CN106946912B - Naphtho-difurane photovoltaic material and preparation method and application thereof - Google Patents
Naphtho-difurane photovoltaic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a naphtho-difuran photovoltaic material, and a preparation method and application thereof, and belongs to the technical field of photovoltaic materials. The structure is represented by formula (I). The invention also provides theA preparation method and application of a naphtho-difuran photovoltaic material. The photovoltaic material is mainly prepared by connecting a naphtho-difurane unit with another aromatic heterocycle or a derivative thereof through a carbon-carbon single junction by a stille coupling method. The synthetic route is simple, the cost is low, the synthetic method has universality, and the method can be well popularized and applied to the synthesis of other naphtho-difurane materials. The prepared naphtho-difuran photovoltaic material has a conjugated structure with a large pi plane, and can obtain a wider ultraviolet-visible absorption spectrum; the silicon nitride has lower HOMO energy level and high stability to oxygen, and is beneficial to preparing a solar cell device with more stable performance; when the naphtho-difurane photovoltaic material is applied to a solar cell, the photoelectric conversion function is good.
Description
Technical Field
The invention relates to the technical field of photovoltaic materials, in particular to a naphtho-difuran photovoltaic material and a preparation method and application thereof.
Background
An ideal small organic molecule electron donor unit needs to have a wide absorption spectrum to obtain high short-circuit current and a deeper HOMO energy level to obtain high open-circuit voltage and stability. The method of combining the power-receiving electronic units hasProved to be the most effective method for obtaining wide absorption and deep HOMO energy level organic small molecules and improving photovoltaic performance. At present, Benzodifuran (BDF) polymer photovoltaic materials show better photovoltaic performance [ Bo Liu, Beibei Qiu, Xuewen Chen, Luxiao, Yongfang Li, Yuehui He, Lihui Jiang, Yingping Zou. Polymer Chemistry,2014,5, 5002-5008; bo Liu, Xuewen Chen, Yingping Zou, Lu Xiao, Xinjun Xu, Yuehui He, LidongLi, and Yongfang Li]. Compared with the BDF unit, the naphtho-difuran (NDF) unit has a larger pi conjugated system, enhances the stacking of pi-pi electrons and enlarges the delocalization effect of the electrons, thereby obtaining a wider absorption spectrum and high carrier mobility. From the research work reported in the literature, NDF has not been reported in the field of organic small molecule solar cells. To date, the structurally similar derivatives to NDF are naphtho [1, 2-b; 4, 5-b']Dithiophenes (NDT) have been synthesized and used as donor units in the field of solar cells. For example, professor Osaka, university of Osaka, Japan, and coworkers thereof reported that a polymer PNDT3NTz-DT, exhibiting an energy conversion efficiency of 4.9% and a hole mobility of 0.54cm 2. V-1. s-1 [ 2 ]Itaru Osaka,Toru Abe,Masafumi Shimawaki,Tomoyuki Koganezawa,and Kazuo Takimiya.ACS MacroLetters.,2012,1,437-440]. The professor Tobin J. marks of northwest university of America combines two NDT-based small molecule photovoltaic materials, when NDT (TDPP)2And zNDT (TDPP)2And PC61After BM are blended according to different proportions, the energy conversion efficiency reaches 4.1% and 4.7% [ Stephen Loser, Carson J.Bruns, Hiroyuki Miyauchi Oci o Ponce Ortiz, Antonio Facchetti, Samuel I.Stupp, and Tobin J.marks.journal of the American chemistry society,2011,133,8142 sand 8145, respectively; stephen Loser, Hiroyuki Miyauchi, Jonathan W.Hennek, Jermey Smith, Chun Huang, Antonio Faccheti, and Tobin J.marks.chemical communications, 2012,48,8511-]。
In view of the wide application prospect of the photovoltaic material in the field of solar cells, the research of the novel naphtho-difurane photovoltaic material has important significance.
Disclosure of Invention
In view of the above, the present invention provides a naphtho-difuran photovoltaic material, and a preparation method and an application thereof, wherein the naphtho-difuran photovoltaic material has a wide absorption spectrum and a suitable electrochemical energy level; the synthetic route is simple, the cost is low, and the synthetic method has universality; the solar cell device made of the compound serving as the electron donor has good light conversion efficiency.
Based on the above purpose, the invention provides a naphtho-difurane photovoltaic material, which has a structure shown in formula (I):
wherein R in the formula (I) is alkyl.
Preferably, R in said formula (I) is selected from one of the following structures:
based on the same inventive concept, the invention also provides a preparation method of the naphtho-furan photovoltaic material, which comprises the following steps: step 1), carrying out mixed reaction on 1, 5-dihydroxynaphthalene, 1-bromo-2-undecanone and potassium carbonate to obtain a crude product of a compound 1, and leaching the crude product with a silica gel column to obtain the compound 1; step 2), reacting the compound 1 with methanesulfonic acid to obtain a crude compound 2, and leaching the crude compound 2 through a silica gel column to obtain a compound 2; step 3), carrying out mixed reaction on the compound 2, n-butyllithium and trimethyltin chloride to obtain a compound 3; step 4), reacting the compound 3 with the compound 4 to obtain a crude product of the naphtho-difuran photovoltaic material, and leaching the crude product of the naphtho-difuran photovoltaic material through a silica gel column to obtain the naphtho-difuran photovoltaic material;
wherein R in the compound 4 is selected from one of the following structures:
when R has a structural formula
Then, the compound obtained was 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-diisooctyl-3, 6-thienyl-2-pyrrolopyrroledione (M1);
when R has a structural formula
Then, the compound obtained was 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-dioctyl-3, 6-thienyl-2-pyrrolopyrroledione (M2);
when R has a structural formula
The compound thus obtained was 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-docosyl-3, 6-thienyl-2-pyrrolopyrroledione (M3).
The preparation route of the naphtho-difurane photovoltaic material is as follows:
preferably, the molar ratio of 1, 5-dihydroxynaphthalene to 1-bromo-2-undecanone to potassium carbonate in step 1) is 1: (2.25-2.5): (1.5-3); the leaching solution adopted by leaching is a mixed solution of dichloromethane and petroleum ether with a volume ratio of (8-10): 1 or a mixed solution of dichloromethane and n-hexane with a volume ratio of (8-10): 1.
Preferably, the molar ratio of the compound 1 to the methanesulfonic acid in the step 2) is 1 (8-12); the leaching solution adopted by leaching is one of petroleum ether, n-hexane or cyclohexane.
Preferably, the molar ratio of the compound 2, n-butyllithium and trimethyltin chloride in the step 3) is 1 (3-4) to (3.5-4.5).
Preferably, the molar ratio of the compound 3 to the compound 4 in the step 4) is 1 (2.3-2.5); the leacheate used for leaching is a mixed solution of petroleum ether and trichloromethane with the volume ratio of 2:1 or a mixed solution of normal hexane and trichloromethane with the volume ratio of 2: 1.
Based on the same inventive concept, the invention also provides application of the naphtho-difuran photovoltaic material in preparation of solar cells.
Preferably, the naphtho-furan-based photovoltaic material and the electron acceptor are mixed and dissolved to prepare a photovoltaic active layer film, and then a metal electrode is prepared on the film.
More preferably, the mass ratio of the naphtho-furan-based photovoltaic material to the electron acceptor is 1 (1-3); the electron acceptor is PC61BM or derivatives thereof.
From the above, it can be seen that the advantages and benefits of the present invention are:
(1) the naphtho-difuran photovoltaic material has a conjugated structure with a large pi plane, and can obtain a wider ultraviolet-visible absorption spectrum compared with a benzodifuran photovoltaic material.
(2) The naphtho-difuran photovoltaic material is prepared by mixing naphtho [1, 2-b; 4, 5-b' ] dithiophene organic molecular materials have lower HOMO energy level and high stability to oxygen, and are beneficial to preparing solar cell devices with more stable performance.
(3) The synthesis route of the naphtho-difuran photovoltaic material is simple, the cost is low, the synthesis method has universality, and the method can be well popularized and applied to synthesis of other naphtho-difuran materials.
(4) The invention utilizes the naphthofuran to prepare the solar cell, obtains higher energy conversion efficiency (PCE is 4.8 percent), and has good application prospect.
Drawings
FIG. 1 shows the results of thermogravimetric analysis of M1 in example of the present invention;
FIG. 2 is an absorption spectrum of M1 in an example of the present invention;
FIG. 3 is a cyclic voltammogram of M1 in an example of the present invention;
fig. 4 shows the photovoltaic performance of M1 in an example of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
Example 1
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-diisooctyl-3, 6-thienyl-2-pyrrolopyrroledione (M1) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.2g,45mmol) and anhydrous potassium carbonate (8g,58mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 10:1 to obtain 7.4g of a light yellow solid compound 1, wherein the reaction yield is 75%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (9.6g,100mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is petroleum ether, so that 2.85g of yellow solid compound 2 is obtained, and the reaction yield is 62%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.0ml of n-butyllithium (2.4mol/L, 7.2mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1 hour, then 8ml of trimethyltin chloride (1mol/L, 8.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.01g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 64%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.25mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 10mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring and reacting at 115 ℃ for 48 hours, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphtho-difurane photovoltaic material, eluting the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 137mg of blue solid M1, wherein the reaction yield is 91%; the structure of R in the compound 4 is as follows:
the characterization of the M1 is as follows: TOF-MS, m/z 1506;
1H NMR(400 MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,58H),0.88(t,36H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 2
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-diisooctyl-3, 6-thienyl-2-pyrrolopyrroledione (M1) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (12.44g,50mmol) and anhydrous potassium carbonate (4.14g,30mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 8:1 to obtain 7.5g of a light yellow solid compound 1, wherein the reaction yield is 77%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400 MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (7.68g,80mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying an organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column by using n-hexane as a leaching solution to obtain 2.80g of a yellow solid compound 2, wherein the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.3ml of n-butyllithium (2.4mol/L, 8.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.5 hours, then 7ml of trimethyltin chloride (1mol/L, 7.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.03g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 65%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.23mmol of Compound 4 were added to 10ml of anhydrous toluene, and 12mg of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) Stirring and reacting for 50 hours at 110 ℃, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphthofuran-type photovoltaic material, leaching the crude product through a silica gel column, and leaching by using a mixed solution of n-hexane and trichloromethane with a volume ratio of 2:1 to obtain the eluentTo 137mg of blue solid M1, reaction yield 91%; the structure of R in the compound 4 is as follows:
the characterization of the M1 is as follows: TOF-MS, m/z 1506;
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,58H),0.88(t,36H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 3
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-diisooctyl-3, 6-thienyl-2-pyrrolopyrroledione (M1) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.94g,48mmol) and anhydrous potassium carbonate (6.07g,44mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and n-hexane in a volume ratio of 9:1 to obtain 7.3g of a light yellow solid compound 1, wherein the reaction yield is 74%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (11.52g,120mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is cyclohexane, so that 2.8g of yellow solid compound 2 is obtained, and the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 2.5ml of n-butyllithium (2.4mol/L, 6.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.3 hours, then 9ml of trimethyltin chloride (1mol/L, 9.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.05g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 67%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.24mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 15mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring at 120 deg.CCooling to room temperature after 45 hours, pouring into 100ml of methanol for precipitation, filtering to obtain a crude product of the naphthofuran-based photovoltaic material, eluting the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 128mg of blue solid M1, wherein the reaction yield is 88%; the structure of R in the compound 4 is as follows:
the characterization of the M1 is as follows: TOF-MS, m/z 1506;
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,58H),0.88(t,36H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 4
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-dioctyl-3, 6-thienyl-2-pyrrolopyrroledione (M2) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.2g,45mmol) and anhydrous potassium carbonate (8g,58mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 10:1 to obtain 7.4g of a light yellow solid compound 1, wherein the reaction yield is 75%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (9.6g,100mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is petroleum ether, so that 2.85g of yellow solid compound 2 is obtained, and the reaction yield is 62%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.0ml of n-butyllithium (2.4mol/L, 7.2mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1 hour, then 8ml of trimethyltin chloride (1mol/L, 8.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.01g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 64%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.25mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 10mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring and reacting at 115 ℃ for 48 hours, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphthofuran-based photovoltaic material, eluting the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 111mg of blue solid M2, wherein the reaction yield is 74%; the structure of R in the compound 4 is as follows:
the characterization of the M2 is as follows:
TOF-MS:m/z＝1506；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 5
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-dioctyl-3, 6-thienyl-2-pyrrolopyrroledione (M2) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (12.44g,50mmol) and anhydrous potassium carbonate (4.14g,30mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 8:1 to obtain 7.5g of a light yellow solid compound 1, wherein the reaction yield is 77%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (7.68g,80mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying an organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column by using n-hexane as a leaching solution to obtain 2.80g of a yellow solid compound 2, wherein the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.3ml of n-butyllithium (2.4mol/L, 8.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.5 hours, then 7ml of trimethyltin chloride (1mol/L, 7.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.03g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 65%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.23mmol of Compound 4 were added to 10ml of anhydrous toluene, and 12mg of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) Stirring and reacting for 50 hours at 110 ℃, cooling to room temperature, pouring into 100ml of methanol for precipitation, filtering to obtain a crude product of the naphthofuran-based photovoltaic material, leaching the crude product through a silica gel column by using a mixed solution of n-hexane and trichloromethane with a volume ratio of 2:1 as a leaching solution to obtain 105mg of blue solid M2, wherein the reaction yield is 70%; the structure of R in the compound 4 is as follows:
the characterization of the M2 is as follows:
TOF-MS:m/z＝1506；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 6
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-dioctyl-3, 6-thienyl-2-pyrrolopyrroledione (M2) comprising the following steps:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.94g,48mmol) and anhydrous potassium carbonate (6.07g,44mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and n-hexane in a volume ratio of 9:1 to obtain 7.3g of a light yellow solid compound 1, wherein the reaction yield is 74%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (11.52g,120mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is cyclohexane, so that 2.8g of yellow solid compound 2 is obtained, and the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 2.5ml of n-butyllithium (2.4mol/L, 6.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.3 hours, then 9ml of trimethyltin chloride (1mol/L, 9.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.05g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 67%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.24mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 15mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring and reacting for 45 hours at the temperature of 120 ℃, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphthofuran-based photovoltaic material, leaching the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 108mg of blue solid M2, wherein the reaction yield is 72%; the structure of R in the compound 4 is as follows:
the characterization of the M2 is as follows:
TOF-MS:m/z＝1506；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C92H120N4O6S4(％):C,73.36；H,8.03；N,3.72.Found(％):C,73.35；H,8.01；N,3.73。
example 7
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-docosyl-3, 6-thienyl-2-pyrrolopyrroledione (M3) comprising the steps of:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.2g,45mmol) and anhydrous potassium carbonate (8g,58mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 10:1 to obtain 7.4g of a light yellow solid compound 1, wherein the reaction yield is 75%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (9.6g,100mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is petroleum ether, so that 2.85g of yellow solid compound 2 is obtained, and the reaction yield is 62%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.0ml of n-butyllithium (2.4mol/L, 7.2mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1 hour, then 8ml of trimethyltin chloride (1mol/L, 8.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.01g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 64%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.25mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 10mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring and reacting at 115 ℃ for 48 hours, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphthofuran-based photovoltaic material, eluting the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 144mg of blue solid M3, wherein the reaction yield is 83%; the structure of R in the compound 4 is as follows:
the characterization of the M3 is as follows:
TOF-MS:m/z＝1730；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C108H152N4O6S4(％):C,74.95；H,8.85；N,3.24.Found(％):C,74.96；H,8.83；N,3.23。
example 8
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-docosyl-3, 6-thienyl-2-pyrrolopyrroledione (M3) comprising the steps of:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (12.44g,50mmol) and anhydrous potassium carbonate (4.14g,30mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 8:1 to obtain 7.5g of a light yellow solid compound 1, wherein the reaction yield is 77%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (7.68g,80mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 3.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying an organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column by using n-hexane as a leaching solution to obtain 2.8g of a yellow solid compound 2, wherein the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 3.3ml of n-butyllithium (2.4mol/L, 8.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.5 hours, then 7ml of trimethyltin chloride (1mol/L, 7.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.03g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 65%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.23mmol of Compound 4 were added to 10ml of anhydrous toluene, and 12mg of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) Stirring and reacting for 50 hours at 110 ℃, cooling to room temperature, pouring into 100ml of methanol for precipitation, filtering to obtain a crude product of the naphthofuran-based photovoltaic material, leaching the crude product through a silica gel column by using a mixed solution of n-hexane and trichloromethane with the volume ratio of 2:1 as a leaching solution to obtain 138mg of blue solid M3, wherein the reaction yield is 80%; the structure of R in the compound 4 is as follows:
the characterization of the M3 is as follows:
TOF-MS:m/z＝1730；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C108H152N4O6S4(％):C,74.95；H,8.85；N,3.24.Found(％):C,74.96；H,8.83；N,3.23。
example 9
Preparation of 3, 7-dinonyl-naphthodifuran-2, 6-bis (2, 5-docosyl-3, 6-thienyl-2-pyrrolopyrroledione (M3) comprising the steps of:
step 1) under the protection of argon, 1, 5-dihydroxynaphthalene (3.20g,20.0mmol), 1-bromo-2-undecanone (11.94g,48mmol) and anhydrous potassium carbonate (6.07g,44mmol) are mixed and dissolved in 100ml of anhydrous acetonitrile, and heated under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring the mixture into water, extracting the mixture by using dichloromethane, washing the mixed phase by using water, drying the mixture by using anhydrous magnesium sulfate, and then spin-drying the organic phase to obtain a crude product of the compound 1, leaching the crude product by using a silica gel column by using a leaching solution which is a mixed solution of dichloromethane and n-hexane in a volume ratio of 9:1 to obtain 7.3g of a light yellow solid compound 1, wherein the reaction yield is 74%;
the characterization of compound 1 is as follows:
GC-MS:m/z＝497；
1H NMR(400MHz,CDCl3,ppm):7.93(d,2H),7.74(d,2H),7.54(d,2H),4.62(t,4H),2.78(t,4H),1.77-1.27(m,28H),0.88(t,6H)；
Elemental analysis:calcd.for C32H48O4(％):C,77.38；H,9.47；O,12.88；found:C,77.27；H,9.60；O,13.03。
step 2) Compound 1(4.96g,10mmol) was dissolved in 50ml dichloromethane, methanesulfonic acid (11.52g,120mmol) was added to give a dark blue solution, and the reaction was stirred under reflux for 4.5 hours; after the reaction is finished, cooling to room temperature, pouring into ice water, extracting with dichloromethane, spin-drying the organic phase to obtain a crude product of the compound 2, leaching the crude product through a silica gel column, wherein the leaching solution adopted for leaching is cyclohexane, so that 2.8g of yellow solid compound 2 is obtained, and the reaction yield is 61%;
the characterization of compound 2 is as follows:
GC-MS:m/z＝461；
1H NMR(400MHz,CDCl3,ppm):8.14(d,2H),7.74(d,2H),7.55(d,2H),2.78(t,4H),1.76-1.26(m,28H),0.88(t,6H)；
Elemental analysis:calc.for C32H44O2(％):C,83.43；H,9.63；O,6.95；found:C,83.37；H,9.60；O,6.83。
step 3) Compound 2(0.92g, 2mmol) was dissolved in 50ml of anhydrous tetrahydrofuran under argon protection, the solution was cooled to-78 deg.C, 2.5ml of n-butyllithium (2.4mol/L, 6.0mmol) solution was slowly added dropwise, the reaction was stirred at room temperature for 1.3 hours, then 9ml of trimethyltin chloride (1mol/L, 9.0mmol) was added at-78 deg.C, and the reaction mixture was stirred at room temperature overnight. After the reaction is finished, pouring the reaction mixture solution into 100ml of ice water, extracting with dichloromethane, and spin-drying the organic phase to obtain a crude product of the compound 3, and recrystallizing the crude product with isopropanol to obtain 1.05g of a yellow needle-shaped solid compound 3, wherein the reaction yield is 67%;
the characterization of compound 3 is as follows:
GC-MS:m/z＝786；
1H NMR(400MHz,CDCl3,ppm):8.11(d,2H),7.66(d,2H),2.74(d,4H),1.59-1.29(m,28H),0.88(t,6H),0.47(s,18H)；
Elemental analysis:calc.for C32H44O2(％):C,58.04；H,7.69；O,4.07；found:C,58.11；H,7.60；O,4.13。
step 4) under argon protection, 0.1mmol of Compound 3 and 0.24mmol of Compound 4 were added to 10ml of anhydrous toluene, followed by 15mg of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Stirring and reacting for 45 hours at the temperature of 120 ℃, cooling to room temperature, pouring into 100ml of methanol for precipitation and filtration to obtain a crude product of the naphthofuran-based photovoltaic material, leaching the crude product through a silica gel column by using a mixed solution of petroleum ether and trichloromethane in a volume ratio of 2:1 to obtain 147mg of blue solid M3, wherein the reaction yield is 85%; the structure of R in the compound 4 is as follows:
the characterization of the M3 is as follows:
TOF-MS:m/z＝1730；
1H NMR(400MHz,CDCl3,ppm):8.96(d,2H),8.88(d,2H),8.14(d,2H),7.74(d,2H),7.55(d,2H),7.25(m,2H),7.00(d,2H),3.97(m,8H),2.78(t,4H),1.76-1.26(m,70H),0.88(t,24H)；
Anal.Calcd for C108H152N4O6S4(％):C,74.95；H,8.85；N,3.24.Found(％):C,74.96；H,8.83；N,3.23。
example 10
Preparation of organic small molecule solar cell
3mg of M1 and 3mg of PC61BM mixing, adding 0.25mL of trichloromethane for dissolving, preparing a film with the thickness of about 120nm on conductive glass modified by PEDOT (PSS) by a spin coating mode, carrying out thermal annealing at 110 ℃ for 10 minutes, and then preparing a metal electrode on the photovoltaic active layer by lithium fluoride by a vacuum evaporation mode. The device performance is as follows: short-circuit current of 11.1mA/cm2(ii) a Open circuit voltage is 0.83V; fill factor 52.1%; simulated sunlight (A.M.1.5, 100 mW/cm)2) The energy conversion efficiency was 4.8%.
Example 11
Preparation of organic small molecule solar cell
2mg of M2 and 4mg of PC61BM mixing, adding 0.25mL of trichloromethane for dissolving, preparing a film with the thickness of about 110nm on the conductive glass modified by PEDOT (PSS) by a spin coating mode, carrying out thermal annealing at 110 ℃ for 10 minutes, and then preparing a metal electrode on the photovoltaic active layer by lithium fluoride by a vacuum evaporation mode. The device performance is as follows: short-circuit current 3.2mA/cm2(ii) a Open circuit voltage is 0.79V; padding factor 530.%; simulated sunlight (A.M.1.5, 100 mW/cm)2) The energy conversion efficiency was 1.3%.
Example 12
Preparation of organic small molecule solar cell
1.5mg of M3 and 4.5mg of PC61BM blendingAdding 0.25mL of trichloromethane for dissolving, preparing a film with the thickness of about 120nm on the conductive glass modified by PEDOT (PSS) by a spin coating mode, carrying out thermal annealing at 110 ℃ for 10 minutes, and then preparing a metal electrode on the photovoltaic active layer by aluminum in a vacuum evaporation mode. The device performance is as follows: short-circuit current 7.66mA/cm2(ii) a Open circuit voltage is 0.82V; filling factor is 50.8%; simulated sunlight (A.M.1.5, 100 mW/cm)2) The energy conversion efficiency was 3.2%.
Example 13
Taking M1 as an example, the thermal stability analysis, the spectral analysis, the electrochemical performance analysis and the photovoltaic performance analysis are carried out on the material.
The results of thermogravimetric analysis of M1 are shown in fig. 1. From the results, it can be seen that: the 5% thermal decomposition temperature of M1 is 317 ℃, which shows that the naphthofuran type photovoltaic material has good thermal stability and can meet the requirement that the material quality does not decay too fast when the material works outdoors for a long time.
The absorption spectrum of M1 is shown in FIG. 2, and the optical results of M1 are shown in Table 1 below. As can be seen from table 1: in the solution state, the absorption side band is 650nm, and the maximum absorption peak is 573 nm; in the thin film state, the absorption sideband of M1 is at 750nm, the contrast solution has obvious red shift, and the optical band gap of M1 is 1.65 eV. As can be seen from the absorption spectrum of FIG. 2, the naphthofuran-based photovoltaic material has a low energy gap and a wide absorption range for light, which is beneficial to obtaining a high photocurrent, and the narrow-bandgap photovoltaic material having a wide absorption range in a visible light region has a wide application prospect in the preparation of solar cells.
Cyclic voltammetry is a commonly used method for determining the HOMO and LUMO energy levels of compounds. FIG. 3 shows the cyclic voltammogram of M1, and the electrochemical results of M1 are shown in Table 1. We can see from the oxidation curve part that the oxidation potential of M1 is 0.78V, the corresponding HOMO level is-5.50 eV, and from the reduction curve part that the reduction potential of M1 is-0.73V, so the corresponding LUMO level is-3.98 eV and the electrochemical bandgap is 1.52 eV. The low HOMO energy level shows that the naphthofuran type photovoltaic material has good air stability and is very suitable for preparing solar cell devices.
The optical and electrochemical results of M1 are shown in table 1:
table 1.
The photovoltaic performance of M1 is shown in fig. 4, and the photovoltaic performance results of M1 are shown in table 2. As can be seen from fig. 4 and table 2: the naphthofuran organic micromolecule solar cell material has excellent photovoltaic performance; such as M1 and PC61When BM blending is carried out, after 20 molecules of thermal annealing are carried out at 120 ℃, the energy conversion efficiency reaches 4.8%, and therefore it can be concluded that the energy conversion efficiency of the solar cell prepared from the naphtho-furan photovoltaic material can be further improved by optimizing a device.
Table 2: the photovoltaic performance results for M1 are shown in table 2:
table 2.
As can be seen from the above examples 1 to 13: the synthesis route of the naphtho-difuran photovoltaic material is simple, the cost is low, the synthesis method is universal, and the naphtho-difuran photovoltaic material can be well popularized and applied to synthesis of other naphtho-difuran materials; the naphthofuran type photovoltaic material can obtain a wider ultraviolet-visible absorption spectrum, has a lower HOMO energy level and high stability to oxygen, is beneficial to preparing a solar cell device with more stable performance, and has a good photoelectric conversion function when being applied to a solar cell.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A naphtho-difuran photovoltaic material is characterized in that the structure of the photovoltaic material is shown as a formula (I):
wherein R in the formula (I) is selected from one of the following structures:
2. a method for preparing the naphtho-difurane photovoltaic material according to claim 1, which comprises the following steps:
step 1), carrying out mixed reaction on 1, 5-dihydroxynaphthalene, 1-bromo-2-undecanone and potassium carbonate to obtain a crude product of a compound 1, and leaching the crude product with a silica gel column to obtain the compound 1;
step 2), reacting the compound 1 with methanesulfonic acid to obtain a crude compound 2, and leaching the crude compound 2 through a silica gel column to obtain a compound 2;
step 3), carrying out mixed reaction on the compound 2, n-butyllithium and trimethyltin chloride to obtain a compound 3;
step 4), reacting the compound 3 with the compound 4 to obtain a crude product of the naphtho-difuran photovoltaic material, and leaching the crude product of the naphtho-difuran photovoltaic material through a silica gel column to obtain the naphtho-difuran photovoltaic material;
wherein R in the compound 4 is selected from one of the following structures:
3. the method for preparing the naphthodifurane-based photovoltaic material according to claim 2, wherein the molar ratio of the 1, 5-dihydroxynaphthalene to the 1-bromo-2-undecanone to the potassium carbonate in the step 1) is 1: (2.25-2.5): (1.5-3); the leaching solution adopted by leaching is a mixed solution of dichloromethane and petroleum ether with a volume ratio of (8-10): 1 or a mixed solution of dichloromethane and n-hexane with a volume ratio of (8-10): 1.
4. The preparation method of the naphtho-furan-based photovoltaic material as claimed in claim 2, wherein the molar ratio of the compound 1 to the methanesulfonic acid in the step 2) is 1 (8-12); the leaching solution adopted by leaching is one of petroleum ether, n-hexane or cyclohexane.
5. The method for preparing the naphthodifurane photovoltaic material as claimed in claim 2, wherein the molar ratio of the compound 2, n-butyllithium and trimethyltin chloride in the step 3) is 1 (3-4) to (3.5-4.5).
6. The preparation method of the naphtho-difurane photovoltaic material as claimed in claim 2, wherein the molar ratio of the compound 3 to the compound 4 in the step 4) is 1 (2.3-2.5); the leacheate used for leaching is a mixed solution of petroleum ether and trichloromethane with the volume ratio of 2:1 or a mixed solution of normal hexane and trichloromethane with the volume ratio of 2: 1.
7. Use of the naphtho-difuran-based photovoltaic material according to claim 1, in the preparation of a solar cell.
8. The use of the naphtho-difuran-based photovoltaic material according to claim 7, wherein the naphtho-difuran-based photovoltaic material is mixed with an electron acceptor and dissolved to prepare a photovoltaic active layer film, and then a metal electrode is prepared on the film.
9. The application of the naphtho-difuran photovoltaic material as claimed in claim 8, wherein the mass ratio of the naphtho-difuran photovoltaic material to the electron acceptor is 1 (1-3); the electron acceptor is PC61BM or derivatives thereof.
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