CN101255130B - Benzofluoranthene alkynes compounds and uses thereof - Google Patents
Benzofluoranthene alkynes compounds and uses thereof Download PDFInfo
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- CN101255130B CN101255130B CN2008100358514A CN200810035851A CN101255130B CN 101255130 B CN101255130 B CN 101255130B CN 2008100358514 A CN2008100358514 A CN 2008100358514A CN 200810035851 A CN200810035851 A CN 200810035851A CN 101255130 B CN101255130 B CN 101255130B
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Abstract
The invention relates to a series of benzo fluoranthene alkine compounds and the use thereof. The invention designs and synthesizes a new style of benzofluoranthene alkine compounds by proper chemical modification for the conjugated compound of benzofluoranthene, and the compounds are used as a sensitizer of dye sensitization nanocrystalline solar energy cells. Proved by experiment, the benzofluoranthene alkine compounds provided in the invention has a favorable sensitizing performance.
Description
Technical field
The present invention relates to a kind of Benzofluoranthene alkynes compounds and uses thereof.
Background technology
Dye-sensitized nano structure solar cell is the newcomer of solar cell family, and it is low with cost, manufacture craft simply reaches advantages such as efficiency of conversion height, has caused the extensive concern of scientists.
So far, the sensitizing agent that is used for dye sensitized nano crystal salar battery mainly is divided into two big classes: metal complex and nonmetal organic dye.Compare with metal complex, nonmetal organic dye has advantages such as the method for higher molar absorptivity, lower preparation cost, preparation and purification is comparatively simple and environmentally friendly.Developing novel nonmetal organic dye (being used for dye sensitized nano crystal salar battery) becomes the research focus of this area, also is the technical issues that need to address of the present invention simultaneously
Summary of the invention
Benzofluoranthrene is a kind of conjugated compound that is widely studied, and it is made up of two naphthalene nucleus of two singly-bound links, can be used as the hotchpotch of molecular crystal in the laser spectrum analyser.Characteristics such as benzofluoranthrene also has the fluorescence quantum efficiency height simultaneously, and chemically modified is strong have been used in material fields such as photochromic, organic electroluminescent.But, up to the present to the synthetic of the light-sensitive coloring agent that contains Benzofluoranthene alkynes and in the also unprecedented relevant report of the research of organic solar batteries application facet.
Given this, the present invention has designed and synthesized the novel Benzofluoranthene alkynes compounds of a class, and with its sensitizing agent as dye sensitized nano crystal salar battery.Experimental results show that: Benzofluoranthene alkynes compounds provided by the present invention has good sensitization performance.
The said Benzofluoranthene alkynes compounds of the present invention, it has structure shown in the formula I:
Among the formula I: Ar
1And Ar
2Be virtue (perfume (or spice)) cyclic group; X is selected from O, S, Se, CH
3CCH
3 
Or it is a kind of among the CH=CH; R
1Be selected from: by-(CH
2)
mCH
2A kind of in the represented substituting group of L, wherein: m is 0～30, and L is hydrogen (H), cyano group (CN), hydroxyl (OH) a, alkoxyl group or contain the alkyl of aromatic ring; R
2Be group shown in formula II, formula III, formula IV or the formula V:
Among the formula II: R
3Be alkyl, Y is halogen (F, Cl, Br or I).
In an optimal technical scheme of the present invention: Ar
1And Ar
2Be selected from C respectively
6～C
20Virtue (perfume (or spice)) cyclic group in a kind of; Preferred Ar
1And Ar
2Be selected from C respectively
6～C
10Virtue (perfume (or spice)) cyclic group in a kind of; Best Ar
1Be phenyl, best Ar
2Be " trivalent " naphthyl shown in the formula VI:
Curve representation among the formula VI replaces the position.
In another optimal technical scheme of the present invention: X is O, S or CH
3CCH
3 
Best X is CH
3CCH
3
In another optimal technical scheme of the present invention: R
1Be selected from: by-(CH
2)
mCH
2A kind of in the represented substituting group of L, wherein: m is 0～19, L be hydrogen (H) or hydroxyl (OH); Preferred m is 0～5.
In another optimal technical scheme of the present invention: R
2Be group shown in formula II, formula III or the formula IV, wherein, R
3Be C
1～C
6Alkyl, Y are Cl, Br or I.
Benzofluoranthene alkynes compounds provided by the invention (compound shown in the formula I) can be used as the sensitizing agent of dye sensitized nano crystal salar battery.
Description of drawings:
Fig. 1 is a Compound I-1 at methylene dichloride: (concentration of Compound I-1 is 1 * 10 to the uv-absorbing spectrogram in ethanol=1: 1 solution
-5Mol);
Fig. 2 is that Compound I-1 is adsorbed on the uv-absorbing spectrogram on the titanium dioxide electrodes;
Fig. 3 is with the dye sensitization solar battery I-V graphic representation of Compound I-1 as sensitizing agent.
Embodiment
Prepare Benzofluoranthene alkynes compounds of the present invention (compound shown in the formula I), its main synthetic route is as follows:
Wherein: Ar
1, Ar
2And R
1Implication described identical with preamble, specifically comprise the steps:
1, the back flow reaction in dimethylbenzene with compd A and compd B, reaction solution adds sherwood oil through cold after really again, filters, and the gained solid is a Compound C;
2, with Compound C back flow reaction in containing the dichloromethane solution of trifluoroacetic acid, reaction solution collecting precipitation thing after cooling off promptly gets Compound D;
3, with Compound D and compd E by Sonogashira react compound F 17-hydroxy-corticosterone;
The wherein preparation of compd E is with Ar
2For the group shown in the formula VI (" trivalent " naphthyl) is an example, its synthetic route is as follows:
Wherein: X, Y and R
1Implication described identical with preamble.Its key step is as follows:
(3-1) with compd E-1 and haloalkane (R
1Y) refluxed about 20 hours in acetonitrile, reaction solution has solids to separate out after cooling, filters, and the gained solids is a compd E-2;
(3-2) with compd E-2, aqueous sodium hydroxide solution and toluene stir about 2 hours under room temperature, filter, filtrate places separating funnel, removes water, organic phase after washing, drying and steaming desolventize compd E-3;
(3-3) under the condition that is lower than 15 ℃ (preferred 10 ℃～15 ℃), compd E-3 is joined in the mixture of being made up of phosphorus oxychloride and aprotic polar solvent (as DMF), 15 ℃～40 ℃ reactions at least 30 minutes.This reaction solution is poured in the mixture of ice and water, and reconciling its pH value is 8～11, uses extracted with diethyl ether, organic phase (ether layer) drying of extraction gained, steam desolventize and purify (silicagel column is purified, and haloalkane is an eluent) after compd E-4;
(3-4) having under protection of inert gas and the condition of ice bath, compd E-4, trimethyl silicane ethyl-acetylene, triphenyl phosphorus, two (triphenyl phosphorus) palladium chloride and cuprous iodide are being joined in the triethylamine, refluxing then about 10 hours.Steaming desolventizes, and extracts the gained resistates with haloalkane, and extraction gained organic phase drying, steaming get compd E-5 after removing extraction agent and purification (silicagel column purification, eluent are the miscellany of haloalkane and ethyl acetate);
(3-5) having under the protection of inert gas condition; with compd E-5, carbonate (salt of wormwood or yellow soda ash) and aliphatic monobasic alcohol; stirred 4～10 hours at 20 ℃～50 ℃; steaming desolventizes; extract the gained resistates with haloalkane, extraction gained organic phase drying, steaming get compd E-6 after removing extraction agent and purification (silicagel column purification, eluent are the miscellany of haloalkane and ethyl acetate).
According to the instruction of aforesaid method [step (3-1)～(3-5)], those of ordinary skill in the art need not creative work and can prepare and work as Ar
2Compd E during for other virtue (perfume (or spice)) cyclic group.
4, with compound F 17-hydroxy-corticosterone and reagent corresponding (as indoles halogen, cyanoacetic acid or rhodanine acid etc.) reaction, can obtain target compound (Compound I).
The preparation of the starting raw material (compd A and compd B) that the present invention is used is referring to (Mitchell, R.H, J.Org.Chem, 44,1979,4733-4735; Mitchell, Reginald H, Can, J.Chem, 70,4,1992,1015-1021; Benderradji, Farah, Syn.Lett, 13,2006,2035-2038.), other used reagent is commercially available product.
Preparation is the method for the dye sensitized nano crystal salar battery device of sensitizing agent with Benzofluoranthene alkynes compounds of the present invention (compound shown in the formula I), comprises the steps:
A, with after the nano titanium oxide heated by electrodes to 80 that bakes ℃, be mixed with by Compound I, concentration is 3 * 10
-4Soak sensitization in the acetonitrile solution of mol after 12 hours, rinse out the dyestuff of not absorption and dry up with dehydrated alcohol;
B, dripping a LiI/I through the photoanode surface of processing of step A
2Redox electrolytes matter solution, then the platinized ITO conductive glass of a slice conducting surface is put in TiO down
2On the film, use clamp, coat the HY-914 resin all around, promptly constitute the sandwich-like dye sensitization solar battery.
The present invention is further elaborated below by embodiment, and purpose is better to understand content of the present invention, and therefore, the cited case should not be considered as limiting the scope of the invention.In addition, the compound that does not provide concrete synthetic method in an embodiment is that the synthetic method that provides by previously described existing document or supplier is synthetic.
Embodiment 1
6g compound 1 refluxed 24 hours in 50mL dimethylbenzene with 3.7g compound 2, and adding 250mL sherwood oil filters faint yellow needle-like solid (compound 3), not purifiedly after the drying directly entered next step reaction.
10.3g (20.5mmol) compound 3 refluxed 18 hours in the dichloromethane solution (50mL) of trifluoroacetic acid (5mL), filtered yellow mercury oxide and promptly got product 4.2g (compound 4) yield 44.5%.
1H-NMR(CDCl
3，400MHz)，δ：7.88(d，J＝8.0Hz，1H)，7.67(m，8H)，7.55(m，5H)，7.40(m，3H)，6.62(d，J＝6.8Hz，1H)，6.40(d，J＝7.6Hz，1H)。
10g (37.4mmol) 7-bromo-1,1,2-trimethylammonium-1H-benzo [e] indoles, the mixture heating up of 19.16g (0.1mol) butyl iodide and 30mL acetonitrile refluxed 20 hours, became mazarine liquid gradually.Then reaction mixture is cooled to room temperature, in refrigerator overnight, separate out a large amount of solids, filter the solid of separating out, wash with ethyl acetate, blue solid is washed light gray gradually, dried overnight in vacuum drier obtains 14g pink solid (7-bromo-3-butyl-1,1,2-dimethyl-1H-benzo [e] indoles salt compounded of iodine), yield is 85%.
In the 250mL there-necked flask, 6g (12.7mmol) 7-bromo-3-butyl-1,1,2-dimethyl-1H-benzo [e] indoles salt compounded of iodine is dissolved in the 35mL toluene, adds the aqueous sodium hydroxide solution of 50mL 0.8mol/L again, at room temperature stirred 2 hours fast with mechanical stirring, filter, behind the elimination impurity, solution is put into separating funnel, tell organic layer, wash with water 3 times.Organic layer is spent the night with anhydrous magnesium sulfate drying, and the rotation solvent evaporated obtains the brown heavy-gravity liquid of 4.21g, and yield is 96.5%, need not purifying and is directly used in next step reaction.
Under the ice bath cooling, use magnetic agitation, in 10mL DMF, drip 2.98g (19.4mmol) phosphorus oxychloride, the control rate of addition makes temperature remain on 10～15 ℃, Dropwise 5 .85g (16.2mmol) 7-bromo-3-butyl-2-methylene radical-1 under uniform temp then, the 10mL dimethyl formamide solution of 1-dimethylbiphenyl [e] indoline.After dropwising, continue reaction 40 minutes at 35 ℃.After the reaction mixture cooling, under agitation pour in the 100g mixture of ice and water,, use extracted with diethyl ether three times with pH value to 10～11 of saturated sodium hydroxide solution adjusting mixture.The ether layer anhydrous magnesium sulfate drying, the rotary evaporation solvent is purified the solid that obtains with silicagel column, with the methylene dichloride is eluent, obtains 3.81g product [2-(7-bromo-3-butyl-1,1-dimethyl-1H-benzo [e] indoline-2-subunit) acetaldehyde], yield 63%, m.p.110～110 ℃.
1H-NMR(CDCl
3，500MHz)，δ：10.13(d，J＝8.87Hz，1H)，8.02(s，1H)，7.94(d，J＝9.1Hz，1H)，7.73(d，J＝8.7Hz，1H)，7.57(d，J＝9.0Hz，1H)，7.18(d，J＝8.7Hz，1H)，5.45(d，J＝8.8Hz，1H)，3.76(t，J＝7.7Hz，2H)，1.96(s，6H)，1.73(m，2H)，1.45(m，2H)，0.98(t，J＝7.4Hz，3H)。
0.82g (2.2mmol) 2-(7-bromo-3-butyl-1,1-dimethyl-1H-benzo [e] indoline-2-subunit) acetaldehyde, 0.43g (4.4mmol) trimethyl silicane ethyl-acetylene, 5.7mg (0.022mmol) triphenyl phosphorus, 21.2mg (0.022mmol) two (triphenyl phosphorus) palladium chlorides and 6.8mg (0.044mmol) cuprous iodide join in the 10mL triethylamine.Under condition of ice bath, carry out nitrogen protection.After finishing, reflux 10 hours.After solvent is spin-dried for Rotary Evaporators, resistates methylene dichloride, the extraction of washing dichloromethane layer.Organic phase is spent the night with anhydrous magnesium sulfate drying.After the methylene dichloride removal, solid is purified with silicagel column, and eluent is dichloromethane/ethyl acetate=10/1, obtains 0.83g brown oil [2-{7-[2-(trimethyl silicon based) ethynyl]-3-butyl-1,1-dimethyl-1H-benzo [e] indoline-2-subunit } acetaldehyde], yield 98%.
1H-NMR(CDCl
3，500MHz)，δ：10.13(d，J＝8.9Hz，1H)，8.07(s，1H)，7.90(d，J＝8.8Hz，1H)，7.63(d，J＝8.7Hz，1H)，7.52(d，J＝8.8Hz，1H)，7.14(d，J＝8.7Hz，1H)，5.46(d，J＝8.9Hz，1H)，3.75(t，J＝7.8Hz，2H)，1.96(s，6H)，1.70(m，2H)，1.46(m，2H)，0.97(t，J＝7.3Hz，3H)，0.26(s，9H)。
In the 50mL single necked round bottom flask, 0.91g (2.34mmol) 2-{7-[2-(trimethyl silicon based) ethynyl]-3-butyl-1,1-dimethyl-1H-benzo [e] indoline-2-subunit } acetaldehyde and 0.03g (0.0234mmol) salt of wormwood joins in the 20mL methyl alcohol.After the argon shield, mixture stirred 4 hours down at 40 ℃.Remove solvent with Rotary Evaporators, resistates methylene dichloride, the extraction of washing dichloromethane layer.Organic layer spends the night with anhydrous magnesium sulfate drying.Purify with silicagel column revolving the solid that obtains after the steaming, dichloromethane/ethyl acetate=10/1 is an eluent.Obtain 0.6g solid [2-(7-ethynyl-3-butyl-1,1-dimethyl-1H-benzo [e] indoline-2-subunit) acetaldehyde], yield 80%, m.p.128～130 ℃.
1H-NMR(CDCl
3，500MHz)，δ：10.15(d，J＝8.4Hz，1H)，8.14(s，1H)，7.98(d，J＝8.9Hz，1H)，7.79(d，J＝8.7Hz，1H)，7.55(d，J＝9.0Hz，1H)，7.18(d，J＝8.7Hz，1H)，5.46(d，J＝8.9Hz，1H)，3.67(t，J＝7.8Hz，2H)，3.18(s，1H)，1.96(s，6H)，1.73(m，2H)，1.44(m，2H)，0.98(t，J＝7.3Hz，3H)。
In the 100mL single necked round bottom flask; 0.86g (1.8mmol) compound 4; 0.47g (1.5mmol) 2-(7-ethynyl-3-butyl-1; 1-dimethyl-1H-benzo [e] indoline-2-subunit) acetaldehyde; 5.7mg (0.022mmol) triphenyl phosphorus; 21.2mg (0.022mmol) two (triphenyl phosphorus) palladium chlorides and 6.8mg (0.044mmol) cuprous iodide join in the mixed solvent of 30mL triethylamine and 30mL tetrahydrofuran (THF), under the argon shield, and reflux 24 hours.After solvent was spin-dried for Rotary Evaporators, resistates was with methylene dichloride and water extraction.Organic phase is spent the night with anhydrous magnesium sulfate drying.After the methylene dichloride removal, solid is purified with silicagel column, and eluent is dichloromethane/ethyl acetate=10/1, obtains 0.3g yellow solid (compound 5), yield 28%.
1H-NMR(CDCl
3，400MHz)，δ：10.12(d，J＝8.8Hz，1H)，8.15(m，2H)，8.05(d，J＝9.2Hz，1H)，7.85(d，J＝8.8Hz，1H)，7.68(m，8H)，7.58(m，5H)，7.55(d，J＝8.8Hz，1H)，7.45(m，3H)，7.20(d，J＝8.8Hz，1H)，6.65(d，J＝6.8Hz，1H)，6.60(d，J＝7.6Hz，1H)，5.55(d，J＝8.8Hz，1H)，3.80(t，J＝8.0Hz，2H)，2.00(s，6H)，1.75(m，2H)，1.45(m，2H)，1.00(t，J＝7.2Hz，3H)。
In the 25mL single necked round bottom flask, 100mg (0.14mmol) compound 5 and 53.82mg (0.14mmol) indoles salt compounded of iodine are joined in the 8mL acetic anhydride, control oil bath temperature at 100～110 ℃, stirring reaction 1 hour.Reaction mixture pours in the 50mL water.Solution in stirring at room, is precipitated in a large number up to appearance.Solid is leached, with twice of 10mL water washing.Crude product is purified with silicagel column, and eluent is DMF/ ethanol=50/1, obtains 106mg purple solid (Compound I-1), productive rate 70%.
1H-NMR(CDCl
3，400MHz)，δ：8.52(m，1H)，8.15(m，2H)，8.05(m，2H)，7.85(m，3H)，7.65(m，8H)，7.50(m，5H)，7.40(m，4H)，7.20(d，J＝8.8Hz，1H)，7.15(d，J＝8.8Hz，1H)，7.05(s，1H)，6.65(d，J＝6.8Hz，1H)，6.60(d，J＝7.6Hz，1H)，4.35(t，J＝6.9Hz，2H)，4.25(t，J＝6.7Hz，2H)，2.00(s，6H)，1.88(m，4H)，1.75(s，6H)，1.55(m，4H)，1.00(m，6H)。
Compound I-1 is at methylene dichloride: the uv-absorbing spectrogram in ethanol=1: 1 solution sees that (concentration of Compound I-1 is 1 * 10 to Fig. 1
-5Mol);
The uv-absorbing spectrogram that Compound I-1 is adsorbed on the titanium dioxide electrodes is seen Fig. 2.
Embodiment 2
In the there-necked flask of 50mL; add 0.14g (0.19mmol) compound 5; cyanoacetic acid 0.081g (0.95mmol); add tetrahydrofuran (THF) 25mL; and drip two piperidines and make catalyzer, the argon shield back flow reaction is spent the night, and reaction stops the back being spin-dried for solvent with Rotary Evaporators after; the resistates methylene dichloride, the extraction of washing dichloromethane layer.Organic phase is spent the night with anhydrous magnesium sulfate drying.After the methylene dichloride removal, solid is purified with silicagel column, and eluent is a trichloromethane, obtains 0.068g yellow solid (Compound I-2), yield 40%.
1H-NMR(CDCl
3，400MHz)，δ：8.23(m，2H)，8.12(m，1H)，7.82(m，1H)，7.65(m，8H)，7.49(m，5H)，7.37(m，4H)，7.24(d，J＝8.8Hz，1H)，7.17(d，J＝8.8Hz，1H)，7.05(s，1H)，6.64(d，J＝6.8Hz，1H)，6.59(d，J＝7.6Hz，1H)，4.28(t，J＝6.7Hz，2H)，2.03(s，6H)，1.84(m，2H)，1.53(m，2H)，1.02(m，3H)。
Embodiment 3
In the 25mL single necked round bottom flask, add 143.8mg (0.20mmol) compound 5, rhodanine acid 47.8mg (0.25mmol), ammonium acetate 50mg, acetic acid 8mL, reflux 6 hours, be spin-dried for solution after the cooling, resistates is purified with silicagel column, and eluent is that post is crossed in methylene dichloride/ethanol=20/1, obtain 76.0mg product (Compound I-3), yield 30%.
1H-NMR(CDCl
3，400MHz)，δ：8.17(m，2H)，8.08(m，1H)，7.89(m，1H)，7.63(m，8H)，7.50(m，5H)，7.40(m，4H)，7.20(d，J＝8.8Hz，1H)，7.15(d，J＝8.8Hz，1H)，7.05(s，1H)，6.65(d，J＝6.8Hz，1H)，6.60(d，J＝7.6Hz，1H)，4.38(s，2H)4.26(t，J＝6.7Hz，2H)，2.03(s，6H)，1.84(m，2H)，1.57(m，2H)，1.05(m，3H)。
Embodiment 4
In the 250mL there-necked flask, add the different Fu Er ketone of 15g, 11.3g ethyl cyanacetate, 1.54g ammonium acetate, 6mL acetic acid and 50mL toluene respectively, back flow reaction 18h under the argon shield.Reactant is poured in the 200mL water, fully stirs the back separatory, and 155-160 ℃ of cut got in underpressure distillation after the organic layer drying, obtains 17.3g deep yellow thick liquid (compound 6), productive rate 74%.
In the 50mL there-necked flask, add 58.25mg (0.25mmol) compound 6 respectively, 143.8mg (0.2mmol) compound 5,15mL acetonitrile and 1mL piperidines, back flow reaction 12h under the argon shield.Need not purify after reaction solution is spin-dried for, add 30mL ethanol, abundant dissolving back adds the 4.92g one hydronium(ion) oxidation lithium that is dissolved in the 30mL deionized water, and 50 ℃ are reacted 8h down.Reaction finishes the back and is neutralized to acidity with 1M HCl, and filter and obtain solid, chloroform: normal hexane=recrystallization obtained Compound I-4 in 1: 2, productive rate 73%.
1H-NMR(CDCl
3，400MHz)，δ：8.17(m，2H)，8.08(m，1H)，7.89(m，1H)，7.63(m，8H)，7.50(m，5H)，7.40(m，4H)，7.20(d，J＝8.8Hz，1H)，7.15(d，J＝8.8Hz，1H)，7.05(s，1H)，6.88(d，J＝16.0Hz，1H)，6.82-6.79(dd，J＝3.2Hz，J＝8.0Hz，1H)6.65(d，J＝6.8Hz，1H)，6.60(d，J＝7.6Hz，1H)，4.38(s，2H)4.26(t，J＝6.7Hz，2H)，2.68(s，1H)，2.45(s，1H)，2.03(s，6H)，1.84(m，2H)，1.57(m，2H)，1.09(s，3H)，1.06(s，3H)，1.01(m，3H)。
The present invention is said to contain the photosensitizers that the compound shown in the Benzofluoranthene alkynes sensitizing agent formula I-1 can be used as dye sensitization solar battery, makes the dye sensitization solar battery device with Compound I-1 as photosensitizers:
With after the nano titanium oxide heated by electrodes to 80 that bakes ℃, Compound I-1 be mixed with 3 * 10
-4Soak sensitization 12 hours in the mol acetonitrile solution.Sensitization is taken out after finishing, and rinses out the not dyestuff of absorption with dehydrated alcohol, dries up.Drip a LiI/I at the dye sensitization photoanode surface
2Redox electrolytes matter solution, the platinized ITO conductive glass of a slice conducting surface is swept away be put in TiO then
2On the film, use clamp, coat the HY-914 resin all around, promptly constitute the sandwich-like dye sensitization solar battery.Measuring its open circuit voltage under the irradiation of 750W xenon source is 0.54V, and short-circuit current is 19.53mAcm
-2, packing factor is 0.58, electricity conversion is 8.14%.Its photoelectric current and photovoltage curve are seen Fig. 3.
Claims (5)
1. Benzofluoranthene alkynes compounds, it has structure shown in the formula I:
Among the formula I: Ar
1And Ar
2Be selected from C respectively
6～C
10Aromatic ring yl in a kind of; X is CH
3CCH
3R
1Be selected from: by-(CH
2)
mCH
2A kind of in the represented substituting group of L, wherein m is 0～5, and L is a hydrogen; R
2Be group shown in formula II, formula III, formula IV or the formula V:
Among the formula II: R
3Be C
1～C
6Alkyl, Y are halogen.
2. Benzofluoranthene alkynes compounds as claimed in claim 1 is characterized in that, wherein Ar
1Be phenyl.
3. Benzofluoranthene alkynes compounds as claimed in claim 1 is characterized in that, wherein Ar
2Be the naphthyl shown in the formula VI:
Curve representation among the formula VI replaces the position.
4. Benzofluoranthene alkynes compounds as claimed in claim 1 is characterized in that, wherein R
2Be group shown in formula II, formula III or the formula IV, wherein, R
3Be C
1～C
6Alkyl, Y are Cl, Br or I.
As any described Benzofluoranthene alkynes compounds in the claim 1～4 as the sensitizing agent of dye sensitized nano crystal salar battery.
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| CN101255130B true CN101255130B (en) | 2010-06-02 |
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| Wen-hai Zhan, et al..Photovoltaic properties of new cyanine-naphthalimidedyadssynthesized by ‘Click’ chemistry.Tetr. Lett.48 14.2007,48(14),2461-2465. * |
| Wenjun Wu,et al..Photovoltaic properties of three new cyanine dyes for dye-sensitized solar cells.Photochem. Photobiol. Sci.7 1.2007,7(1),63-68. |
| Wenjun Wu,et al..Photovoltaic properties of three new cyanine dyes for dye-sensitized solar cells.Photochem. Photobiol. Sci.7 1.2007,7(1),63-68. * |
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| Yinghua Jin,et al..Synthesis, characterization and photovoltaic properties of twonovel near-infrared absorbing perylene dyes containingbenzo[e]indole for dye-sensitized solar cells.Synthetic Metals158 1-2.2008,158(1-2),64-71. * |
| YinghuaJin et al..Synthesis |
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