CN104610775A - Phenanthro-carbazole dye and preparation method thereof, as well as dye-sensitized solar cell - Google Patents

Phenanthro-carbazole dye and preparation method thereof, as well as dye-sensitized solar cell Download PDF

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CN104610775A
CN104610775A CN201510018781.1A CN201510018781A CN104610775A CN 104610775 A CN104610775 A CN 104610775A CN 201510018781 A CN201510018781 A CN 201510018781A CN 104610775 A CN104610775 A CN 104610775A
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carbonatoms
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CN104610775B (en
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王鹏
姚朝阳
张敏
李仁志
马文涛
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention provides phenanthro-carbazole dye which has a structure represented as the formula I. In the formula I, R1 is selected from an alkyl group with the carbon atom number ranging from 1 to 36; R2 and R3 are independently selected from hydrogen, fluorine and the alkyl group with the carbon atom number ranging from 1 to 36; R4 is selected from a carbonyl-substituted aryl group; R5 is selected from hydrogen, the aryl group or the alkyl group with the carbon atom number ranging from 1 to 36. The invention provides a preparation method of the phenanthro-carbazole dye. The preparation method comprises steps as follows: a compound with a structure represented as the formula I and a compound with a structure represented as the formula II have a coupling reaction, and the phenanthro-carbazole dye is obtained. The invention provides a dye-sensitized solar cell which comprises the phenanthro-carbazole dye provided by the technical scheme. The provided phenanthro-carbazole dye has electron donor unit phenanthro-carbazole; a phenanthro-carbazole structure unit has high fluorescence quantum yield and long excited state lifetime; the dye-sensitized solar cell prepared from the phenanthro-carbazole dye has higher power conversion efficiency.

Description

A kind of phenanthro-carbazoles dye well its preparation method and dye-sensitized solar cells
Technical field
The present invention relates to technical field of solar cells, particularly relate to a kind of phenanthro-carbazoles dye well its preparation method and dye-sensitized solar cells.
Background technology
In recent years, along with the develop rapidly of China's economy, also day by day increase the demand of the energy, China has become first energy importation state in the world; Meanwhile, the environmental problem brought by the energy consumption of ore class is also serious gradually, therefore seeks the clean continuable energy very necessary.Sun power, as a kind of renewable and clean energy resource, becomes one of the focus in energy research field.
At present, inorganic semiconductor solar cell can realize higher photoelectric transformation efficiency and be widely used in the every field of national product.In inorganic semiconductor solar cell, the technical development of crystal-silicon solar cell is the most ripe, but the manufacturing cost of silion cell is high, processing condition are harsh, and can cause serious environmental pollution in refining silicon process.Subsequently, people have developed the solar cell of other material, as gallium arsenide III-V, Cadmium Sulfide and cadmium telluride thin-film battery etc., although comparatively amorphous silicon film solar battery efficiency is high for the efficiency of these batteries, also comparatively monocrystalline silicon battery is low for cost, and be also easy to scale operation, but arsenic wherein, cadmium etc. there is severe toxicity, also can cause serious pollution to environment.Therefore, inorganic semiconductor solar cell is not desirable solar cell.
1991, the three core ruthenium dye RuL that the people such as Amadelli reported by study group 2(μ-(CN) Ru (CN) L ' 2) 2(L=2,2 '-dipyridyl-4,4 '-dicarboxylic acid, L '=2,2 '-dipyridyl) is adsorbed on high-quality TiO as sensitizing agent 2nano-crystal thin-film makes device, obtains the solar cell of the photoelectric transformation efficiency of under simulated solar irradiation 7.1%, the research prelude of Open from This Side dye-sensitized solar cells.Compared with traditional inorganic semiconductor solar cell, the manufacturing cost of dye-sensitized solar cells is lower, lighter in weight, can fold, curling, and various colors, attractive in appearance, can be made into translucent product, can be widely used in daily life.
The dyestuff that the high efficiency dye sensitization solar cell of current report adopts mostly is the title complex containing noble ruthenium, and China's ruthenium resource shortage, studies nonmetal organic dye even more important; But the power-conversion efficiencies of the dye-sensitized cell that existing nonmetal organic dye prepares is lower, is difficult to meet practical application.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of phenanthro-carbazoles dye well its preparation method and dye-sensitized solar cells, the dye-sensitized solar cells that phenanthro-carbazoles preparation of dyestuff provided by the invention obtains has higher power-conversion efficiencies.
The invention provides a kind of phenanthro-carbazoles dyestuff, there is the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
Preferably, the R in described formula I 1be selected from the alkyl that carbonatoms is 2 ~ 18;
R 2and R 3the phenyl replaced independently selected from hydrogen, carbonatoms be 2 ~ 18 alkyl, the carbonatoms alkyl that is 2 ~ 18 or carbonatoms are the phenyl that replaces of alkoxyl group of 2 ~ 18.
Preferably, the R in described formula I 4be selected from the one in formula A ~ formula C:
Preferably, the R in described formula I 5be selected from the one in formula D ~ formula H:
R in formula D 6, and the R in formula H 12, R 13independently selected from hydrogen, carbonatoms be 1 ~ 36 alkyl or carbonatoms be the alkoxyl group of 1 ~ 36;
R in formula E 7, R 8, the R in formula F 9, and the R in formula G 10, R 11be the alkyl of 1 ~ 36 independently selected from hydrogen or carbonatoms;
Y in formula D 1, y in formula E 2, y in formula F 3with the y in formula H 4independently selected from 0 or 1.
Preferably, described phenanthro-carbazoles dyestuff has the structure shown in formula II or formula III:
Phenanthro-carbazoles dyestuff provided by the invention adopts donor monomer phenanthro-carbazole and is subject to body unit aryne and the chromophoric group of thiadiazoles formation dyestuff, be aided with the relative energy-level of different modification group Molecular regulators, phenanthro-carbazole structure unit has high-fluorescence quantum yield and long lifetime of excited state, make this dyestuff provided by the invention have longer lifetime of excited state, thus provide space for the further contraction of its energy gap and the further lifting of device efficiency; Therefore the dye-sensitized solar cells that phenanthro-carbazoles preparation of dyestuff provided by the invention obtains has higher power-conversion efficiencies.
The invention provides a kind of preparation method of phenanthro-carbazoles dyestuff, comprising:
The compound with structure shown in formula 1 is carried out linked reaction with the compound with structure shown in formula 2, obtains phenanthro-carbazoles dyestuff;
In formula 1, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36;
In formula 2, R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 14be selected from the aryl that ester group replaces;
Described phenanthro-carbazoles dyestuff has the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
Preferably, the preparation method described in the compound of structure shown in formula 1 is:
The compound with structure shown in formula 4 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1;
In formula 4, R 15be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
Preferably, the preparation method described in the compound of structure shown in formula 1 is:
The compound with structure shown in formula 6 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1;
In formula 6, R 16be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
Preferably, the temperature of described linked reaction is 110 DEG C ~ 130 DEG C.
The phenanthro-carbazoles dyestuff that method provided by the invention prepares has longer lifetime of excited state, and the dye-sensitized solar cells adopting this preparation of dyestuff to obtain has higher power-conversion efficiencies.In addition, preparation method's technique of phenanthro-carbazoles dyestuff provided by the invention is simple, cost is lower, safety and environmental protection.
The invention provides a kind of dye-sensitized solar cells, comprise the phenanthro-carbazoles dyestuff described in technique scheme, or the phenanthro-carbazoles dyestuff that the method described in technique scheme prepares.
Dyestuff in dye-sensitized solar cells provided by the invention is the phenanthro-carbazoles dyestuff described in technique scheme, and this dyestuff has longer lifetime of excited state, thus makes dye-sensitized solar cells provided by the invention have higher power-conversion efficiencies.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the J-V curve of the dye-sensitized solar cells that the embodiment of the present invention 3 prepares.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of phenanthro-carbazoles dyestuff, there is the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
In an embodiment of the present invention, the R in described formula I 1the alkyl that carbonatoms is 2 ~ 18 can be selected from; In other examples, the R in described formula I 1the alkyl that carbonatoms is 5 ~ 10 can be selected from.In an embodiment of the present invention, R in described formula I 2and R 3alkyl, the carbonatoms that can be 2 ~ 18 independently selected from carbonatoms be 2 ~ 18 the phenyl that replaces of alkyl or carbonatoms be 2 ~ 18 the phenyl that replaces of alkoxyl group; In other examples, R in described formula I 2and R 3alkyl, the carbonatoms that can be 5 ~ 10 independently selected from carbonatoms be 5 ~ 10 the phenyl that replaces of alkyl or carbonatoms be 5 ~ 10 the phenyl that replaces of alkoxyl group.In a preferred embodiment of the invention, the R in described formula I 2and R 3be selected from hydrogen.
In an embodiment of the present invention, the R in described formula I 4the one in formula A ~ formula C can be selected from:
In a preferred embodiment of the invention, the R in described formula I 4be selected from formula A.
In an embodiment of the present invention, the R in described formula I 5be selected from aryl; In a preferred embodiment of the invention, the R in described formula I 5be selected from the one in formula D ~ formula H:
R in described formula D 6, and the R in formula H 12, R 13independently selected from hydrogen, carbonatoms be 1 ~ 36 alkyl or carbonatoms be the alkoxyl group of 1 ~ 36;
R in formula E 7, R 8, the R in formula F 9, and the R in formula G 10, R 11be the alkyl of 1 ~ 36 independently selected from hydrogen or carbonatoms;
Y in formula D 1, y in formula E 2, y in formula F 3with the y in formula H 4independently selected from 0 or 1.
In a preferred embodiment of the invention, the R in described formula I 5formula D or formula G can be selected from.In an embodiment of the present invention, the R in described formula D 6, and the R in formula H 12, R 13can independently selected from carbonatoms be 2 ~ 18 alkyl or carbonatoms be the alkoxyl group of 2 ~ 18; In other examples, the R in described formula D 6, and the R in formula H 12, R 13can independently selected from carbonatoms be 5 ~ 10 alkyl or carbonatoms be the alkoxyl group of 5 ~ 10; In a preferred embodiment of the invention, the R in described formula D 6, and the R in formula H 12, R 13can be the alkoxyl group of 1 ~ 36 independently selected from carbonatoms.In an embodiment of the present invention, the R in described formula E 7, R 8, the R in formula F 9, and the R in formula G 10, R 11can be the alkyl of 2 ~ 18 independently selected from carbonatoms; In other examples, the R in described formula E 7, R 8, the R in formula F 9, and the R in formula G 10, R 11can be the alkyl of 5 ~ 10 independently selected from carbonatoms.In a preferred embodiment of the invention, the y in described formula D 1, y in formula E 2, y in formula F 3with the y in formula H 4can independently selected from 0.
In a preferred embodiment of the invention, described phenanthro-carbazoles dyestuff has the structure shown in formula II or formula III:
Phenanthro-carbazoles dyestuff provided by the invention adopts donor monomer phenanthro-carbazole and is subject to body unit aryne and the chromophoric group of thiadiazoles formation dyestuff, be aided with the relative energy-level of different modification group Molecular regulators, phenanthro-carbazole structure unit has high-fluorescence quantum yield and long lifetime of excited state, make this dyestuff provided by the invention have longer lifetime of excited state, thus provide space for the further contraction of its energy gap and the further lifting of device efficiency; Therefore the dye-sensitized solar cells that phenanthro-carbazoles preparation of dyestuff provided by the invention obtains has higher power-conversion efficiencies.
The invention provides a kind of preparation method of phenanthro-carbazoles dyestuff, comprising:
The compound with structure shown in formula 1 is carried out linked reaction with the compound with structure shown in formula 2, obtains phenanthro-carbazoles dyestuff;
In formula 1, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36;
In formula 2, R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 14be selected from the aryl that ester group replaces;
Described phenanthro-carbazoles dyestuff has the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
The linked reaction that the compound with structure shown in formula 1 and the compound with structure described in formula 2 carry out is designated as the first reaction by the present invention.In an embodiment of the present invention, described first reaction can be carried out under the condition of anaerobic and protective gas.In an embodiment of the present invention, described protective gas can be argon gas.In an embodiment of the present invention, described first reaction can be carried out in a solvent.In an embodiment of the present invention, described solvent can be selected from Isosorbide-5-Nitrae-dioxane aqueous solution.In an embodiment of the present invention, the mass concentration of described Isosorbide-5-Nitrae-dioxane aqueous solution can be 80% ~ 85%.
In an embodiment of the present invention, described first reaction can be carried out in the presence of a catalyst.In an embodiment of the present invention, the catalyzer of described first reaction comprises cesium carbonate, three (dibenzalacetone) two palladium and tri-tert phosphorus (P (t-Bu) 3).In an embodiment of the present invention, described cesium carbonate, three (dibenzalacetone) two palladium and tri-tert phosphorus (P (t-Bu) 3) mass ratio can be (20 ~ 30): (1.5 ~ 2): 1; In other examples, described cesium carbonate, three (dibenzalacetone) two palladium and tri-tert phosphorus (P (t-Bu) 3) mass ratio can be (24 ~ 28): (1.6 ~ 1.8): 1.
In an embodiment of the present invention, the temperature of described first reaction can be 110 DEG C ~ 130 DEG C; In other examples, the temperature of described first reaction can be 115 DEG C ~ 125 DEG C.In an embodiment of the present invention, the time of described first reaction can be 20 hours ~ 30 hours; In other examples, the time of described first reaction can be 24 hours ~ 26 hours.
In the present invention, the R in described formula 1 1with the R described in technique scheme 1unanimously, do not repeat them here.In the present invention, the R in described formula 1 5with the R described in technique scheme 5unanimously, do not repeat them here.In a preferred embodiment of the invention, described formula 1 has formula 7 or the structure shown in formula 8:
In an embodiment of the present invention, the preparation method described in the compound of structure shown in formula 1 is:
The compound with structure shown in formula 4 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1.
In formula 4, R 15be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
The linked reaction that the compound with structure shown in formula 4 and the compound with structure shown in formula 5 carry out is designated as the second reaction by the present invention.In an embodiment of the present invention, described second reaction can be carried out under the condition of protective gas.In an embodiment of the present invention, the protective gas in described second reaction can be selected from nitrogen.In an embodiment of the present invention, described second reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent in described second reaction can be selected from Isosorbide-5-Nitrae-dioxane aqueous solution.In an embodiment of the present invention, the mass concentration of described Isosorbide-5-Nitrae-dioxane aqueous solution can be 80% ~ 85%.
In an embodiment of the present invention, described second reaction can be carried out in the presence of a catalyst.In an embodiment of the present invention, the catalyzer in described second reaction comprises potassiumphosphate, palladium (Pd (OAc) 2) and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (Sphos).In an embodiment of the present invention, described potassiumphosphate, palladium and 2-dicyclohexyl phosphine-2 ', the mass ratio of 6 '-dimethoxy-biphenyl can be (235 ~ 245): 1:(1 ~ 2); In other examples, described potassiumphosphate, palladium and 2-dicyclohexyl phosphine-2 ', the mass ratio of 6 '-dimethoxy-biphenyl can be (238 ~ 242): 1:(1.2 ~ 1.6).
In an embodiment of the present invention, the temperature of described second reaction can be 110 DEG C ~ 130 DEG C; In other examples, the temperature of described second reaction can be 115 DEG C ~ 125 DEG C.In an embodiment of the present invention, the time of described second reaction can be 2 hours ~ 5 hours; In other examples, the temperature of described second reaction can be 3 hours ~ 4 hours.
In the present invention, the R in described formula 5 1with the R described in technique scheme 1unanimously, do not repeating at this.In a preferred embodiment of the invention, the compound described in structure shown in formula 5 has the structure shown in formula 14:
The source of the present invention to the compound with structure shown in formula 5 does not have special restriction, can be bought and obtain, can prepare according to method well known to those skilled in the art yet by market; As in an embodiment of the present invention, described in there is structure shown in formula 14 compound can prepare according to the method disclosed in document (W.Jiang, H.Qian, Y.Li, Z.Wang, J.Org.Chem.2008,73,7369.).
In the present invention, the R in described formula 4 5with the R described in technique scheme 5unanimously, do not repeat them here.In a preferred embodiment of the invention, the compound described in structure shown in formula 4 has the structure shown in formula 9:
In an embodiment of the present invention, the preparation method described in the compound of structure shown in formula 4 can be:
The compound and connection boric acid pinacol ester with structure shown in formula 10 are carried out linked reaction, obtain the compound with structure shown in formula 4:
I-R 15formula 10;
In formula 10, R 15be selected from aryl.
The linked reaction that the compound and connection boric acid pinacol ester with structure shown in formula 10 carry out is designated as the 3rd reaction.In an embodiment of the present invention, described 3rd reaction can be carried out under the condition of anaerobic and protective gas.In an embodiment of the present invention, the protective gas of described 3rd reaction can be argon gas.In an embodiment of the present invention, described 3rd reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent in described 3rd reaction can be dimethyl sulfoxide (DMSO).In an embodiment of the present invention, described 3rd reaction can be carried out in the presence of a catalyst.In an embodiment of the present invention, the catalyzer in described 3rd reaction comprises potassium acetate and [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride (Pd (dppf) Cl 2).In an embodiment of the present invention, the mass ratio of described potassium acetate and [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride can be (4.5 ~ 5.5): 1; In other examples, the mass ratio of described potassium acetate and [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride can be (4.8 ~ 5.2): 1.
In an embodiment of the present invention, the temperature of described 3rd reaction can be 40 DEG C ~ 50 DEG C; In other examples, the temperature of described 3rd reaction can be 44 DEG C ~ 48 DEG C.In an embodiment of the present invention, the time of described 3rd reaction can be 20 hours ~ 30 hours; In other examples, the time of described 3rd reaction can 24 hours ~ 28 hours.
In a preferred embodiment of the invention, the R in described formula 10 15for aryl, described aryl and the R described in technique scheme 5in aryl consistent, do not repeat them here.In a preferred embodiment of the invention, the compound described in structure shown in formula 10 has the structure shown in formula 11:
The present invention does not have special restriction to the described source with the compound of structure described in formula 10, can be bought and obtain, can prepare according to method well known to those skilled in the art yet by market.As in an embodiment of the present invention, described in there is the compound of structure shown in formula 11 preparation method can be:
The compound and 2-hexyl decyl-4-toluene sulfonic acide ester with structure shown in formula 12 are carried out nucleophilic substitution reaction, obtain the compound with structure shown in formula 11:
The nucleophilic substitution reaction that the compound and 2-hexyl decyl-4-toluene sulfonic acide ester with structure shown in formula 12 carry out is designated as the 4th reaction by the present invention.In an embodiment of the present invention, described 4th reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent of described 4th reaction can be DMF.In an embodiment of the present invention, described 4th reaction can be carried out in the basic conditions, carrying out nucleophilic substitution reaction by having the compound of structure shown in formula 12,2-hexyl decyl-4-toluene sulfonic acide ester and basic cpd, obtaining the compound with structure shown in formula 11.In an embodiment of the present invention, the basic cpd in described 4th reaction can be alkali metal hydroxide.In an embodiment of the present invention, described alkali metal hydroxide can be potassium hydroxide or sodium hydroxide; In a preferred embodiment of the invention, described alkali metal hydroxide can be potassium hydroxide.
In an embodiment of the present invention, the temperature of described 4th reaction can be 95 DEG C ~ 105 DEG C; In other examples, the temperature of described 4th reaction can be 98 DEG C ~ 102 DEG C.In an embodiment of the present invention, the time of described 4th reaction can be 20 hours ~ 30 hours; In other examples, the time of described 4th reaction can be 24 hours ~ 28 hours.
The source of the present invention to the compound and 2-hexyl decyl-4-toluene sulfonic acide ester with structure shown in formula 12 does not have special restriction, can be bought obtain by market.In an embodiment of the present invention, the mass ratio of the compound and 2-hexyl decyl-4-toluene sulfonic acide ester described in structure shown in formula 12 can be 1:(1.5 ~ 2.5); In other examples, the mass ratio of the compound and 2-hexyl decyl-4-toluene sulfonic acide ester described in structure shown in formula 12 can be 1:(1.8 ~ 2.2).The consumption of the present invention to the solvent in described 4th reaction and basic cpd does not have special restriction, meets actually operating condition.
In an embodiment of the present invention, the described 4th reacted after, the 4th reaction product obtained can be carried out successively extracting, dry, concentrated and chromatography, obtain the compound with structure shown in formula 11.In an embodiment of the present invention, the described 4th extraction agent of having reacted rear employing is chloroform, and dry reagent is anhydrous sodium sulphate, to be boiling point the be sherwood oil of 60 DEG C ~ 90 DEG C of chromatography column agent during chromatography.
In an embodiment of the present invention, the compound described in structure shown in formula 10 and the mass ratio joining boric acid pinacol ester are (1 ~ 1.5): 1; In other examples, the compound described in structure shown in formula 10 and the mass ratio joining boric acid pinacol ester are (1.2 ~ 1.3): 1.In an embodiment of the present invention, there is the mass ratio of the potassium acetate in the compound of structure shown in formula 10 and catalyzer for (2 ~ 3) described in: 1; In other examples, there is the mass ratio of the potassium acetate in the compound of structure shown in formula 10 and catalyzer for (2.4 ~ 2.6): 1.The present invention does not have special restriction to the consumption of solvent in described 3rd reaction, meets actually operating condition.
In an embodiment of the present invention, the described 3rd reacted after, the 3rd reaction product obtained is carried out successively extract, dry, concentrated and chromatography, obtains the compound with structure shown in formula 4.In an embodiment of the present invention, the described 3rd reagent having reacted rear extraction can be chloroform, and dry reagent can be anhydrous sodium sulphate, and the chromatography column agent of chromatography can be the ethyl acetate of 1:50 and the mixture of sherwood oil for volume ratio.
In an embodiment of the present invention, the mass ratio of the compound described in structure shown in formula 5 and the compound with structure shown in formula 4 can be 1:(1 ~ 1.5); In other examples, the mass ratio of the compound described in structure shown in formula 5 and the compound with structure shown in formula 4 can be 1:(1.2 ~ 1.3).In an embodiment of the present invention, the mass ratio described in the potassiumphosphate in the compound of structure shown in formula 5 and catalyzer can be 1:(2 ~ 3); In other examples, the mass ratio described in the potassiumphosphate in the compound of structure shown in formula 5 and catalyzer can be 1:(2.4 ~ 2.6).The present invention does not have special restriction to the consumption of solvent in described second reaction, meets actually operating condition.
In an embodiment of the present invention, described second reacted after, the second reaction product obtained is carried out successively extract, dry, concentrated and chromatography, obtains the compound with structure shown in formula 1.In an embodiment of the present invention, the described second reagent having reacted rear extraction can be chloroform, and dry reagent can be anhydrous sodium sulphate, and the chromatography column agent of chromatography can be the ethyl acetate of 1:50 and the mixture of sherwood oil for volume ratio.
In an embodiment of the present invention, the preparation method described in the compound of structure shown in formula 1 can be:
The compound with structure shown in formula 6 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1;
In formula 6, R 16be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
The linked reaction that the compound with structure shown in formula 6 and the compound with structure shown in formula 5 carry out is designated as the 5th reaction by the present invention.In an embodiment of the present invention, described 5th reaction can be carried out under the condition of anaerobic and protective gas.In an embodiment of the present invention, the protective gas in described 5th reaction can be nitrogen.In an embodiment of the present invention, described 5th reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent of described 5th reaction can be selected from toluene.In an embodiment of the present invention, described 5th reaction can be carried out in the presence of a catalyst.In an embodiment of the present invention, the catalyzer of described 5th reaction comprises sodium tert-butoxide, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene (XantPhos).In an embodiment of the present invention, described sodium tert-butoxide, three (dibenzalacetone) two palladium and 4,5-two (diphenylphosphine)-9,9-the mass ratio of dimethyl xanthene can be (15 ~ 25): 1:(1 ~ 1.5); In other examples, described sodium tert-butoxide, three (dibenzalacetone) two palladium and 4,5-two (diphenylphosphine)-9,9-the mass ratio of dimethyl xanthene can be (17 ~ 20): 1:(1.2 ~ 1.3).
In an embodiment of the present invention, the temperature of described 5th reaction can be 110 DEG C ~ 130 DEG C; In other examples, the temperature of described 5th reaction can be 115 DEG C ~ 125 DEG C.In an embodiment of the present invention, the time of described 5th reaction can be 20 hours ~ 30 hours; In other examples, the time of described 5th reaction can be 24 hours ~ 28 hours.
In the present invention, the R in described formula 6 16for aryl, R described in described aryl and technique scheme 5in aryl consistent, do not repeat them here.In a preferred embodiment of the invention, the compound described in structure shown in formula 6 has the structure shown in formula 13:
In the present invention, described in have the compound of structure shown in formula 5 consistent with the compound with structure shown in formula 5 described in technique scheme, do not repeat them here.The present invention does not have special restriction to the described compound with structure shown in formula 5 and the source of the compound with structure shown in formula 6, can be bought and obtain, can prepare according to method well known to those skilled in the art yet by market.In an embodiment of the present invention, the mass ratio of the compound described in structure shown in formula 5 and the compound with structure shown in formula 6 can be (1 ~ 1.5): 1; In other examples, the mass ratio of the compound described in structure shown in formula 5 and the compound with structure shown in formula 6 can be (1 ~ 1.5): 1.In an embodiment of the present invention, the mass ratio described in the sodium tert-butoxide in the compound of structure shown in formula 5 and catalyzer can be (0.8 ~ 1.2): 1; In other examples, the mass ratio described in the sodium tert-butoxide in the compound of structure shown in formula 5 and catalyzer can be (1 ~ 1.1): 1.The present invention does not have special restriction to the consumption of solvent in described 5th reaction, meets actually operating condition.
In an embodiment of the present invention, the described 5th reacted after, the 5th reaction product obtained is carried out successively extract, dry, concentrated and chromatography, obtains the compound with structure shown in formula 1.In an embodiment of the present invention, the described 5th reagent having reacted rear extraction can be chloroform, and dry reagent can be anhydrous sodium sulphate, and the chromatography column agent of chromatography can be the toluene of 1:5 and the mixture of sherwood oil for volume ratio.
In the present invention, the R in described formula 2 2with the R described in technique scheme 2unanimously, do not repeat them here.In the present invention, the R in described formula 2 3with the R described in technique scheme 3unanimously, do not repeat them here.In an embodiment of the present invention, the R in described formula 2 14be selected from the aryl that carbonatoms is the ester group replacement of 3 ~ 10; In other examples, the R in described formula 2 14be selected from the aryl that carbonatoms is the ester group replacement of 4 ~ 6.In a preferred embodiment of the invention, the compound described in structure shown in formula 2 has the structure shown in formula 15:
In an embodiment of the present invention, the preparation method described in structural compounds shown in formula 2 can be:
The compound and tetrabutyl ammonium fluoride with structure shown in formula 16 are reacted, obtains the compound with structure shown in formula 2;
In formula 16, R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 14be selected from the aryl that ester group replaces.
The reaction that the compound and tetrabutyl ammonium fluoride with structure shown in formula 16 carry out is designated as the 6th reaction by the present invention.In an embodiment of the present invention, described 6th reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent of described 6th reaction can be selected from methylene dichloride.In an embodiment of the present invention, the temperature of described 6th reaction can be 20 DEG C ~ 30 DEG C; In other examples, the temperature of described 6th reaction can be 24 DEG C ~ 28 DEG C.In an embodiment of the present invention, the time of described 6th reaction can be 0.5 hour ~ 1.5 hours; In other examples, the time of described 6th reaction can be 0.8 hour ~ 1.2 hours.
In the present invention, the R in described formula 16 2with the R described in technique scheme 2unanimously, do not repeat them here.In the present invention, the R in described formula 16 3with the R described in technique scheme 3unanimously, do not repeat them here.In the present invention, the R in described formula 16 14with the R described in technique scheme 14unanimously, do not repeat them here.In a preferred embodiment of the invention, the compound described in structure shown in formula 16 has the structure shown in formula 17:
In an embodiment of the present invention, the preparation method described in the compound of structure shown in formula 16 can be:
The compound and triisopropylsilyl acetylene with structure shown in formula 18 are carried out linked reaction, obtain the compound with structure shown in formula 16:
In formula 18, R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 14be selected from the aryl that ester group replaces.
The linked reaction that the compound and triisopropylsilyl acetylene with structure shown in formula 18 carry out is designated as the 7th reaction by the present invention.In an embodiment of the present invention, described 7th reaction can be carried out under the condition of anaerobic, protective gas.In an embodiment of the present invention, the protective gas in described 7th reaction can be nitrogen.In an embodiment of the present invention, described 7th reaction can be carried out in a solvent.In an embodiment of the present invention, the solvent in described 7th reaction can be Isosorbide-5-Nitrae-dioxane.In an embodiment of the present invention, described 7th reaction can be carried out in the presence of a catalyst.In an embodiment of the present invention, the catalyzer of described 7th reaction comprises cesium carbonate, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-butyl phosphine (P (t-Bu) 3).In an embodiment of the present invention, described cesium carbonate, three (dibenzalacetone) two the mass ratio of palladium and tri-butyl phosphine can be (20 ~ 30): (1.5 ~ 2.5): 1; In other examples, described cesium carbonate, three (dibenzalacetone) two the mass ratio of palladium and tri-butyl phosphine can be (24 ~ 27): (1.8 ~ 2.0): 1.
In an embodiment of the present invention, the temperature of described 7th reaction can be 110 DEG C ~ 130 DEG C; In other examples, the temperature of described 7th reaction can be 115 DEG C ~ 125 DEG C.In an embodiment of the present invention, the time of described 7th reaction can be 20 hours ~ 30 hours; In other examples, the time of described 7th reaction can be 24 hours ~ 28 hours.
In a preferred embodiment of the invention, the compound described in structure shown in formula 18 has the structure shown in formula 19:
The present invention does not have special restriction to the described source with the compound of structure shown in formula 18, can be bought by market and obtain, also can prepare according to method well known to those skilled in the art, as in an embodiment of the present invention, the described compound with structure shown in formula 19 can according to document (Zhang, M.; Wang, Y.; Xu, M.; Ma, W.; Li, R.; Wang, P.Energy Environ.Sci.2013,6,2944-2949.) disclosed in method prepare.
In an embodiment of the present invention, the mass ratio of the compound and triisopropylsilyl acetylene described in structure shown in formula 18 can be 1:(1 ~ 1.5); In other examples, the mass ratio of the compound and triisopropylsilyl acetylene described in structure shown in formula 18 can be 1:(1.2 ~ 1.3).
In an embodiment of the present invention, the described 7th reacted after, the 7th reaction product obtained can be carried out successively extracting, dry, concentrated and chromatography, obtain the compound with structure shown in formula 16.In an embodiment of the present invention, the solvent that described 7th reaction terminates rear extraction is chloroform, and dry reagent is anhydrous sodium sulphate, and the chromatography column agent of chromatography is volume ratio is the trichloromethane of 1:2 and the mixture of sherwood oil.
In an embodiment of the present invention, the mass ratio of the compound and tetrabutyl ammonium fluoride described in structure shown in formula 16 can be 1:(2 ~ 5); In other examples, the mass ratio of the compound and tetrabutyl ammonium fluoride described in structure shown in formula 16 can be 1:(3 ~ 4).The consumption of the present invention to the solvent in described 6th reaction does not have special restriction, meets actually operating condition.
In an embodiment of the present invention, the described 6th reacted after, the 6th reaction product obtained can be carried out successively extracting, dry and concentrated, obtain the compound with structure shown in formula 2.In an embodiment of the present invention, the described 6th reagent having reacted rear extraction can be chloroform, and dry reagent can be anhydrous sodium sulphate.
In an embodiment of the present invention, the mass ratio of the compound described in structure shown in formula 1 and the compound with structure shown in formula 2 can be (2 ~ 3.5): 1; In other examples, the mass ratio of the compound described in structure shown in formula 1 and the compound with structure shown in formula 2 can be (2.4 ~ 3): 1.In an embodiment of the present invention, the mass ratio described in the cesium carbonate in the compound of structure shown in formula 1 and catalyzer can be (2 ~ 3): 1; In other examples, the mass ratio described in the cesium carbonate in the compound of structure shown in formula 1 and catalyzer can be (2.4 ~ 2.6): 1.The consumption of the present invention to the solvent in described first reaction does not have special restriction, meets actually operating condition.
In an embodiment of the present invention, described first reacted after, the first reaction product obtained can be carried out alkali cleaning and pickling successively, obtain having the compound of structure shown in formula I.In an embodiment of the present invention, the reagent of described alkali cleaning can be potassium hydroxide.In an embodiment of the present invention, described alkali cleaning can be carried out in a solvent.In an embodiment of the present invention, the solvent of described alkali cleaning can be tetrahydrofuran aqueous solution.In an embodiment of the present invention, the mass concentration of described tetrahydrofuran aqueous solution can be 75% ~ 85%.In an embodiment of the present invention, the temperature of described alkali cleaning can be 75 DEG C ~ 85 DEG C; In other examples, the temperature of described alkali cleaning can be 78 DEG C ~ 82 DEG C.
In an embodiment of the present invention, the reagent of described pickling can be phosphoric acid; In other examples, the reagent of described pickling can be phosphate aqueous solution.In an embodiment of the present invention, the volumetric molar concentration of described phosphate aqueous solution can be 0.15mol/L ~ 0.4mol/L; In other examples, the volumetric molar concentration of described phosphate aqueous solution can be 0.2mol/L ~ 0.3mol/L.In an embodiment of the present invention, the temperature of described pickling can be 20 DEG C ~ 30 DEG C; In other examples, the temperature of described pickling can be 24 DEG C ~ 28 DEG C.
In an embodiment of the present invention, after described pickling completes, the product after pickling can be carried out successively extracting, dry, concentrated and chromatography, obtain having the compound of structure shown in formula I.In an embodiment of the present invention, the reagent of extraction after described pickling completes can be chloroform, and dry reagent can be anhydrous sodium sulphate, and the chromatography column agent of chromatography can be the trichloromethane of 1:20 and the mixture of methyl alcohol for volume ratio.
In a preferred embodiment of the invention, the phenanthro-carbazoles dyestuff with structure shown in formula II can be prepared by the following method:
At 90 DEG C ~ 110 DEG C, be 1:(1.5 ~ 2.5 by mass ratio): the compound with structure shown in formula 12 of (1 ~ 1.5), 2-hexyl decyl-4-toluene sulfonic acide ester and potassium hydroxide carry out the reaction of 20 hours ~ 30 hours in DMF;
To obtain reaction product adopts chloroform to extract successively, and anhydrous sodium sulphate carries out drying, the product after concentrate drying, is adopted by the product after concentrated boiling point to be that the sherwood oil of 60 DEG C ~ 90 DEG C carries out chromatography, obtains the compound with structure shown in formula 11;
At 40 DEG C ~ 50 DEG C, be (10 ~ 15) by mass ratio: (8 ~ 12): (3 ~ 7): the compound with structure shown in formula 11 of 1, connection boric acid pinacol ester, potassium acetate and [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride carry out the reaction of 20 hours ~ 30 hours in dimethyl sulfoxide (DMSO);
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the ethyl acetate of 1:50 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 9;
At 110 DEG C ~ 130 DEG C, be (30 ~ 40) by mass ratio: (35 ~ 45): (20 ~ 30): (1.5 ~ 2.5): the compound with structure shown in formula 19 of 1, triisopropylsilyl acetylene, cesium carbonate, three (dibenzalacetone) two palladium and tri-butyl phosphine in Isosorbide-5-Nitrae-dioxane, carry out the reaction of 20 hours ~ 30 hours;
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the trichloromethane of 1:2 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 17;
At 20 DEG C ~ 30 DEG C, be 1:(3 ~ 4 by mass ratio) the compound with structure shown in formula 17 and tetrabutyl ammonium fluoride in methylene dichloride, carry out the reaction of 0.5 hour ~ 1.5 hours;
Adopt chloroform to extract successively the reaction product obtained, adopt anhydrous sodium sulphate to carry out drying, dried product is concentrated, obtains the compound with structure shown in formula 15;
At 110 DEG C ~ 130 DEG C, be (95 ~ 105) by mass ratio: (130 ~ 140): (235 ~ 245): 1:(1.5 ~ 2.5) there is the compound of structure shown in the compound of structure shown in formula 14, formula 9, potassiumphosphate, palladium and 2-dicyclohexyl phosphine-2', 6'-dimethoxy-biphenyl carries out the reaction of 2.5 hours ~ 3.5 hours;
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the ethyl acetate of 1:50 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 20:
At-5 DEG C ~ 5 DEG C, be (4.5 ~ 5.5) by mass ratio: the compound with structure shown in formula 20 of 1 and N-bromo-succinimide carry out the reaction of 2.5 hours ~ 3.5 hours in tetrahydrofuran (THF);
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the ethyl acetate of 1:20 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 7;
At 110 DEG C ~ 130 DEG C, be (60 ~ 70) by mass ratio: (20 ~ 30): (20 ~ 30): (1.5 ~ 2.5): the compound with structure shown in formula 7 of 1, the compound with structure shown in formula 15, cesium carbonate, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-butyl phosphine (P (t-Bu) 3) in Isosorbide-5-Nitrae-dioxane, carry out the reaction of 20 hours ~ 30 hours;
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the toluene of 1:2 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 21:
At 75 DEG C ~ 85 DEG C, be (2.5 ~ 3.5) by mass ratio: the compound with structure shown in formula 21 of 1 and potassium hydroxide carry out the reaction of 3 hours ~ 7 in tetrahydrofuran (THF), obtain alkali cleaning product;
At 20 DEG C ~ 30 DEG C, the phosphate aqueous solution being 0.15mol/L ~ 0.3mol/L by described alkali cleaning product employing volumetric molar concentration carries out pickling;
Product pickling obtained adopts chloroform to extract successively, anhydrous sodium sulphate carries out drying, dried product is concentrated, adopts volume ratio to be that the trichloromethane of 1:20 and the mixture of methyl alcohol carry out chromatography the product after concentrated, obtain having the compound of structure shown in formula II.
In a preferred embodiment of the invention, the preparation method described in the phenanthro-carbazoles dyestuff of structure shown in formula III can be:
At 110 DEG C ~ 130 DEG C, be (15 ~ 25) by mass ratio: (30 ~ 60): (15 ~ 25): 1:(1 ~ 1.5) the compound with structure shown in formula 14, the compound with structure shown in formula 13, sodium tert-butoxide, three (dibenzalacetone) two palladium and 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene carries out the reaction of 20 hours ~ 30 hours in toluene;
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate carries out drying, dried product is concentrated, adopts volume ratio to be that the toluene of 1:5 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 22;
At-5 DEG C ~ 5 DEG C, be (8 ~ 11) by mass ratio: the compound with structure shown in formula 22 of 1 and N-bromo-succinimide carry out the reaction of 2.5 hours ~ 3.5 hours in tetrahydrofuran (THF);
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the ethyl acetate of 1:50 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 8;
At 110 DEG C ~ 130 DEG C, be (120 ~ 140) by mass ratio: (15 ~ 25): (20 ~ 30): (1.5 ~ 2.5): the compound with structure shown in formula 8 of 1, the compound with structure shown in formula 15, cesium carbonate, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-butyl phosphine (P (t-Bu) 3) in Isosorbide-5-Nitrae-dioxane, carry out the reaction of 20 hours ~ 30 hours;
Chloroform is adopted to extract successively the reaction product obtained, anhydrous sodium sulphate is adopted to carry out drying, dried product is concentrated, adopts volume ratio to be that the toluene of 1:2 and the mixture of sherwood oil carry out chromatography the product after concentrated, obtain the compound with structure shown in formula 23:
At 75 DEG C ~ 85 DEG C, be (4 ~ 6) by mass ratio: the compound with structure shown in formula 23 of 1 and potassium hydroxide carry out the reaction of 3 hours ~ 7 in tetrahydrofuran (THF), obtain alkali cleaning product;
At 20 DEG C ~ 30 DEG C, the phosphate aqueous solution being 0.15mol/L ~ 0.3mol/L by described alkali cleaning product employing volumetric molar concentration carries out pickling;
Product pickling obtained adopts chloroform to extract successively, anhydrous sodium sulphate carries out drying, dried product is concentrated, adopts volume ratio to be that the trichloromethane of 1:20 and the mixture of methyl alcohol carry out chromatography the product after concentrated, obtain having the compound of structure shown in formula III.
The phenanthro-carbazoles dyestuff that method provided by the invention prepares has longer lifetime of excited state, and the dye-sensitized solar cells adopting this preparation of dyestuff to obtain has higher power-conversion efficiencies.In addition, preparation method's technique of phenanthro-carbazoles dyestuff provided by the invention is simple, cost is lower, safety and environmental protection.
The invention provides a kind of dye-sensitized solar cells, comprise the phenanthro-carbazoles dyestuff described in technique scheme, or the phenanthro-carbazoles dyestuff that the method described in technique scheme prepares.
The preparation method of the present invention to described dye-sensitized solar cells does not have special restriction, adopts the technology of preparing scheme of dye-sensitized solar cells well known to those skilled in the art.As in an embodiment of the present invention, can prepare dye-sensitized solar cells according to the method disclosed in document (Energy Environ.Sci., 2010,3,1924), detailed process is:
By TiO 2electrode soaks in phenanthro-carbazoles dyestuff, obtains the electrode of composite dye;
The electrode of described composite dye and glass electrode are carried out assembling and sealing successively, obtains battery container;
In described battery container, inject ionogen, obtain dye-sensitized solar cells.
In an embodiment of the present invention, by TiO 2electrode soaks in phenanthro-carbazoles dyestuff, obtains the electrode of composite dye.In an embodiment of the present invention, the time of described immersion can be 8 hours ~ 20 hours; In other examples, the time of described immersion can be 10 hours ~ 15 hours.In an embodiment of the present invention, the temperature of described immersion can be 20 DEG C ~ 30 DEG C.
The present invention is to described TiO 2kind and the source of electrode do not have special restriction, adopt the TiO preparing dye-sensitized solar cells and adopt well known to those skilled in the art 2electrode, can be bought by market and obtain.In an embodiment of the present invention, described TiO 2electrode can be TiO 2structure duplicature electrode.
In an embodiment of the present invention, described phenanthro-carbazoles dyestuff is consistent with the phenanthro-carbazoles dyestuff described in technique scheme, does not repeat them here.In a preferred embodiment of the invention, described phenanthro-carbazoles dyestuff has the structure shown in formula II or formula III.In a preferred embodiment of the invention, described phenanthro-carbazoles dyestuff can be phenanthro-carbazoles dye solution.In an embodiment of the present invention, the solvent in described phenanthro-carbazoles dye solution can be selected from the mixture of ethanol and toluene.In an embodiment of the present invention, the volume ratio of described ethanol and toluene can be (5 ~ 20): 1; In other examples, the volume ratio of described ethanol and toluene can be (10 ~ 15): 1.In an embodiment of the present invention, the volumetric molar concentration of described phenanthro-carbazoles dye solution can be 50 μm of ol/L ~ 200 μm ol/L; In other examples, the volumetric molar concentration of described phenanthro-carbazoles dye solution can be 100 μm of ol/L ~ 150 μm ol/L.
In an embodiment of the present invention, after obtaining the electrode of composite dye, the electrode of described composite dye and glass electrode are carried out assembling and sealing successively, obtains battery container.The method of the present invention to described assembling does not have special restriction, adopts the technical scheme preparing electrode assembling in dye-sensitized solar cells process well known to those skilled in the art.In an embodiment of the present invention, the method for described sealing can seal for adopting hot melt ring.The present invention does not have special restriction to the kind of described glass electrode and source, adopts and well known to those skilled in the artly prepares the glass electrode adopted in dye-sensitized solar cells process, can buy acquisition by market.In an embodiment of the present invention, described glass electrode can for covering the glass electrode of Platinum Nanoparticles.
In an embodiment of the present invention, after obtaining battery container, in described battery container, inject ionogen, obtain dye-sensitized solar cells.The present invention does not have special restriction to described electrolytical kind, adopts the ionogen that dye-sensitized solar cells well known to those skilled in the art adopts.In an embodiment of the present invention, described ionogen can be iodine/salt compounded of iodine ionogen, ionic liquid electrolyte, and the one in cobalt/cobalt salt composite electrolyte.The present invention does not have special restriction to described electrolytical source, adopts the electrolyte preparation method in battery well known to those skilled in the art to prepare.Dyestuff in dye-sensitized solar cells provided by the invention is the phenanthro-carbazoles dyestuff described in technique scheme, and this dye-sensitized solar cells has higher power-conversion efficiencies.
Detect the performance of dye-sensitized solar cells provided by the invention, solar spectrum dye-sensitized solar cells provided by the invention being placed in solar simulator simulation is AM1.5G, radiation amount is 100mW cm -2sunlight in, described dye-sensitized solar cells is applied to the applying bias reduced gradually, tests the J-V curve of described dye-sensitized solar cells, by testing the open circuit voltage V of dye-sensitized solar cells described in the J-V curve calculation that obtains oc, short-circuit current density j sc, load voltage V m, load current j m, peak power P m, calculate the packing factor FF of described dye-sensitized solar cells according to the following equation:
FF = V m × j m V oc × j sc = P m V oc × j sc ;
Calculate the power conversion efficiency of described dye-sensitized solar cells according to the following equation:
Power conversion efficiency=V oc× j sc× FF.
Test result is, the open circuit voltage of dye-sensitized solar cells provided by the invention is 860mV ~ 910mV; Short-circuit current density is 15mA cm -2~ 17mA cm -2; Packing factor is 0.68 ~ 0.73; Power conversion efficiency is 9.5% ~ 10.5%.
Raw material used by following examples of the present invention is commercial goods, and the compound with structure shown in formula 19 is according to document (Zhang, M.; Wang, Y.; Xu, M.; Ma, W.; Li, R.; Wang, P.EnergyEnviron.Sci.2013,6,2944-2949.) disclosed in method prepare; The compound with structure shown in formula 14 is prepare according to the method disclosed in document (W.Jiang, H.Qian, Y.Li, Z.Wang, J.Org.Chem.2008,73,7369.).
Embodiment 1
In three neck round-bottomed flasks, by the N of compound dissolution at 20mL with structure shown in formula 12 of 2.00g, in dinethylformamide, add in described three neck round-bottomed flasks the 2-hexyl decyl-4-toluene sulfonic acide ester of 3.60g and the potassium hydroxide of 2.55g 100 DEG C, carry out the reaction of 24 hours under the condition that stirs;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after concentrated described filtration, the sherwood oil being 80 DEG C using the filtrate employing boiling point after described concentrating carries out chromatography as developping agent post, obtain first product of 4.04g, the yield of described first product is 97%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described first product, the characterization data of nucleus magnetic resonance is as follows:
1H NMR(400MHz,CDCl 3)δ:7.55(d,J＝8.9Hz,2H),6.69(d,J＝8.9Hz,2H),3.80(d,J＝5.7Hz,2H),1.79(m,1H),1.42(m,4H),1.32(m,20H),0.91(t,J＝6.5Hz,6H)。
13C NMR(100MHz,CDCl 3)δ:159.47,138.30,117.17,82.49,71.22,38.09,32.12,32.06,31.56,31.54,30.22,29.80,29.55,27.04,27.02,22.90,14.33。
The data of mass spectroscopy are: 445.19 ([M+H]+).
The data of ultimate analysis are: C, 59.46; H, 8.37.
From above data, described first product is for having the compound of structure shown in formula 11;
In the Schlenk reaction flask of drying; by the compound with structure shown in formula 11 of 3.00g; the connection boric acid pinacol ester of 2.23g, the potassium acetate of 1.19g is dissolved in the dimethyl sulfoxide (DMSO) of 20mL, adds Pd (dppf) Cl of 247mg under the protection of argon gas 2, at 45 DEG C, carry out the reaction of 24 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the ethyl acetate of 1:50 and the mixture of sherwood oil carry out chromatography as developping agent post, obtain second product of 2.82g, the yield of described second product is 94%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described second product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,CDCl 3)δ:7.76(d,J＝5.6Hz,2H),6.90(d,J＝5.6Hz,2H),3.87(d,J＝5.7Hz,2H),1.80(m,1H),1.45(m,4H),1.34(br,14H),1.28(br,18H),0.90(t,J＝6.5Hz,6H)。
13C NMR(100MHz,CDCl 3)δ:162.32,136.69,114.18,83.67,71.03,38.20,32.06,31.67,30.22,29.89,29.78,29.52,27.06,25.07,22.87,14.27。
Analytical data of mass spectrum is: 444.33 ([M+]).
Elemental analysis data is: C, 75.64; H, 11.10.
From above data, described second product is for having the compound of structure shown in formula 9;
In the Schlenk reaction flask of drying, by the compound with structure shown in formula 19 of 1.46g, the triisopropylsilyl acetylene of 1.70g, the cesium carbonate of 1.11g is dissolved in 1 of 20mL, in 4-dioxane, in the glove box being full of nitrogen, in described Schlenk reaction flask, add the Pd of 85mg 2(dba) 3with the P (t-Bu) of 44mg 3, at 120 DEG C, carry out the reaction of 24 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after filtration is concentrated, be that the trichloromethane of 1:2 and the mixture of sherwood oil carry out chromatography as developping agent post using the filtrate volume ratio obtained after concentrated, obtain third product, the yield of described third product is 87%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described third product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:7.22(d,J＝8.6Hz,1H),7.03(d,J＝8.8Hz,2H),6.91(d,J＝8.8Hz,2H),6.64(d,J＝8.6Hz,1H),3.93(t,J＝6.2Hz,2H),1.69(m,2H),1.41(m,2H),1.07(s,18H),0.88(m,3H)。
13C NMR(100MHz,THF-d 8)δ:196.64,167.27,156.09,149.12,140.40,133.04,130.82,127.11,119.57,115.61,114.70,108.11,88.65,68.53,25.98,22.82,19.09,14.22,11.67。
Analytical data of mass spectrum is: 493.23 ([M+H]+).
Elemental analysis data is: C, 68.27; H, 7.34; N, 5.69.
From above data, described third product is for having the compound of structure shown in formula 17;
In three-necked flask, by 1.33g there is the compound of structure shown in formula 17 and the tetrabutyl ammonium fluoride of 4.55g is dissolved in the methylene dichloride of 20mL, at 25 DEG C, carry out the reaction of 1 hour;
After described reaction terminates, in the reaction product obtained, add the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; By described organic phase distilled water flushing three times, after adopting the organic phase after rinsing described in anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained is concentrated, obtain the 4th product after described filtration.
In three neck round-bottomed flasks; by the compound with structure shown in formula 14 of 2.00g; the compound with structure shown in formula 9 of 2.69g; the potassiumphosphate of 4.78g is dissolved in 1 of 20mL; in the mixed solvent of the water composition of 4-dioxane and 4mL; under argon shield, in described three neck round-bottomed flasks, add the Pd (OAc) of 20mg 2with the 2-dicyclohexyl phosphine-2 of 37mg ', 6 '-dimethoxy-biphenyl, carries out the reaction of 3 hours at 120 DEG C;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, filtrate after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the ethyl acetate of 1:50 and the mixture of sherwood oil are as developping agent column chromatography, obtain the 5th product, the yield of described 5th product is 83%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described 5th product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,CDCl 3)δ:8.68(m,2H),8.13(m,2H),7.91(d,J＝8.7Hz,1H),7.78(m,3H),7.72(s,1H),7.63(d,J＝8.4Hz,2H),7.10(d,J＝8.4Hz,2H),4.57(d,J＝7.2Hz,2H),3.96(d,J＝5.5Hz,2H),2.31(m,1H),1.86(m,1H),1.55(m,4H),1.37(m,30H),1.19(m,14H),0.90(m,6H),0.82(m,6H)。
13C NMR(100MHz,CDCl 3)δ:158.98,137.48,134.43,132.41,132.32,131.48,130.74,130.69,128.93,128.24,125.17,125.05,124.92,124.65,124.53,123.51,120.97,120.74,117.59,116.73,114.66,114.21,113.59,71.25,50.17,40.07,38.32,32.17,32.06,31.99,31.95,31.71,30.32,30.13,29.99,29.84,29.71,29.61,29.47,27.15,26.66,22.95,22.83,14.37,14.31,14.26。
The data of mass spectroscopy are: 806.61 ([M+H] +).
The data of ultimate analysis are: C, 86.41; H, 9.86; N, 1.73.
From above data, described 5th product is for having the compound of structure shown in formula 20;
In the Schlenk reaction flask of drying, by the compound dissolution with structure shown in formula 20 of 3.00g in the tetrahydrofuran (THF) of 20mL, in described Schlenk reaction flask, add the N-bromo-succinimide of 592mg, carry out the reaction of 3 hours at 0 DEG C;
After described reaction terminates, in the reaction product obtained, add the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the ethyl acetate of 1:20 and the mixture of sherwood oil carry out chromatography as developping agent post, obtain the 6th product of 2.80g, the yield of described 6th product is 95%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described 6th product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,CDCl 3)δ:8.45(d,J＝7.7Hz,1H),8.36(d,J＝7.6Hz,1H),8.17(d,J＝8.2Hz,1H),8.13(d,J＝8.2Hz,1H),7.73(d,J＝8.0Hz,1H),7.68(m,4H),7.51(s,1H),7.20(d,J＝8.6Hz,2H),4.05(m,4H),2.06(br,1H),1.95(m,1H),1.62(m,4H),1.46(m,20H),1.30(m,24H),1.02(m,6H),0.92(m,6H)。
13C NMR(100MHz,CDCl 3)δ:159.00,137.61,134.62,132.10,131.42,131.18,130.15,129.81,127.83,127.47,124.98,124.58,124.48,124.26,123.89,121.04,120.96,117.09,116.66,116.29,115.77,114.64,113.81,71.19,49.73,39.77,38.34,32.20,32.18,32.07,32.00,31.79,31.74,30.35,29.90,29.81,29.72,29.64,29.49,27.18,26.51,22.98,22.85,14.40,14.33,14.28。
The data of mass spectroscopy are: 884.53 ([M+H] +).
The data of ultimate analysis are: C, 78.71; H, 8.87, N, 1.59.
From above data, described 6th product is for having the compound of structure shown in formula 7;
In the Schlenk reaction flask of drying, by the compound with structure shown in formula 7 of 1.00g, above-mentioned 4th product of 380mg, the cesium carbonate of 405mg is dissolved in 1 of 10mL, in 4-dioxane, in the glove box being full of nitrogen, in described Schlenk reaction flask, add the Pd of 31mg 2(dba) 3with the P (t-Bu) of 16mg 3, at 120 DEG C, carry out the reaction of 24 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the toluene of 1:2 and the mixture of sherwood oil carry out chromatography as developping agent post, obtain the 7th product of 1.03g, the yield of described 7th product is 80%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described 7th product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:8.77(m,1H),8.65(m,2H),8.12(m,5H),7.90(m,3H),7.69(m,2H),7.59(m,3H),7.09(m,2H),4.42(m,4H),3.96(m,2H),2.18(m,1H),1.86(m,1H),1.72(m,4H),1.44(m,32H),1.10(m,16H),1.00(m,8H),0.76(m,6H)。
13C NMR(100MHz,THF-d 8)δ:166.46,160.10,156.68,156.60,154.10,154.00,142.31,142.25,142.16,139.88,139.80,135.04,134.76,132.56,132.43,132.21,131.45,131.26,130.60,130.38,130.15,130.07,129.36,129.22,129.05,126.29,126.21,125.61,125.56,125.14,124.84,122.23,122.03,119.16,118.92,118.74,117.09,116.53,115.35,114.99,114.91,98.95,91.05,71.72,65.46,50.65,50.57,40.78,39.35,33.08,32.96,32.91,32.70,32.62,32.02,31.25,31.06,30.79,30.62,30.52,30.42,28.05,27.41,23.78,23.65,20.37,14.68,14.62,14.36。
The data of mass spectroscopy are: 1140.69 ([M+H]+).
The data of ultimate analysis are: C, 81.09; H, 8.25, N, 3.65.
From above data, described 7th product is for having the compound of structure shown in formula 21;
In three neck round-bottomed flasks, by the compound dissolution with structure shown in formula 21 of 1.03g in the tetrahydrofuran (THF) of 12mL and the water of 3mL, in described three neck round-bottomed flasks, add the potassium hydroxide of 362mg, under the condition stirred, at 80 DEG C, carry out the reaction of 5 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, the volumetric molar concentration adding 20mL in described reaction product is the phosphate aqueous solution of 0.2mol/L, by the mixed solution chloroform extraction that obtains three times, merges organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the trichloromethane of 1:20 and the mixture of methyl alcohol carry out chromatography as developping agent post, obtain the phenanthro-carbazoles dyestuff of 1.02g, the yield of described phenanthro-carbazoles dyestuff is 99%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described phenanthro-carbazoles dyestuff, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:8.81(d,J＝6.3Hz,1H),8.66(d.J＝4.0Hz,2H),8.10(m,6H),7.91(m,3H),7.70(m,2H),7.59(d,J＝5.6Hz,2H),7.09(d,J＝5.0Hz,2H),4.49(br,2H),3.99(br,2H),2.26(br,2H),2.05(m,2H),1.87(m,2H),1.45(m,40H),1.14(m,16H),0.91(br,6H),0.77(br,6H)。
13C NMR(100MHz,THF-d 8)δ:167.67,160.14,156.70,154.15,142.10,139.93,135.05,134.87,133.40,132.59,132.20,131.78,131.57,131.31,130.75,130.09,129.33,129.12,126.29,125.70,125.55,125.15,124.96,122.31,122.14,119.29,119.08,118.67,117.18,116.59,115.37,114.99,98.77,91.02,71.71,50.66,40.82,39.35,36.38,33.07,32.95,32.91,32.72,32.62,31.25,31.06,30.90,30.79,30.62,30.51,30.40,28.18,28.04,27.41,26.59,23.77,23.65,14.67,14.60。
The data of mass spectroscopy are: 1083.63457.
The data of ultimate analysis are: C, 80.85; H, 7.90, N, 3.86.
From above data, described phenanthro-carbazoles dyestuff has the structure shown in formula II:
Embodiment 2
In the Schlenk reaction flask of drying, by the compound with structure shown in formula 14 of 2.88g, the compound with structure shown in formula 13 of 6.29g, the sodium tert-butoxide of 2.43g is dissolved in the toluene of 20mL, adds the Pd of 139mg in the glove box being full of nitrogen in described Schlenk reaction flask 2(dba) 3with 4,5-of 176mg two (diphenylphosphine)-9,9-dimethyl xanthene, at 120 DEG C, carry out the reaction of 24 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate that described filtration obtains is concentrated, using described concentrated after filtrate volume ratio be that the toluene of 1:5 and sherwood oil carry out chromatography as developping agent post, obtain first product of 6.39g, the yield of described first product is 73%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described first product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:8.62(d,J＝4.3Hz,1H),8.60(d,J＝4.3Hz,1H),8.04(d,J＝8.1Hz,2H),7.82(d,J＝8.8Hz,1H),7.79(s,1H),7.75(d,J＝8.8Hz,1H),7.73(m,2H),7.69(m,1H),7.62(m,2H),7.58(m,1H),7.10(d,J＝8.0Hz,4H),7.01(d,J＝8.0Hz,4H),2.76(m,4H),2.53(m,4H),2.16(m,5H),1.61(m,16H),1.56(m,12H),1.32(br,18H),1.21(m,16H),1.16(m,32H),0.89(m,16H),0.88(m,20H),0.84(m,18H),0.80(m,6H)。
13C NMR(100MHz,THF-d 8)δ:149.23,148.65,145.38,143.23,140.89,136.59,134.56,133.65,131.90,131.29,130.03,129.86,129.45,128.91,127.87,126.98,126.78,125.97,125.68,125.54,124.41,124.01,123.48,122.60,121.95,121.66,118.41,116.71,114.50,50.59,41.03,36.35,32.99,32.90,32.79,31.00,30.71,30.60,30.38,30.18,29.87,28.96,27.98,27.53,23.70,14.70。
The data of mass spectroscopy are: 1731.48 ([M+H]+).
The data of ultimate analysis are: C, 87.43; H, 10.95, N, 1.63.
From above data, described first product is for having the compound of structure shown in formula 22;
In the Schlenk reaction flask of drying, by the compound dissolution with structure shown in formula 22 of 5.37g in the tetrahydrofuran (THF) of 20mL, in described Schlenk reaction flask, add the N-bromo-succinimide of 552mg, carry out the reaction of 3 hours at 0 DEG C;
After described reaction terminates, in the reaction product obtained, add the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, anhydrous sodium sulphate after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the ethyl acetate of 1:50 and the mixture of sherwood oil carry out chromatography as developping agent post, obtain second product of 5.28g, the yield of described second product is 94%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described second product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:8.64(d,J＝4.3Hz,1H),8.61(d,J＝4.3Hz,1H),8.04(d,J＝8.1Hz,2H),7.83(d,J＝8.8Hz,1H),7.78(s,1H),7.74(d,J＝8.8Hz,1H),7.72(m,1H),7.69(m,1H),7.62(m,2H),7.58(m,1H),7.10(d,J＝8.0Hz,4H),7.01(d,J＝8.0Hz,4H),2.76(m,4H),2.53(m,4H),2.16(m,5H),1.61(m,16H),1.56(m,12H),1.32(br,18H),1.23(m,16H),1.16(m,32H),0.89(m,16H),0.88(m,20H),0.86(m,18H),0.81(m,6H)。
13C NMR(100MHz,THF-d 8)δ:148.23,147.56,144.36,143.23,140.89,136.59,134.56,133.65,131.90,131.29,130.03,129.86,129.45,128.91,127.87,126.98,126.78,125.97,125.68,125.54,124.41,124.01,123.48,122.60,121.95,120.66,118.41,116.71,114.50,50.59,41.03,36.35,32.99,32.90,32.79,31.00,30.71,30.60,30.49,30.16,29.84,28.96,27.98,26.93,23.68,14.71。
The data of mass spectroscopy are: 1809.39 ([M+H]+).
The data of ultimate analysis are: C, 83.62; H, 10.41; N, 1.59.
Passable by above data, described second product is for having the compound of structure shown in formula 8:
In the Schlenk reaction flask of drying, by the compound with structure shown in formula 8 of 2.60g, the 4th product that the embodiment 1 of 380mg prepares, the cesium carbonate of 520mg is dissolved in 1 of 10mL, in 4-dioxane, in the glove box being full of nitrogen, in described Schlenk reaction flask, add the Pd of 40mg 2(dba) 3with the P (t-Bu) of 20mg 3, at 120 DEG C, carry out the reaction of 24 hours;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, in described reaction product, adds the water of 20mL, by the mixed solution chloroform extraction that obtains three times, merge organic phase; After described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, filtrate after described filtration is concentrated, the mixture being 1:2 toluene and sherwood oil using the filtrate volume ratio after described concentrating carries out chromatography as developping agent post, obtain the third product of 2.11g, the yield of described third product is 71%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described third product, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:8.69(m,1H),8.46(m,2H),8.21(m,8H),7.90(m,5H),7.73(m,1H),7.51(d,J＝7.9Hz,1H),7.18(d,J＝7.2Hz,4H),7.07(d,J＝7.8Hz,4H),6.94(m,1H),6.78(s,1H),4.42(m,2H),2.83(m,8H),2.56(t,J＝7.5Hz,4H),2.23(m,6H),1.60(m,32H),1.44(m,64H),1.15(br,32H),0.93(m,16H),0.78(m,16H)。
13C NMR(100MHz,THF-d 8)δ:166.49,159.66,156.68,154.13,147.00,146.09,142.87,142.34,141.67,135.99,133.09,132.70,132.45,131.44,131.37,130.85,130.80,130.45,130.17,129.39,128.97,128.56,128.38,127.54,126.30,125.93,124.83,124.59,124.53,122.78,121.82,119.66,118.95,118.86,117.69,116.31,114.84,106.12,99.17,91.10,71.88,65.46,60.55,50.62,40.83,39.05,36.47,33.07,33.01,32.99,32.94,32.83,32.76,32.57,32.44,32.03,31.21,31.10,30.86,30.77,30.68,30.51,30.43,30.24,27.97,27.93,27.46,23.76,23.65,20.37,14.66,14.60,14.34。
The data of mass spectroscopy are: 2065.57 ([M+H]+).
The data of ultimate analysis are: C, 84.33; H, 9.86; N, 2.71.
From above data, described third product is for having the compound of structure shown in formula 23;
In three neck round-bottomed flasks, by the compound dissolution with structure shown in formula 23 of 2.00g in the tetrahydrofuran (THF) and 3mL water of 12mL, in described three neck round-bottomed flasks, add the potassium hydroxide of 400mg, 80 DEG C, carry out the reaction of 5 hours under the condition that stirs;
After described reaction terminates, the reaction product obtained is cooled to 25 DEG C, the volumetric molar concentration adding 20mL in described reaction product is the phosphate aqueous solution of 0.2mol/L, by the mixed solution chloroform extraction that obtains three times, merges organic phase; By described organic phase anhydrous sodium sulfate drying, cross the anhydrous sodium sulphate filtered in described organic phase, the filtrate obtained after described filtration is concentrated, using described concentrated after filtrate volume ratio be that the trichloromethane of 1:20 and the mixture of methyl alcohol carry out chromatography as developping agent post, obtain the phenanthro-carbazoles dyestuff of 1.94g, the yield of described phenanthro-carbazoles dyestuff is 99%.
Adopt nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method to carry out structural characterization to described phenanthro-carbazoles dyestuff, nucleus magnetic resonance characterization data is as follows:
1H NMR(400MHz,THF-d 8)δ:9.10(d,J＝8.4Hz,1H),8.96(m,6H),8.49(d,J＝8.7Hz,1H),8.23(m,6H),8.06(m,4H),7.52(d,J＝8.2Hz,4H),7.09(m,5H),6.98(d,J＝8.6Hz,1H),4.42(m,2H),2.83(m,8H),2.56(m,4H),2.23(m,5H),1.60(m,32H),1.44(m,56H),1.15(br,32H),0.93(m,16H),0.78(m,16H)。
13C NMR(100MHz,THF-d 8)δ:166.44,159.80,159.07,156.59,154.02,142.61,142.24,140.78,140.42,140.33,136.91,134.55,134.00,133.04,132.72,132.43,131.69,131.35,131.26,130.45,130.41,130.08,129.43,129.25,127.32,126.65,126.48,126.13,125.35,124.71,124.10,123.88,122.13,122.02,120.73,120.29,118.59,118.52,116.55,113.63,113.38,98.61,91.10,71.91,65.43,64.81,53.88,39.38,39.27,36.54,33.04,33.00,32.90,32.86,32.61,32.48,32.14,32.00,31.18,31.09,30.80,30.75,30.62,30.41,30.29,28.06,28.03,23.74,23.66,20.35,14.70,14.65,14.38。
The data of mass spectroscopy are: 2008.49561.
The data of ultimate analysis are: C, 84.29; H, 9.73; N, 2.79.
From above data, described phenanthro-carbazoles dyestuff has the structure shown in formula III:
Embodiment 3
Prepare dye-sensitized solar cells according to the method disclosed in document (Energy Environ.Sci., 2010,3,1924), detailed process is:
Phenanthro-carbazoles preparation of dyestuff embodiment 1 prepared becomes volumetric molar concentration to be the phenanthro-carbazoles dye solution of 150 μm of ol/L, and the solvent of described phenanthro-carbazoles dye solution is volume ratio is the ethanol of 9:1 and the mixing solutions of toluene;
By TiO 2the duplicature electrode of structure soaks 12 hours in above-mentioned phenanthro-carbazoles dye solution, takes out electrode, obtains the electrode of composite dye, by the electrode of described composite dye and the rear hot melt ring sealing of glass electrode assembling covering Platinum Nanoparticles, obtains battery container;
In described battery container, inject cobalt/cobalt salt ionogen, obtain dye-sensitized solar cells, described cobalt/cobalt salt electrolyte preparation method is: by the Co (phen) of 7.2mg 3[TFSI] 3with the Co (phen) of 27.2mg 3[TFSI] 2the concentration being dissolved in 100uL is the TBP of 0.5M and concentration is namely form cobalt/cobalt salt ionogen in the acetonitrile solution of the LiTFSI of 0.1M; Wherein phen is 1,10-Féraud beautiful jade, and TFSI is two (trimethyl fluoride sulfonyl) imines, and TBP is 4-tert .-butylpyridine, and LiTFSI is two (trimethyl fluoride sulfonyl) imine lithium, and above reagent is all purchased from Sigma-Aldrich Reagent Company.Co (phen) 3[TFSI] 3with Co (phen) 3[TFSI] 2synthesis reference literature (Xu, M.; Zhou, D.; Cai, N.; Liu, J.; Li R.; Wang, P.Energy Environ.Sci.2011,4,4735) the method preparation disclosed in.
According to the method described in technique scheme, the J-V curve of the dye-sensitized solar cells that the test embodiment of the present invention 3 prepares, test result as shown in Figure 1, Fig. 1 is the J-V curve of the dye-sensitized solar cells that the embodiment of the present invention 3 prepares, according to Fig. 1, according to the method described in technique scheme, calculate the open circuit voltage V of the dye-sensitized solar cells that the embodiment of the present invention 3 prepares oc, short-circuit current density j sc, packing factor FF and power-conversion efficiencies, test result is as shown in table 1, and table 1 is the performance test results of the dye-sensitized solar cells that the embodiment of the present invention and comparative example prepare.
Embodiment 4
Dye-sensitized solar cells is prepared according to the method described in embodiment 3, as different from Example 3, the phenanthro-carbazoles dyestuff that the phenanthro-carbazoles dyestuff alternative embodiment 1 adopting embodiment 2 to prepare prepares.
According to the method described in embodiment 3, the open circuit voltage V of the dye-sensitized cell that the test embodiment of the present invention 4 prepares oc, short-circuit current density j sc, packing factor FF and power-conversion efficiencies, test result is as shown in table 1.
Comparative example 1
Prepare dyestuff C261 according to the method disclosed in document (Adv.Energy Mater., 2014,4,1400244), and be the dye-sensitized solar cells of dyestuff with C261;
The molecular structure of C261 is as follows:
According to the method described in embodiment 3, test the open circuit voltage V of the dye-sensitized cell that comparative example 1 of the present invention prepares oc, short-circuit current density j sc, packing factor FF and power-conversion efficiencies, test result is as shown in table 1.
The performance test results of the dye-sensitized solar cells that table 1 embodiment of the present invention and comparative example prepare
As shown in Table 1, the dye-sensitized solar cells that the phenanthro-carbazoles preparation of dyestuff that the embodiment of the present invention provides obtains has higher power-conversion efficiencies.
As seen from the above embodiment, the invention provides a kind of phenanthro-carbazoles dyestuff, there is the structure shown in formula I; In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36; R 2and R 3be the alkyl of 1 ~ 36 independently selected from hydrogen, fluorine, carbonatoms; R 4be selected from the aryl of carboxyl substituted; R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.The invention provides a kind of preparation method of phenanthro-carbazoles dyestuff, comprising: the compound with structure shown in formula 1 is carried out linked reaction with the compound with structure shown in formula 2, obtains phenanthro-carbazoles dyestuff.The invention provides a kind of dye-sensitized solar cells, comprise the phenanthro-carbazoles dyestuff described in such scheme.Phenanthro-carbazoles dyestuff provided by the invention has donor monomer phenanthro-carbazole, and phenanthro-carbazole structure unit has high-fluorescence quantum yield and long lifetime of excited state; The dye-sensitized solar cells that phenanthro-carbazoles preparation of dyestuff provided by the invention is obtained has higher power-conversion efficiencies.

Claims (10)

1. a phenanthro-carbazoles dyestuff, has the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
2. phenanthro-carbazoles dyestuff according to claim 1, is characterized in that, the R in described formula I 1be selected from the alkyl that carbonatoms is 2 ~ 18;
R 2and R 3the phenyl replaced independently selected from hydrogen, carbonatoms be 2 ~ 18 alkyl, the carbonatoms alkyl that is 2 ~ 18 or carbonatoms are the phenyl that replaces of alkoxyl group of 2 ~ 18.
3. phenanthro-carbazoles dyestuff according to claim 1, is characterized in that, the R in described formula I 4be selected from the one in formula A ~ formula C:
4. phenanthro-carbazoles dyestuff according to claim 1, is characterized in that, the R in described formula I 5be selected from the one in formula D ~ formula H:
R in formula D 6, and the R in formula H 12, R 13independently selected from hydrogen, carbonatoms be 1 ~ 36 alkyl or carbonatoms be the alkoxyl group of 1 ~ 36;
R in formula E 7, R 8, the R in formula F 9, and the R in formula G 10, R 11be the alkyl of 1 ~ 36 independently selected from hydrogen or carbonatoms;
Y in formula D 1, y in formula E 2, y in formula F 3with the y in formula H 4independently selected from 0 or 1.
5. phenanthro-carbazoles dyestuff according to claim 1, is characterized in that, described phenanthro-carbazoles dyestuff has the structure shown in formula II or formula III:
6. a preparation method for phenanthro-carbazoles dyestuff, comprising:
The compound with structure shown in formula 1 is carried out linked reaction with the compound with structure shown in formula 2, obtains phenanthro-carbazoles dyestuff;
In formula 1, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36;
In formula 2, R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 14be selected from the aryl that ester group replaces;
Described phenanthro-carbazoles dyestuff has the structure shown in formula I:
In formula I, R 1be selected from the alkyl that carbonatoms is 1 ~ 36;
R 2and R 3the phenyl replaced independently selected from hydrogen, fluorine, carbonatoms be 1 ~ 36 alkyl, the carbonatoms alkyl that is 1 ~ 36 or carbonatoms are the phenyl that replaces of alkoxyl group of 1 ~ 36;
R 4be selected from the aryl of carboxyl substituted;
R 5be selected from the alkyl that hydrogen, aryl or carbonatoms are 1 ~ 36.
7. method according to claim 6, is characterized in that, described in there is the compound of structure shown in formula 1 preparation method be:
The compound with structure shown in formula 4 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1;
In formula 4, R 15be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
8. method according to claim 6, is characterized in that, described in there is the compound of structure shown in formula 1 preparation method be:
The compound with structure shown in formula 6 is carried out linked reaction with the compound with structure shown in formula 5, obtains the compound with structure shown in formula 1;
In formula 6, R 16be selected from aryl;
In formula 5, R 1be selected from the alkyl that carbonatoms is 1 ~ 36.
9. method according to claim 6, is characterized in that, the temperature of described linked reaction is 110 DEG C ~ 130 DEG C.
10. a dye-sensitized solar cells, comprises the phenanthro-carbazoles dyestuff described in any one in Claims 1 to 5, or the phenanthro-carbazoles dyestuff that the method in claim 6 ~ 9 described in any one prepares.
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