crude product of compound Silicagel column elution is crossed, the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 5:1 for volume ratio is eluted, obtains 1.52g Orange solids compound 3, reaction yield 88%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t, 2H), 1.43- 1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H,5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.38g, It 2.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (2.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (208mg, 0.18mmol) be cooled to room temperature after reacting 24 hours at 95 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 1:1 for volume ratio, it is red to obtain 1.02g Color solid chemical compound 4, reaction yield 70%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.11-4.06(t,4H),1.92(t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H,5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.32g, 0.44mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 15mg3)4), it is stirred to react 48 hours at 115 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M2 crude product, M2 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and chloroform that volume ratio is 1:2 mixed solution, obtain 291mg black solid M2, reaction produces Rate is 78%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M2's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.82-7.77 (d, 4H), 7.70 (d, 2H), 7.64-7.62 (d, 4H), 7.51 (s, 2H), 7.16-7.13(d,4H),6.91(d,2H),6.75(t,4H),4.11-4.06(t,8H),2.89-2.87(d,4H),1.97- 1.89(m,8H),1.76-1.72(m,8H),1.46-1.32(m,50H),0.91-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 5
The preparation of different octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M2), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (3.74g, 10.48mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.92g, 0.8mmol), after, 85 DEG C back flow reaction 30 hours.After reaction, it is cooled to room temperature, will react Mixture is poured into water, and is extracted with dichloromethane 3 times, and organic phase is dry, filters, removes extra organic solvent, obtained change 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the n-hexane and two that the leacheate used is 7:1 for volume ratio The mixed liquor of chloromethanes obtains 2.29g orange solids compound 2, reaction yield 86%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.94 (d, 2H), 7.27 (d, 2H), 6.99 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (35mL) and chloroform (50mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.86g, 10.40mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 24 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, obtains 1.44g orange solids compound 3, reaction yield 83%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t, 2H), 1.43- 1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H,5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (1.14g, It 6.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (3.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (289mg, 0.25mmol) be cooled to room temperature after reacting 48 hours at 90 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, it is red to obtain 0.98g Color solid chemical compound 4, reaction yield 67%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.11-4.06(t,4H),1.92(t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H,5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.59g, 0.80mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 18mg3)4), it is stirred to react 48 hours at 110 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M2 crude product, M2 crude product is crossed into silicagel column elution, elution uses Leacheate be petroleum ether and chloroform that volume ratio is 1:5 mixed solution, obtain 306mg black solid M2, reaction produces Rate is 82%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M2's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.82-7.77 (d, 4H), 7.70 (d, 2H), 7.64-7.62 (d, 4H), 7.51 (s, 2H), 7.16-7.13(d,4H),6.91(d,2H),6.75(t,4H),4.11-4.06(t,8H),2.89-2.87(d,4H),1.97- 1.89(m,8H),1.76-1.72(m,8H),1.46-1.32(m,50H),0.91-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 6
The preparation of different octyloxy-[2.1.3] benzoxadiazole-thiophene benzofuran (M2), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.13g, 5.24mmol), 2- (three normal-butyls) furans (6.55g, 18.34mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.58g, 0.50mmol), after, 95 DEG C back flow reaction 20 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, obtains 2 crude product of compound is crossed silicagel column elution by 2 crude product of compound, elute the leacheate that uses for volume ratio be 6:1 petroleum ether and The mixed liquor of chloroform obtains 1.76g orange solids compound 2, reaction yield 66%；
The compound 2 is characterized as below:
TOF-MS:m/z=509；
1HNMR(CDCl3): δ=7.94 (d, 2H), 7.27 (d, 2H), 6.99 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H40N2O5(%): C, 70.84；H,7.93；N, 5.51.Found (%): C, 70.85； H,7.95；N,5.52.
Step 2) is protected from light under protection, by compound 2 (1.32g, 2.60mmol), glacial acetic acid (20mL) and chloroform (65mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.392g, 7.80mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 12 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 6:1 for volume ratio, obtains 1.39g orange solids compound 3, reaction yield 80%；
The compound 3 is characterized as below:
TOF-MS:m/z=666；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.11-4.07 (t, 4H), 1.92 (t, 2H), 1.43- 1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 54.07；H,5.75；N, 4.20.Found (%): C, 54.06；H,5.77；N,4.22.
Step 3) argon gas protection under, by compound 3 (1.33g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.76g, It 4.0mmol) is dissolved in 40mL toluene, adds 10mL sodium carbonate (2.5mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (347mg, 0.3mmol) be cooled to room temperature, mixture is poured into water, dichloro after reacting 36 hours at 92 DEG C Methane extraction, organic phase is dry, filters, removes extra organic solvent, obtains 4 crude product of compound, 4 crude product of compound is crossed silicon Rubber column gel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 3:1 for volume ratio, obtains 0.91g red Solid chemical compound 4, reaction yield 62%；
The compound 4 is characterized as below:
TOF-MS:m/z=732；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.11-4.06(t,4H),1.92(t,2H),1.43-1.31(m,16H),0.92-0.88(m,12H)；
Anal.Calcd for C37H42BrF3N2O5(%): C, 60.74；H,5.79；N, 3.83.Found (%): C, 60.76；H,5.78；N,3.84.
Under the protection of step 4) argon gas, compound 4 (0.29g, 0.40mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 12mg3)4), it is stirred to react 24 hours at 120 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M2 crude product, M2 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and methylene chloride that volume ratio is 1:3 mixed solution, obtain 272mg black solid M2, reaction produces Rate is 73%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M2's is characterized as below:
TOF-MS:m/z=1864；
1HNMR(CDCl3): δ=7.82-7.77 (d, 4H), 7.70 (d, 2H), 7.64-7.62 (d, 4H), 7.51 (s, 2H), 7.16-7.13(d,4H),6.91(d,2H),6.75(t,4H),4.11-4.06(t,8H),2.89-2.87(d,4H),1.97- 1.89(m,8H),1.76-1.72(m,8H),1.46-1.32(m,50H),0.91-0.88(m,24H)；
Anal.Calcd for C108H124F6N4O11S3(%): C, 69.58；H,6.70；N, 3.01.Found (%): C, 69.57；H,6.71；N,3.00.
Embodiment 7
The preparation of n-dodecane oxygroup-[2.1.3] benzoxadiazole-thiophene benzofuran (M3), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.39g, 5.24mmol), 2- (three normal-butyls) furans (4.64g, 13.00mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.74g, 0.64mmol), after, 90 DEG C back flow reaction 24 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, is changed 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the petroleum ether and two that the leacheate used is 4:1 for volume ratio The mixed liquor of chloromethanes obtains 2.96g orange solids compound 2, reaction yield 91%；
The compound 2 is characterized as below:
TOF-MS:m/z=621；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C38H56N2O5(%): C, 73.51；H,9.09；N, 4.51.Found (%): C, 73.52； H,9.07；N,4.52.
Step 2) is protected from light under protection, by compound 2 (1.61g, 2.60mmol), glacial acetic acid (25mL) and chloroform (60mL) is added in 150mL single port bottle, then divides three for N- bromo-succinimide (1.16g, 6.50mmol) in 1 hour It is secondary to be added in reaction system, after, continue to be protected from light and react 18 hours at room temperature.After reaction, mixture is poured into water, Methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by 3 crude product of compound Silicagel column elution is crossed, the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 5:1 for volume ratio is eluted, obtains 1.68g Orange solids compound 3, reaction yield 83%；
The compound 3 is characterized as below:
TOF-MS:m/z=779；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 58.61；H,6.99；N, 3.60.Found (%): C, 58.62；H,6.97；N,3.62.
Step 3) argon gas protection under, by compound 3 (1.56g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.38g, It 2.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (2.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (208mg, 0.18mmol) be cooled to room temperature after reacting 24 hours at 95 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of petroleum ether and methylene chloride that the leacheate used is 1:1 for volume ratio, it is red to obtain 1.13g Color solid chemical compound 4, reaction yield 67%；
The compound 4 is characterized as below:
TOF-MS:m/z=844；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C45H58BrF3N2O5(%): C, 64.05；H,6.93；N, 3.32.Found (%): C, 64.06；H,6.94；N,3.34.
Under the protection of step 4) argon gas, compound 4 (0.37g, 0.44mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 15mg3)4), it is stirred to react 48 hours at 115 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M3 crude product, M3 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and chloroform that volume ratio is 1:2 mixed solution, obtain 376mg black solid M3, reaction produces Rate is 90%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M3's is characterized as below:
TOF-MS:m/z=2089；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,82H),0.92-0.88(m,24H)；
Anal.Calcd for C124H156F6N4O11S3(%): C, 71.30；H,7.35；N, 2.68.Found (%): C, 71.29；H,7.34；N,2.69.
Embodiment 8
The preparation of n-dodecane oxygroup-[2.1.3] benzoxadiazole-thiophene benzofuran (M3), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.39g, 5.24mmol), 2- (three normal-butyls) furans (3.74g, 10.48mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.92g, 0.8mmol), after, 85 DEG C back flow reaction 30 hours.After reaction, it is cooled to room temperature, will react Mixture is poured into water, and is extracted with dichloromethane 3 times, and organic phase is dry, filters, removes extra organic solvent, obtained change 2 crude product of object is closed, 2 crude product of compound is crossed into silicagel column elution, elutes the n-hexane and two that the leacheate used is 7:1 for volume ratio The mixed liquor of chloromethanes obtains 2.73g orange solids compound 2, reaction yield 84%；
The compound 2 is characterized as below:
TOF-MS:m/z=621；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C38H56N2O5(%): C, 73.51；H,9.09；N, 4.51.Found (%): C, 73.52； H,9.07；N,4.52.
Step 2) is protected from light under protection, by compound 2 (1.61g, 2.60mmol), glacial acetic acid (35mL) and chloroform (50mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.86g, 10.40mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 24 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, obtains 1.26g orange solids compound 3, reaction yield 62%；
The compound 3 is characterized as below:
TOF-MS:m/z=779；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 58.61；H,6.99；N, 3.60.Found (%): C, 58.62；H,6.97；N,3.62.
Step 3) argon gas protection under, by compound 3 (1.56g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (1.14g, It 6.00mmol) is dissolved in 40mL toluene, adds 10mL potassium carbonate (3.0mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (289mg, 0.25mmol) be cooled to room temperature after reacting 48 hours at 90 DEG C, mixture is poured into water, and two Chloromethanes extraction, organic phase is dry, filters, removes extra organic solvent, 4 crude product of compound is obtained, by 4 crude product mistake of compound Silicagel column elution, elutes the mixed liquor of n-hexane and methylene chloride that the leacheate used is 4:1 for volume ratio, it is red to obtain 1.33g Color solid chemical compound 4, reaction yield 79%；
The compound 4 is characterized as below:
TOF-MS:m/z=844；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C45H58BrF3N2O5(%): C, 64.05；H,6.93；N, 3.32.Found (%): C, 64.06；H,6.94；N,3.34.
Under the protection of step 4) argon gas, compound 4 (0.68g, 0.80mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 18mg3)4), it is stirred to react 48 hours at 110 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M3 crude product, M3 crude product is crossed into silicagel column elution, elution uses Leacheate be petroleum ether and chloroform that volume ratio is 1:5 mixed solution, obtain 347mg black solid M3, reaction produces Rate is 83%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M3's is characterized as below:
TOF-MS:m/z=2089；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,82H),0.92-0.88(m,24H)；
Anal.Calcd for C124H156F6N4O11S3(%): C, 71.30；H,7.35；N, 2.68.Found (%): C, 71.29；H,7.34；N,2.69.
Embodiment 9
The preparation of n-dodecane oxygroup-[2.1.3] benzoxadiazole-thiophene benzofuran (M3), includes the following steps:
Step 1) argon gas protection under, by compound 1 (3.39g, 5.24mmol), 2- (three normal-butyls) furans (6.55g, 18.34mmol), dry toluene (150mL) is added in the there-necked flask of 250mL, is further continued for that tetrakis triphenylphosphine palladium (Pd is added (PPh3)4) (0.58g, 0.50mmol), after, 95 DEG C back flow reaction 20 hours.After reaction, it is cooled to room temperature, it will be anti- It answers mixture to be poured into water, is extracted with dichloromethane 3 times, organic phase is dry, filters, removes extra organic solvent, obtains 2 crude product of compound is crossed silicagel column elution by 2 crude product of compound, elute the leacheate that uses for volume ratio be 6:1 petroleum ether and The mixed liquor of chloroform obtains 2.86g orange solids compound 2, reaction yield 88%；
The compound 2 is characterized as below:
TOF-MS:m/z=621；
1HNMR(CDCl3): δ=7.96 (d, 2H), 7.29 (d, 2H), 6.93 (t, 2H), 4.19-4.06 (t, 4H), 1.76- 1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C38H56N2O5(%): C, 73.51；H,9.09；N, 4.51.Found (%): C, 73.52； H,9.07；N,4.52.
Step 2) is protected from light under protection, by compound 2 (1.61g, 2.60mmol), glacial acetic acid (20mL) and chloroform (65mL) is added in 150mL single port bottle, then by N- bromo-succinimide (1.392g, 7.80mmol) point in 1 hour It is added in reaction system three times, after, continue to be protected from light and react 12 hours at room temperature.After reaction, mixture pours into water In, methylene chloride extraction, organic phase is dry, filters, removes extra organic solvent, 3 crude product of compound is obtained, by compound 3 Crude product crosses silicagel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 6:1 for volume ratio, obtains 1.52g orange solids compound 3, reaction yield 75%；
The compound 3 is characterized as below:
TOF-MS:m/z=779；
1HNMR(CDCl3): δ=7.18 (d, 2H), 6.73 (t, 2H), 4.19-4.06 (t, 4H), 1.76-1.72 (m, 4H), 1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C30H38Br2N2O5(%): C, 58.61；H,6.99；N, 3.60.Found (%): C, 58.62；H,6.97；N,3.62.
Step 3) argon gas protection under, by compound 3 (1.56g, 2.00mmol), 4- trifluoromethylbenzene boronic acid (0.76g, It 4.0mmol) is dissolved in 40mL toluene, adds 10mL sodium carbonate (2.5mol/L) solution, be eventually adding four (triphenylphosphines) Palladium (Pd (PPh3)4) (347mg, 0.3mmol) be cooled to room temperature, mixture is poured into water, dichloro after reacting 36 hours at 92 DEG C Methane extraction, organic phase is dry, filters, removes extra organic solvent, obtains 4 crude product of compound, 4 crude product of compound is crossed silicon Rubber column gel column elution, elutes the mixed liquor of petroleum ether and chloroform that the leacheate used is 3:1 for volume ratio, obtains 1.25g red Solid chemical compound 4, reaction yield 74%；
The compound 4 is characterized as below:
TOF-MS:m/z=844；
1HNMR(CDCl3): δ=7.83-7.79 (d, 2H), 7.66-7.62 (d, 2H), 7.17-7.14 (d, 2H), 6.73 (t,2H),4.19-4.06(t,4H),1.76-1.72(m,4H),1.43-1.31(m,36H),0.92-0.88(m,6H)；
Anal.Calcd for C45H58BrF3N2O5(%): C, 64.05；H,6.93；N, 3.32.Found (%): C, 64.06；H,6.94；N,3.34.
Under the protection of step 4) argon gas, compound 4 (0.34g, 0.40mmol) and compound 5 (0.18g, 0.20mmol) are added Enter into 15ml dry toluene, adds the tetrakis triphenylphosphine palladium (Pd (PPh of 12mg3)4), it is stirred to react 24 hours at 120 DEG C Afterwards, it is cooled to room temperature, pours into precipitating in 100ml methanol, filter, obtain M3 crude product, M3 crude product is crossed into silicagel column elution, elution uses Leacheate be n-hexane and methylene chloride that volume ratio is 1:3 mixed solution, obtain 384mg black solid M3, reaction produces Rate is 92%；
R structure is as follows in the compound 1, compound 2, compound 3 and compound 4:
The M3's is characterized as below:
TOF-MS:m/z=2089；
1HNMR(CDCl3): δ=7.83-7.79 (d, 4H), 7.72 (d, 2H), 7.66-7.62 (d, 4H), 7.50 (s, 2H), 7.17-7.14(d,4H),6.90(d,2H),6.73(t,4H),4.19-4.06(t,8H),2.88-2.86(d,4H),1.95- 1.83(m,8H),1.76-1.72(m,8H),1.43-1.31(m,82H),0.92-0.88(m,24H)；
Anal.Calcd for C124H156F6N4O11S3(%): C, 71.30；H,7.35；N, 2.68.Found (%): C, 71.29；H,7.34；N,2.69.
Embodiment 10
The preparation of organic molecule solar cell
The PC of the M1 and 3.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=10.69mA/cm2；Open-circuit voltage= 0.74V；Fill factor=49.6%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=3.9%.
Embodiment 11
The preparation of organic molecule solar cell
The PC of the M1 and 9.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=1.8mA/cm2；Open-circuit voltage= 0.76V；Fill factor=43.0%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=0.6%.
Embodiment 12
The preparation of organic molecule solar cell
The PC of the M2 and 3.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=11.85mA/cm2；Open-circuit voltage= 0.75V；Fill factor=59.3%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=5.3%.
Embodiment 13
The preparation of organic molecule solar cell
The PC of the M2 and 9.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=7.1mA/cm2；Open-circuit voltage= 0.75V；Fill factor=40.0%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=2.1%.
Embodiment 14
The preparation of organic molecule solar cell
The PC of the M3 and 3.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=11.15mA/cm2；Open-circuit voltage= 0.74V；Fill factor=54.9%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=4.6%.
Embodiment 15
The preparation of organic molecule solar cell
The PC of the M3 and 9.0mg of 3.0mg61BM mixing is added the dissolution of 0.30mL o-dichlorohenzene, is being passed through by spin coating mode The film that one layer of about 120nm thickness is prepared on the electro-conductive glass of PEDOT:PSS modified, is then used by way of vacuum evaporation Aluminium prepares metal electrode on polymer.Its device performance shows themselves in that short circuit current=1.2mA/cm2；Open-circuit voltage= 0.76V；Fill factor=51.0%；Simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency=0.5%.
Embodiment 16
By taking M1 as an example, thermal stability analysis, spectrum analysis and chemical property analysis are carried out to it, and to M1, M2 and M3 Carry out photovoltaic performance analysis.
The thermogravimetic analysis (TGA) result of M1 is as shown in Figure 1.As can be seen from the results: 5% thermal decomposition temperature of M1 is 311 DEG C, is shown [2.1.3] benzoxadiazole class photovoltaic material good thermal stability, can satisfy for a long time that quality of materials will not in outside work Decay too fast demand.
The absorption spectrum of M1 is as shown in Fig. 2, the optical results of M1 are as shown in table 1 below.As seen from Figure 2: under filminess, M1 has obvious absorption in 300~680nm range interior focusing, and optical band gap 1.82ev illustrates that M1 can be absorbed in visible region More sunlights obtain high short circuit current.Filminess is mainly due to TBF than absorption spectrum Einstein shift under solution state and draws Enter into A- π-D- π-A molecule, forms charge transfer state, to reduce band gap, reach broader light absorption range.It is this kind of [2.1.3] benzoxadiazole organic micromolecule material has broad application prospects in the preparation of solar battery.
Cyclic voltammetry is to measure compound HOMO and the frequent method used of lumo energy.What Fig. 3 was indicated is following for M1 The electrochemical results of ring volt-ampere curve, M1 are as shown in table 1.We can find out that the oxidizing potential of M1 is from oxidation curved portion 0.94V, corresponding HOMO energy level are -5.65eV, can be seen that the reduction potential of M1 is -0.76V from reduction curved portion, so Corresponding lumo energy is -3.95eV, and electrochemistry band gap is 1.70eV.Low HOMO energy level shows [2.1.3] benzoxadiazole Class photovoltaic material has good air stability, is very suitable to prepare solar cell device.
The optics and electrochemical results of M1 is as shown in table 1:
Table 1.
The photovoltaic performance of M1, M2 and M3 as shown in figure 4, the photovoltaic performance of M1, M2 and M3 the results are shown in Table 2.By Fig. 4 and Table 2 is it can be seen that [2.1.3] benzoxadiazole organic micromolecule solar cell material has excellent photovoltaic performance；Such as M2 and PC61When BM=1:1 is blended, without any post-processing, energy conversion efficiency reaches 5.3%, it is possible thereby to infer The energy conversion efficiency of the solar battery of [2.1.3] benzoxadiazole class photovoltaic material preparation can be obtained by optimised devices Further promoted.
The results are shown in Table 2 for the photovoltaic performance of M1, M2 and M3:
Table 2.
By above-described embodiment 1~16 it can be seen that heretofore described [2.1.3] benzoxadiazole class photovoltaic material is opposite For diazosulfide organic micromolecule photovoltaic material, there is more smooth planar conjugate structure, be expected to obtain higher Carrier mobility；And [2.1.3] benzoxadiazole class photovoltaic material is relative to diazosulfide organic micromolecule photovoltaic For material, there is lower HOMO energy level, it is high to the stability of oxygen, be conducive to the more stable solar battery of processability Device when being applied in solar battery, has good energy conversion function；And [2.1.3] benzoxadiazole class light The synthetic route for lying prostrate material is simple, and at low cost and synthetic method has universality, can preferably be applied to other benzene And the synthesis of furodiazole photovoltaic material.
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 (10)

1. a kind of [2.1.3] benzoxadiazole class photovoltaic material, which is characterized in that shown in the structure of the photovoltaic material such as formula (I):
Wherein, R is alkyl in the formula (I).
2. [2.1.3] benzoxadiazole class photovoltaic material according to claim 1, which is characterized in that R in the formula (I) Selected from one of flowering structure:
3. a kind of preparation method of [2.1.3] benzoxadiazole class photovoltaic material as described in claim 1, which is characterized in that Include the following steps:
Step 1) compound 1 and 2- (three normal-butyls) furans react to obtain 2 crude product of compound, cross silicagel column and elute to obtain compound 2；
Step 2) compound 2 and N- bromo-succinimide react to obtain 3 crude product of compound, cross silicagel column and elute to obtain compound 3；
Step 3) compound 3 and 4- trifluoromethylbenzene boronic acid react to obtain 4 crude product of compound, cross silicagel column and elute to obtain compound 4；
Step 4) compound 4 and compound 5 react described [2.1.3] benzoxadiazole class photovoltaic material crude product, cross silicagel column Elute described [2.1.3] benzoxadiazole class photovoltaic material；
Wherein, the R in the compound 1 is selected from one of flowering structure:
4. the preparation method of [2.1.3] benzoxadiazole class photovoltaic material according to claim 3, which is characterized in that institute Stating the molar ratio of compound 1 and 2- (three normal-butyls) furans in step 1) is 1:(2~3.5)；Reaction temperature is 85~95 DEG C, instead It is 20~30 hours between seasonable；The leacheate used that elutes is liquid A: liquid B=(4~7): 1 (V/V), the liquid A For n-hexane or petroleum ether, the liquid B is dichloromethane or chloroform.
5. the preparation method of [2.1.3] benzoxadiazole class photovoltaic material according to claim 3, which is characterized in that institute Stating the molar ratio of compound 2 and N- bromo-succinimide in step 2) is 1:(2.5~4)；Room temperature reaction 12~24 hours；Institute The leacheate that uses of elution is stated as liquid A: liquid B=(4~6): 1 (V/V), the liquid A are n-hexane or petroleum ether, described Liquid B is dichloromethane or chloroform.
6. the preparation method of [2.1.3] benzoxadiazole class photovoltaic material according to claim 3, which is characterized in that institute Stating the molar ratio of compound 3 and 4- trifluoromethylbenzene boronic acid in step 3) is 1:(1~3)；Reaction temperature is 90~95 DEG C, reaction Time is 24~48 hours；The leacheate used that elutes is liquid A: liquid B=(1~4): 1 (V/V), the liquid A are N-hexane or petroleum ether, the liquid B are dichloromethane or chloroform.
7. the preparation method of [2.1.3] benzoxadiazole class photovoltaic material according to claim 3, which is characterized in that institute Stating the molar ratio of compound 4 and compound 5 in step 4) is (2~4): 1；Reaction temperature is 110~120 DEG C, and the reaction time is 24~48 hours；The leacheate used that elutes is liquid A: liquid B=1:(2~5) (V/V), the liquid A is n-hexane Or petroleum ether, the liquid B are dichloromethane or chloroform.
8. a kind of application of [2.1.3] benzoxadiazole class photovoltaic material as described in claim 1, which is characterized in that described [2.1.3] benzoxadiazole class photovoltaic material is preparing the application in solar battery.
9. the application of [2.1.3] benzoxadiazole class photovoltaic material according to claim 8, which is characterized in that described After [2.1.3] benzoxadiazole class photovoltaic material and electron acceptor mixed dissolution, conductive film is prepared, is then prepared on film Metal electrode.
10. the application of [2.1.3] benzoxadiazole class photovoltaic material according to claim 9, which is characterized in that described The mass ratio of [2.1.3] benzoxadiazole class photovoltaic material and electron acceptor is 1:(1~3)；The electron acceptor is PC61BM or Its derivative.
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