CN104151861B - Taking phenanthrene and carbazole as the organic dye of core and an its preparation method, and organic dye sensitized solar cell - Google Patents
Taking phenanthrene and carbazole as the organic dye of core and an its preparation method, and organic dye sensitized solar cell Download PDFInfo
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Abstract
The present invention provides a kind of organic dye, has structure shown in formula (1). The present invention taking phenanthrene and carbazole as core, it may also be useful to the triphenylamine of replacement regulates and controls the level structure of dye molecule to body and cyanoacrylate acid acceptor, thus has designed and synthesized multiple efficient to acceptor organic dye. The dye-sensitized solar cells prepared with this dye molecule, power-conversion efficiencies breaches 10%, far above other taking phenanthrene and carbazole as the organic dye sensitized solar cell of core, and organic dye provided by the invention, in preparation process, avoid the use of heavy metal, its abundant raw material source, cost is lower, and suitability for industrialized production is more friendly to environment.
Description
Technical field
The present invention relates to organic dye technical field, particularly relate to a kind of taking phenanthrene and carbazole as the organic dye of core and its preparation method, and organic dye sensitized solar cell.
Background technology
Along with the increase of energy demand, seeking the research focus that the cleaning sustainable energy becomes global gradually, wherein, sun power is as a kind of renewable and clean energy resource, and its exploitation are one of the important topics in energy research field.
Current silicon system solar cell has reached higher photoelectric transformation efficiency and has been widely used in comprising the every field of the national product of aerospace. Wherein the technology of crystal-silicon solar cell is most widely used, and accounts for more than the 80% of solar cell. But there is manufacturing cost height, processing condition are harsh and refine the shortcomings such as energy consumption is big, seriously polluted in silicon process. In order to find the substitute of crystal silicon cell, people have developed the solar cell of other material, wherein mainly comprise gallium arsenide III-V, Cadmium Sulfide and cadmium telluride thin-film battery etc. In above-mentioned battery, although the efficiency of gallium arsenide, Cadmium Sulfide, cadmium telluride polycrystalline hull cell relatively amorphous silicon thin-film solar cell efficiency height, relatively silicon single crystal battery is low for cost, and is also easy to scale operation, but owing to arsenic, cadmium etc. have severe toxicity, environment can be caused serious pollution. Therefore, these are not the optimal substitute of crystal silicon solar energy battery.
The solar cell of inorganic materials development is replaced to become the active and important research direction of energy field gradually with organic photoelectrical material in recent years. 1991,Three core ruthenium dyestuff RuL2 (��-(CN) Ru (CN) L ' 2) 2 (L=2 that the people such as Amadelli were reported by study group, 2 '-dipyridyl-4,4 '-dicarboxylic acid, L '=bipy 2,2' bipyridyl) it is adsorbed on, as sensitizing agent, the high quality TiO that they develop with great concentration for many years2Nano-crystal thin-film is made device, obtains the photoelectric transformation efficiency of under simulated solar irradiation 7.1%, the development course of organic photovoltaic cell has the meaning of milestone, has thus started the research boom of dye-sensitized solar cells.
Compared with silica-based solar cell, the manufacturing cost of dye-sensitized solar cells is lower, and its photoelectric transformation efficiency is higher, close to thin-film silicon cell, thus has a good application prospect.
Dyestuff in the high efficiency dye sensitization solar cell of report mostly is the title complex containing precious metal at present, such as [Ru(bpy)2(dppzi) (J.Am.Chem.Soc.2008,130,10720-10728). But, owing to the reserves of precious metal are limited, thus limit the practical application of precious metal dyestuff. And the pure organic dye sensitized cells top efficiency not containing precious metal is only 8.8%, with ruthenium based dye than efficiency still has bigger gap.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of taking phenanthrene and carbazole as the organic dye of core and its preparation method, and organic dye sensitized solar cell, with organic dye sensitized solar cell prepared by described organic dye, there is higher efficiency.
The present invention provide a kind of taking phenanthrene and carbazole as the organic dye of core, there is structure shown in formula (1):
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0 or 1.
Preferably, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
Preferably, described organic dye has the concrete structure shown in formula II or formula III:
Present invention also offers a kind of taking phenanthrene and carbazole as the preparation method of the organic dye of core, comprising:
By compound shown in formula IV and N, dinethylformamide and phosphorus oxychloride reaction, and then with triphenylamine boric ester derivative shown in formula (V), react under palladium, Sphos and potassiumphosphate effect, finally react under ammonium acetate effect with alpha-cyanoacrylate again, obtain the organic dye shown in formula (1);
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0;
X is halogen.
Preferably, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
Present invention also offers a kind of taking phenanthrene and carbazole as the preparation method of the organic dye of core, comprising:
By the triphenylamine derivative shown in formula VI and triisopropyl silico acetylene, at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, then with the reaction of tetrabutyl fluoride amine, then with compound shown in formula (VII), at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, last and alpha-cyanoacrylate reacts under ammonium acetate effect, obtains the organic dye shown in formula (1);
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 1;
X is halogen.
Preferably, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
Present invention also offers a kind of taking phenanthrene and carbazole as the organic dye sensitized solar cell of core, it is characterised in that, dyestuff layer is above-mentioned organic dye, or organic dye prepared by above-mentioned preparation method.
Preferably, described organic dye has the concrete structure shown in following formula II or formula III:
Compared with prior art, the present invention provide a kind of taking phenanthrene and carbazole as the organic dye of core, there is structure shown in formula (1). The present invention taking phenanthrene and carbazole as core, it may also be useful to the triphenylamine of replacement regulates and controls the level structure of dye molecule to body and cyanoacrylate acid acceptor, thus has designed and synthesized multiple efficient to acceptor organic dye. The dye-sensitized solar cells prepared with this dye molecule, power-conversion efficiencies breaches 10%, far above existing other taking phenanthrene and carbazole as the organic dye sensitized solar cell of core. And organic dye provided by the invention, in preparation process, avoids the use of heavy metal, its abundant raw material source, and cost is lower, and suitability for industrialized production is more friendly to environment.
Embodiment
The present invention provide a kind of taking phenanthrene and carbazole as the organic dye of core, there is structure shown in formula (1):
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0 or 1.
The present invention taking phenanthrene and carbazole as core, it may also be useful to the triphenylamine of replacement regulates and controls the level structure of dye molecule to body and cyanoacrylate acid acceptor, thus has designed and synthesized multiple efficient to acceptor organic dye. The dye-sensitized solar cells prepared with this dye molecule, power-conversion efficiencies breaches 10%, far above existing other taking phenanthrene and carbazole as the organic dye sensitized solar cell of core. And organic dye provided by the invention, in preparation process, avoids the use of heavy metal, its abundant raw material source, and cost is lower, and suitability for industrialized production is more friendly to environment.
Organic dye provided by the invention, has structure shown in formula (1), wherein,
R1For alkyl, it is preferable to C1��C18Alkyl, it is more preferable to be C10��C18Alkyl, it is more preferable to be C12��C18Alkyl, it is more preferable to be C14��C16Alkyl, it is most preferred that be 2-own base-1-base in the last of the ten Heavenly stems.
R2��R3Independent is preferably H, C1��C18Alkyl or C1��C18Any one in alkoxyl group; It is more preferably H, C1��C12Alkyl or C1��C12Any one in alkoxyl group, it is more preferable to be H, C1��C10Alkyl or C1��C10Any one in alkoxyl group, it is more preferable to be H, C1��C8Alkyl or C1��C8Any one in alkoxyl group, it is most preferred that be own base. The present invention is to R2��R3The position of substitution there is no special restriction, it is possible to replace in the optional position of phenyl ring.
Y is 0 or 1.
When y is 0, described organic dye preferably has concrete structure shown in following formula II:
When y is 1, described organic dye preferably has concrete structure shown in following formula III:
Present invention also offers a kind of taking phenanthrene and carbazole as the preparation method of the organic dye of core, comprising:
By compound shown in formula IV and N, dinethylformamide and phosphorus oxychloride reaction, and then with triphenylamine boric ester derivative shown in formula (V), react under palladium, Sphos and potassiumphosphate effect, finally react under ammonium acetate effect with alpha-cyanoacrylate again, obtain the organic dye shown in formula (1);
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0;
X is halogen.
First by compound shown in formula IV and N, dinethylformamide and phosphorus oxychloride reaction, reaction scheme is as follows:
Concrete, first compound shown in formula IV is mixed with 1,2-ethylene dichloride, ice bath is cooled to 0 DEG C��5 DEG C, then adds N, dinethylformamide and phosphorus oxychloride, it is warming up to 30 DEG C��60 DEG C reactions to spend the night, obtains compound shown in formula (VII).
In the present invention, the quality and 1 of compound shown in described formula IV, 2-ethylene dichloride, N, the ratio of the volume of dinethylformamide, phosphorus oxychloride is preferably 2g:(10mL��30mL): (0.1mL��0.4mL): (0.2mL��0.5mL), it is more preferable to be 2g:(15mL��25mL): (0.2mL��0.35mL): (0.3mL��0.45mL).
After reaction terminates, product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably ethyl acetate and sherwood oil, and volume ratio is preferably 1:20.
After obtaining compound shown in formula (VII), by triphenylamine boric ester derivative shown in itself and formula (V), reacting under palladium, Sphos and potassiumphosphate effect, reaction scheme is as follows:
In the present invention, the solvent of described reaction is preferably the mixed solvent of dioxane and water, and the volume ratio of described dioxane and water is preferably (4��6): 1; The mol ratio of compound and described triphenylamine boric ester derivative shown in described formula (VII) is preferably 1:(0.95��1.05); Compound shown in described formula (VII) and palladium, Sphos (2-dicyclohexylphosphontetrafluoroborate-2 ', 6 '-dimethoxy-1,1 '-biphenyl), the mass ratio of potassiumphosphate be preferably 1:(0.006��0.013): (0.01��0.024): (1.5��6). The temperature of described reaction is preferably 30 DEG C��50 DEG C, and the time of described reaction is preferably 10 hours��15 hours. In the present invention, described reaction preferably carries out under protection of inert gas, and described rare gas element is preferably argon gas.
After reaction terminates, reaction product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, then chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably chloroform and sherwood oil, and volume ratio is preferably 1:2.
After obtaining compound shown in formula (IV-2), itself and alpha-cyanoacrylate being reacted under ammonium acetate effect, can obtain the organic dye shown in formula (1), reaction scheme is as follows:
Wherein, y=0.
The solvent of described reaction is preferably the mixed solvent of acetonitrile and methylene dichloride, and the volume ratio of described acetonitrile and methylene dichloride is preferably 1:(1��3); Described reaction is preferably back flow reaction, and the time of described reaction is preferably 36 hours��60 hours. The mass ratio of compound and alpha-cyanoacrylate shown in described formula (IV-2) is preferably 1:(0.95��2); The mass ratio of compound and ammonium acetate shown in described formula (IV-2) is preferably 1:(0.1��0.3).
After reaction terminates, reaction product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, then chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably methyl alcohol and chloroform, and volume ratio is preferably 1:20.
In the present invention, the R occurred in above-mentioned reaction scheme1��R2��R3With X all with the R of above-mentioned record1��R2��R3Identical with the scope of X, do not repeat them here.
The source of above-mentioned each starting compound and solvent, catalyzer be there is no special restriction by the present invention, it is possible to for generally commercially available, or be prepared according to method well known in the art.
Present invention also offers a kind of taking phenanthrene and carbazole as the preparation method of the organic dye of core, comprising:
By the triphenylamine derivative shown in formula VI and triisopropyl silico acetylene, at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, then with the reaction of tetrabutyl fluoride amine, then with compound shown in formula (VII), at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, last and alpha-cyanoacrylate reacts under ammonium acetate effect, obtains the organic dye shown in formula (1).
First, by the triphenylamine derivative shown in formula VI and triisopropyl silico acetylene, at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, reaction scheme is as follows:
In the present invention, the mol ratio of the triphenylamine derivative shown in described formula VI and triisopropyl silico acetylene is preferably 1:(1��1.05); Triphenylamine derivative shown in described formula VI and Pd (PPh3)2Cl2, cuprous iodide, triethylamine mass ratio be preferably 100:(10��15): (3��4): (0.1��0.5). In the present invention, the solvent of described reaction is preferably toluene; Described reaction preferably carries out under protection of inert gas, and described rare gas element is preferably argon gas. In the present invention, described reaction is preferably back flow reaction, and the time of described reaction is preferably 8 hours��12 hours.
After reaction terminates, reaction product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, then chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably ethyl acetate and sherwood oil, and volume ratio is preferably 1:50.
After obtaining compound shown in formula (VI-1), itself and tetrabutyl fluoride amine are reacted, then with compound shown in formula (VII), at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, reaction scheme is as follows:
First compound shown in formula (VI-1) and tetrabutyl fluoride amine are reacted, slough silicon ether protective group. Concrete, compound shown in formula (VI-1) and tetrabutyl fluoride amine are reacted in methylene dichloride, shown in described formula (VI-1), the mass ratio of compound and tetrabutyl fluoride amine is 1:(3��10), the temperature of described reaction is preferably room temperature, and the time of described reaction is preferably 3 hours��5 hours; Reaction product is purified after terminating by described reaction, it is preferable that, after adding distilled water, adopt chloroform to extract, the present invention preferably extracts more than 3 times, then merges organic phase, concentrated after dry, obtains the compound after deprotection.
After obtaining the compound after described deprotection, by compound shown in itself and formula (VII), at Pd (PPh3)2Cl2, cuprous iodide (CuI) and triethylamine (Et3N) react under effect.
The present invention is preferred, mol ratio preferably 1:(1��1.05 of the compound after described deprotection and compound shown in formula (VII)), compound and Pd (PPh shown in described formula (VII)3)2Cl2, cuprous iodide, triethylamine amount ratio be preferably 100:(10��15): (1��5): (0.1��0.5), it is more preferable to be 100:(11��13): (2��4): (0.2��0.45); The solvent of described reaction is preferably toluene; Described reaction is preferably back flow reaction, and the time of described reaction is preferably 8 hours��12 hours; Described reaction preferably carries out under the protection of rare gas element, and described rare gas element is preferably argon gas.
After reaction terminates, reaction product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, then chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably ethyl acetate and sherwood oil, and volume ratio is preferably 1:20.
After obtaining compound shown in formula (VI-2), itself and alpha-cyanoacrylate being reacted under ammonium acetate effect, obtain the organic dye shown in formula (1), reaction scheme is as follows:
Wherein, y=1.
The solvent of described reaction is preferably the mixed solvent of acetonitrile and methylene dichloride, and the volume ratio of described acetonitrile and methylene dichloride is preferably 1:(1��3); Described reaction is preferably back flow reaction, and the time of described reaction is preferably 36 hours��60 hours. The mass ratio of compound and alpha-cyanoacrylate shown in described formula (IV-2) is preferably 1:(0.5��1.05); The mass ratio of compound and ammonium acetate shown in described formula (IV-2) is preferably 1:(0.05��0.3).
After reaction terminates, reaction product is purified, it is preferable that, reaction system is cooled to room temperature, add 10mL��30mL water and stir 1 hour��3 hours, then chloroform extracts, and the present invention preferably extracts more than 3 times, then merges organic phase, concentrate after dry, carrying out pillar layer separation, the developping agent of pillar layer separation of the present invention is preferably methyl alcohol and chloroform, and volume ratio is preferably 1:20.
In the present invention, the R occurred in above-mentioned reaction scheme1��R2��R3With X all with the R of above-mentioned record1��R2��R3Identical with the scope of X, do not repeat them here.
The source of above-mentioned each starting compound and solvent, catalyzer be there is no special restriction by the present invention, it is possible to for generally commercially available, or be prepared according to method well known in the art.
Present invention also offers a kind of organic dye sensitized solar cell, dyestuff layer is above-mentioned organic dye, or organic dye prepared by above-mentioned preparation method.
The present invention is preferred, and described organic dye has the concrete structure shown in following formula II or formula III:
The preparation method of described dye-sensitized cell be there is no special restriction by the present invention, it is possible to be prepared according to preparation method well known to those skilled in the art, as long as its dyestuff layer is above-mentioned organic dye, the present invention is preferred, by TiO2Structure duplicature electrode soaks in the solution of described organic dye, after taking out electrode, will cover the molten ring sealing of glass electrode heat of nanometer platinum, and will finally be injected into by ionogen in the gap of two electrodes, namely constitute dye-sensitized solar cells. The solvent of described organic dye solution is preferably the mixing solutions of ethanol and chloroform, and the volume ratio of described ethanol and chloroform is preferably (5��20): 1; The concentration of described organic dye solution is preferably 50 ��m of ol/L��200 ��m ol/L; The time of described immersion is preferably 8 hours��20 hours, and the temperature of described immersion is preferably room temperature.
Dye-sensitized cell provided by the invention, power-conversion efficiencies breaches 10%, far above existing other taking phenanthrene and carbazole as the organic dye sensitized solar cell of core.
The present invention provides a kind of organic dye, has structure shown in formula (1). The present invention taking phenanthrene and carbazole as core, it may also be useful to the triphenylamine of replacement regulates and controls the level structure of dye molecule to body and cyanoacrylate acid acceptor, thus has designed and synthesized multiple efficient to acceptor organic dye. And organic dye provided by the invention, in preparation process, avoids the use of heavy metal, its abundant raw material source, and cost is lower, and suitability for industrialized production is more friendly to environment.
In order to the present invention is described further, below in conjunction with embodiment to organic dye provided by the invention and its preparation method, and organic dye sensitized solar cell is described in detail.
Embodiment 1
The preparation of the organic dye of formula II structure, synthetic route is as follows:
Compound 1 is synthesized according to reference (W.Jiang, H.Qian, Y.Li, Z.Wang, J.Org.Chem.2008,73,7369.).
In the Schlenk reaction flask of drying, 2.00g compound 1 is dissolved in 20mL1,2-ethylene dichloride, reaction system ice bath to 0 DEG C, in reaction system, adds 0.31mLN, dinethylformamide and 0.40mL phosphorus oxychloride, be warming up to 40 DEG C of reactions and spend the night.
After reaction terminates, reaction system is cooled to room temperature, add 20mL water and stir 2 hours, chloroform extraction three times, merge organic phase, organic phase anhydrous sodium sulfate drying, it is filtered to remove siccative, concentrated filtrate, by ethyl acetate/petroleum ether (volume ratio 1/20) as developping agent column chromatography, obtain 1.76g intermediate 2, receipts rate 84%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that the intermediate 2 obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl3) ��: 10.23 (s, 1H), 8.99 (d, J=8.2Hz, 1H), 8.20 (m, 2H), 8.05 (d, J=8.2Hz, 1H), 7.69 (m, 1H), 7.63 (m, 1H), 7.47 (m, 2H), 3.70 (d, J=7.2Hz, 2H), 1.81 (m, 1H), 1.13 (m, 24H), 0.81 (m, 6H).
13CNMR(100MHz,CDCl3)��:192.59,133.97,129.98,129.27,128.94,128.85,127.23,126.72,126.42,125.47,125.08,124.14,123.61,123.34,123.05, 122.17,121.20,121.12,120.10,116.46,114.96,49.58,39.77,31.97,31.90,31.73,29.95,29.66,29.60,29.38,26.46,22.76,14.24,14.21��
Mass spectrometry results: 596.24 ([M+H]+)��
Results of elemental analyses: C, 74.48; H, 7.10; N, 2.35.
The synthesis of intermediate 3:
Synthesize hexyloxy according to document (R.Li, J.Liu, N.Cai, M.ZhangandP.Wang, J.Phys.Chem.B, 2010,114,4461.) and replace triphenylamine boric acid ester.
In three neck round-bottomed flasks, the triphenylamine boric acid ester that 1.76g compound 2 and 1.75g hexyloxy replace is dissolved in 20mL1,4-dioxane/water (volume ratio 5/1), adds 13mg palladium under argon gas shielded, 24mgSphos and 3.14g potassiumphosphate. Reaction system is warming up to 40 DEG C of reactions 12 hours.
After reaction terminates, temperature of reaction system is down to room temperature, after adding 30mL distilled water, chloroform extraction three times, merges organic phase, organic phase anhydrous sodium sulfate drying, it is filtered to remove siccative, concentrated filtrate, with chloroform/sherwood oil (volume ratio 1/2) as developping agent column chromatography, obtain 2.25g red liquid intermediate 3, receipts rate 78%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that the intermediate 3 obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d8) ��: 10.27 (s, 1H), 9.21 (d, J=8.2Hz, 1H), 8.65 (d, J=7.6Hz, 1H), 8.60 (d, J=7.6Hz, 1H), 8.21 (d, J=8.2Hz, 1H), 7.98 (s, 1H), 7.79 (m, 1H), 7.73 (m, 1H), 7.64 (s, 1H), 7.53 (d, J=7.0Hz, 2H), 7.17 (d, J=8.9Hz, 4H), 7.12 (d, J=8.6Hz, 2H), 6.90 (d, J=8.9Hz, 4H), 4.29 (d, J=7.4Hz, 2H), 3.95 (t, J=6.4Hz, 4H), 2.15 (m, 1H), 1.77 (m, 4H), 1.50 (m, 4H), 1.36 (m, 10H), 1.28 (m, 6H), 1.12 (m, 18H), 0.91 (m, 6H), 0.77 (m, 6H).
13CNMR(100MHz,THF-d8) ��: 192.70,157.11,149.65,141.79,136.35,134.12,131.73,131.51,131.19,131.10,129.97,128.81,127.89,127.45,125.97,125.69,125.40,125.23,125.09,122.88,122.03,121.87,120.83,116.44,116.30,114.57,68.96,50.47,40.74,32.92,32.85,32.76,32.70,32.65,30.97,30.69,30.54,30.49,30.33,27.36,26.93,23.71,23.62,14.60.
Mass spectrometry results: 961.61 ([M+H]+)��
Results of elemental analyses: C, 83.71; H, 8.39; N, 2.91.
The synthesis of target product II:
In two mouthfuls of round-bottomed flasks of drying, 2.25g compound 3 is dissolved in the mixed solvent of acetonitrile and methylene dichloride (volume ratio 1/2), adds 3.10g alpha-cyanoacrylate and 284mg ammonium acetate. Reaction system is heated to back flow reaction 48 hours.
After reaction terminates, temperature of reaction system is down to room temperature, after adding 30mL distilled water, chloroform extraction three times, merges organic phase, organic phase anhydrous sodium sulfate drying, it is filtered to remove siccative, concentrated filtrate, with methyl alcohol/chloroform (volume ratio 1/20) as developping agent column chromatography, obtains target product II. Then being dissolved in chloroform by II, repeatedly wash in turn with the aqueous hydrochloric acid of 0.2mol/L and distilled water, concentrated organic phase, drying under reduced pressure obtains 2.28g violet solid target product II, receipts rate 95%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that compound shown in the formula II obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d8) ��: 9.20 (s, 1H), 8.69 (m, 2H), 8.63 (d, J=7.6Hz, 1H), 8.22 (m, 2H), 7.78 (m, 2H), 7.61 (s, 1H), 7.51 (d, J=8.4Hz, 2H), 7.15 (d, J=8.9Hz, 4H), 7.10 (d, J=8.4Hz, 2H), 6.90 (d, J=8.9Hz, 4H), 4.22 (m, 2H), 3.96 (t, J=6.4Hz, 4H), 2.16 (m, 1H), 1.77 (m, 4H), 1.50 (m, 4H), 1.36 (m, 10H), 1.28 (m, 10H), 1.12 (m, 12H), 0.93 (m, 6H), 0.77 (m, 6H).
13CNMR(100MHz,THF-d8)��:157.09,151.09,149.59,141.76,136.30,134.07,131.76,131.64,131.56,131.02,130.68,129.71,128.75,127.92,126.73,126.06,125.69,125.39,124.69,122.93,121.82,121.54,120.79,118.45,116.30,116.07,114.47,68.96,50.44,40.75,33.00,32.92,32.80,32.76,30.95,30.78,30.69,30.50,30.47,30.33,28.17,27.40,27.36,26.93,23.71,23.61,14.59��
High resolution mass spectrum analytical results: 1027.62271.
Results of elemental analyses: C, 81.75; H, 7.94; N, 4.09.
Result shows, the present invention has prepared the compound shown in formula II.
Embodiment 2
The preparation of organic dye III
Reaction scheme is as follows:
The synthesis of intermediate 5:
Compound 4 is synthesized according to document (R.Li, J.Liu, N.Cai, M.ZhangandP.Wang, J.Phys.Chem.B, 2010,114,4461.).
In the Schlenk reaction flask of drying, 500mg compound 4 and 218mg triisopropyl silico acetylene are dissolved in 20 milliliters of toluene, under argon gas shielded, add 67mgPd (PPh3)2Cl2, 18mg cuprous iodide and 2mL triethylamine. Reaction system reflux is spent the night.
After reacting completely, system temperature is down to room temperature, after adding 30mL distilled water, chloroform extraction three times, merging organic phase, organic phase anhydrous sodium sulfate drying, is filtered to remove siccative, concentrated filtrate, by ethyl acetate/petroleum ether (volume ratio 1/50) as developping agent column chromatography, obtain 520mg colourless viscous liquid intermediate 5, receipts rate 86%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that the intermediate 5 obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl3) ��: 7.32 (d, J=8.6Hz, 2H), 7.08 (d, J=8.6Hz, 4H), 6.87 (m, 6H), 3.99 (t, J=6.5Hz, 4H), 1.86 (m, 4H), 1.82 (m, 4H), 1.57 (m, 8H), 1.53 (s, 18H), 0.97 (m, 6H).
13CNMR(100MHz,CDCl3)��:157.58,150.60,141.69,134.53,128.59,121.06,117.10,116.18,109.59,90.13,70.01,33.31,31.04,27.46,24.30,20.40,15.70,13.15��
Mass spectrometry results: 626.43 ([M+H]+)��
Results of elemental analyses: C, 78.66; H, 9.50; N, 2.24.
The synthesis of intermediate 6:
In the Schlenk reaction flask of drying, 520mg compound 5 and 2.17g tetrabutyl ammonium fluoride are dissolved in 20mL methylene dichloride, room temperature reaction 4 hours. Chloroform extraction three times after reacting completely, merge organic phase, and organic phase anhydrous sodium sulfate drying, is filtered to remove siccative, concentrated filtrate, obtains colourless oil liquid and is directly used in the next step.
Colourless oil liquid obtained in the previous step is dissolved in toluene, adds compound 2 prepared by 495mg embodiment 1, under argon gas shielded, add 60mgPd (PPh3)2Cl2, 15mg cuprous iodide and 2mL triethylamine. Reaction system reflux is spent the night.
After reacting completely, system temperature is down to room temperature, after adding 30mL distilled water, chloroform extraction three times, merging organic phase, organic phase anhydrous sodium sulfate drying, is filtered to remove siccative, concentrated filtrate, by ethyl acetate/petroleum ether (volume ratio 1/20) as developping agent column chromatography, obtain 654mg colourless viscous liquid intermediate 6, receipts rate 80%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that the intermediate 6 obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d8) ��: 10.35 (s, 1H), 9.21 (d, J=8.3Hz, 1H), 8.58 (m, 2H), 8.42 (d, J=8.1Hz, 1H), 8.03 (s, 1H), 7.81 (m, 3H), 7.53 (d, J=8.6Hz, 2H), 7.11 (d, J=8.8Hz, 4H), 6.95 (d, J=8.6Hz, 2H), 6.89 (d, J=8.8Hz, 4H), 4.28 (d, J=7.4Hz, 2H), 3.95 (t, J=6.4Hz, 4H), 2.14 (m, 1H), 1.78 (m, 4H), 1.50 (m, 4H), 1.37 (m, 16H), 1.13 (m, 16H), 0.93 (m, 6H), 0.78 (m, 6H).
13CNMR(100MHz,THF-d8)��:192.84,157.52,150.39,141.03,135.27,133.44,132.44,130.86,130.77,130.70,129.95,128.28,127.78,127.55,126.21,125.30,125.11,124.36,123.10,122.40,121.40,119.89,117.56,117.03,116.34,115.11,96.63,88.93,68.96,50.60,40.78,32.92,32.87,32.75,30.97,30.70,30.55,30.47,30.34,27.40,26.92,23.20,23.62,14.58��
Mass spectrometry results: 985.62 ([M+H]+)��
Results of elemental analyses: C, 84.10; H, 8.18; N, 2.84.
The synthesis of target product III:
In two mouthfuls of round-bottomed flasks of drying, 654mg compound 6 is dissolved in the mixed solvent of acetonitrile and methylene dichloride (volume ratio 1/2), adds 564mg alpha-cyanoacrylate and 52mg ammonium acetate. Reaction system is heated to back flow reaction 48 hours.
After reacting completely, system temperature is down to room temperature, after adding 30mL distilled water, and chloroform extraction three times, merging organic phase, organic phase anhydrous sodium sulfate drying, is filtered to remove siccative, concentrated filtrate, with methyl alcohol/chloroform (volume ratio 1/20) as developping agent column chromatography, obtain target product III, it is dissolved in chloroform by III, repeatedly wash in turn with the aqueous hydrochloric acid of 0.2mol/L and distilled water, concentrated organic phase, drying under reduced pressure obtains 664mg blue solid target product II, receipts rate 95%.
Adopting nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method that compound shown in the formula III obtained is carried out structural characterization, nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d8) ��: 9.09 (s, 1H), 8.63 (s, 1H), 8.49 (d, J=7.7Hz, 1H), 8.43 (d, J=7.7Hz, 1H), 8.38 (d, J=8.1Hz, 1H), 8.06 (d, J=8.6Hz, 1H), 7.72 (m, 1H), 7.69 (m, 1H), 7.74 (s, 1H), 7.55 (d, J=8.7Hz, 2H), 7.12 (d, J=8.9Hz, 4H), 6.95 (d, J=8.7Hz, 2H), 6.89 (d, J=9.0Hz, 4H), 4.13 (d, J=7.5Hz, 2H), 3.95 (t, J=6.4Hz, 4H), 2.08 (m, 1H), 1.79 (m, 4H), 1.50 (m, 4H), 1.37 (m, 14H), 1.11 (m, 18H), 0.93 (m, 6H), 0.77 (m, 6H).
13CNMR(100MHz,THF-d8)��:165.01,157.48,151.44,150.33,141.05,135.30,133.52,132.38,131.86,130.52,129.87,129.52,128.25,126.66,126.21,125.43,125.25,124.45,124.14,123.08,122.11,121.55,121.48,121.42,119.95,118.04,117.36,116.84,116.33,116.10,115.20,101.43,96.88,89.06,68.96,50.64,40.85,32.93,32.82,32.75,30.95,30.78,30.70,30.49,30.47,30.36,27.48,27.44,26.92,23.70,23.63,14.61,14.59��
High resolution mass spectrum analytical results: 1051.62271.
Results of elemental analyses: C, 82.17; H, 7.76; N, 3.99.
Experimental result shows, the present invention has prepared compound shown in formula III.
Embodiment 3
Organic dye sensitized solar cell is prepared according to document (EnergyEnviron.Sci., 2010,3,1924), concrete:
Organic dye prepared by organic dye embodiment 1 prepared respectively and embodiment 2 is prepared into ethanol/chloroform (volume ratio 19:1) solution of 100 ��m of ol/L, is designated as solution A, solution B respectively.
By TiO2Structure duplicature electrode soaks 12 hours respectively in solution A and solution B, takes out electrode, will cover the molten ring sealing of glass electrode heat of nanometer platinum, and will finally be injected into by ionogen in the gap of two electrodes, namely constitute dye-sensitized solar cells.
At 100mWcm-2, under simulation AM1.5G sunlight, the dye-sensitized solar cells of preparation being carried out Performance Detection, test result is in table 1, and the performance test results that table 1 is the embodiment of the present invention 3 gathers.
The performance test results of table 1 embodiment of the present invention 3 gathers
Show, with organic dye sensitized solar cell prepared by organic dye provided by the invention, there is higher efficiency by above-described embodiment.
Illustrating just for helping the method understanding the present invention and core concept thereof of above embodiment. , it is also possible to the present invention carries out some improvement and modification, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (9)
1. taking phenanthrene and carbazole as an organic dye for core, there is structure shown in formula (1):
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0 or 1.
2. organic dye according to claim 1, it is characterised in that, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
3. organic dye according to claim 2, it is characterised in that, described organic dye has the concrete structure shown in formula II or formula III:
4. taking phenanthrene and carbazole as a preparation method for the organic dye of core, comprising:
By compound shown in formula IV and N, dinethylformamide and phosphorus oxychloride reaction, and then with triphenylamine boric ester derivative shown in formula (V), react under palladium, Sphos and potassiumphosphate effect, finally react under ammonium acetate effect with alpha-cyanoacrylate again, obtain the organic dye shown in formula (1);
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 0;
X is halogen.
5. preparation method according to claim 4, it is characterised in that, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
6. taking phenanthrene and carbazole as a preparation method for the organic dye of core, comprising:
By the triphenylamine derivative shown in formula VI and triisopropyl silico acetylene, at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, then with the reaction of tetrabutyl fluoride amine, then with compound shown in formula (VII), at Pd (PPh3)2Cl2, react under cuprous iodide and triethylamine effect, last and alpha-cyanoacrylate reacts under ammonium acetate effect, obtains the organic dye shown in formula (1);
Wherein,
R1It is selected from C1��C18Alkyl;
R2��R3Independent is selected from H, C1��C18Alkyl or C1��C18Any one in alkoxyl group;
Y is 1;
X is halogen.
7. preparation method according to claim 6, it is characterised in that, described R1It is selected from C10��C18Alkyl, R2��R3Independent is selected from H, C1��C12Alkyl or C1��C12Any one in alkoxyl group.
8. one kind taking phenanthrene and carbazole as the organic dye sensitized solar cell of core, it is characterised in that, dyestuff layer is the organic dye described in claims 1 to 3 any one, or organic dye prepared by the preparation method described in the arbitrary item of claim 4��7.
9. organic dye sensitized solar cell according to claim 8, it is characterised in that, described organic dye has the concrete structure shown in following formula II or formula III:
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| CN104987748B (en) * | 2015-07-29 | 2017-04-19 | 中国科学院长春应用化学研究所 | Organic dye, preparation method thereof and application thereof |
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