CN102002037A - Triphenylamine compound and application thereof - Google Patents

Triphenylamine compound and application thereof Download PDF

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CN102002037A
CN102002037A CN 201010526095 CN201010526095A CN102002037A CN 102002037 A CN102002037 A CN 102002037A CN 201010526095 CN201010526095 CN 201010526095 CN 201010526095 A CN201010526095 A CN 201010526095A CN 102002037 A CN102002037 A CN 102002037A
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compound
formula
heterocyclic radical
heteroatoms
triphenylamine compounds
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CN102002037B (en
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田禾
王成有
李晶
蔡升云
苏建华
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East China University of Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a triphenylamine compound and application thereof. The triphenylamine compound is characterized in that one side is a power supply subbase, another side is a power absorbing subbase, and a Donor-pi-Acceptor system is formed. The nonplanarity of the compound can effectively reduce the pi-pi accumulation of dye on the surface of TiO2 and has wider absorption spectrum, therefore increasing light current and photoelectric conversion efficiency.

Description

Triphenylamine compounds and uses thereof
Technical field
The present invention relates to a kind of triphenylamine compounds and uses thereof, particularly a kind of cyclo triphenylamine compounds and the application in the preparation photoelectric conversion material thereof.
Background technology
Be accompanied by developing rapidly of human industrial civilization, mineral wealth such as coal, oil and natural gas are exhausted day by day, and energy dilemma of Yin Faing and environmental pollution have become the serious problems that need to be resolved hurrily thus.Therefore people press for and seek other new replaced energy.Dye sensitization solar battery (B.O ' Regan, M.
Figure BSA00000325773100011
Nature, 1991,353,737-740),, enjoy the concern of scientists because of it has the potential practical value.
In recent years, nonmetal organic dye sensitized solar cell has received increasing concern, compares the metal Ru based dye, and nonmetal organic dye has advantages such as the low and structurally variable of cost.Yet the electricity conversion of nonmetal organic dye does not reach the level of ruthenium based dye as yet, one very important reasons be accumulation between the non-Organometallic dye serious (but not Organometallic dye is given body and acceptor groups copline all again usually), form and swash a layer mixture, thereby cause electricity conversion greatly to reduce.
The nitrogen of triphenylamine compounds has very strong electron donation and very low ionization energy, be oxidized to radical cation easily and show positive polarity, and the nonplanarity of triphenylamine can effectively reduce dyestuff at TiO 2The pi-pi accumulation on surface, therefore, the triphenylamine compounds has higher hole transport efficient.The present invention mainly concentrate on light-sensitive coloring agent in the dye sensitization of solar designed a series of be the derivative organic dye of parent with a kind of cyclo triphenylamine, adopt and introduce different substituting groups, bridge chain and electronics receive group and regulate the structure of dyestuff, thereby satisfy the application requiring aspect dye sensitization solar battery.
Summary of the invention
The research that the present inventor is extensive and deep has designed and synthesized a kind of novel triphenylamine compounds.This compounds is electron-donating group on one side, and the other side is an electron withdrawing group, has formed a Donor-π-Acceptor system.The nonplanarity of this compounds can effectively reduce dyestuff at TiO 2The pi-pi accumulation on surface has the absorption spectrum of broad again, has increased photoelectric current, has improved its photoelectric transformation efficiency.
One of the object of the invention is, a kind of above-mentioned novel triphenylamine compounds is provided.
The said triphenylamine compounds of the present invention, it has structure shown in the formula I:
Figure BSA00000325773100021
Among the formula I: R 1, R 2, R 3And R 4Independently be selected from respectively: hydrogen (H), C 1～C 18Alkyl, C 1～C 12Alkoxyl group, amino, C 5～C 20Cyclic hydrocarbon radical or aromatic ring yl or C 4～C 20A kind of in the heterocyclic radical, wherein the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (comprising two kinds), the heteroatoms number is 1～3 integer; R 5Be group shown in the formula II:
Among the formula II, A be " divalence " vinyl (CH=CH-) or ethynyl (C ≡ C-); B is the C of " divalence " 6～C 20Aromatic ring yl or C 4～C 20Heterocyclic radical; R 6For hydrogen (H) or cyano group (CN); R 7A kind of for hydrogen (H), metallic cation or non-metal cations; X is 0 or 1; Y is 0 or 1; Z is 0 or 1;
Wherein (among the formula II), the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (containing two kinds), the heteroatoms number is 1～4 integer.
Two of the object of the invention is, the purposes of a kind of above-mentioned triphenylamine compounds (compound shown in the formula I) is provided, i.e. the application of compound shown in the formula I in the sensitizing agent of preparation dye sensitization solar battery.
In addition, the present invention also provides the method for compound shown in a kind of preparation formula I, and said method is to be raw material with compound shown in the formula III, and comprises step (a), (b) and (c):
(a) step of introducing substituted benzene in compound shown in the formula III;
(b) in by step (a) gained compound, introduce R 5Step; With
(c) in by step (a) gained compound, introduce R 1And R 2Step.
Wherein, the order of step (b) and (c) can exchange according to the needs of the different compounds of preparation.
In an optimal technical scheme of the present invention, R 1, R 2, R 3And R 4Independently be selected from respectively: H, C 1～C 6Alkyl, C 1～C 6Alkoxyl group, C 5～C 10Cycloalkyl or aromatic ring yl or C 4～C 15It is a kind of in the heterocyclic radical,
Wherein the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (containing two kinds), the heteroatoms number is 1～3 integer;
Preferred R 1, R 2, R 3And R 4Independently be selected from respectively: H, C 1～C 3Alkyl, C 1～C 3Alkoxyl group or C 5～C 15Contain in the N heterocyclic radical a kind of;
Best R 1, R 2, R 3And R 4Independently be selected from respectively: H, methoxyl group or
Figure BSA00000325773100031
In a kind of, wherein the curve place represents to replace the position.
In another optimal technical scheme of the present invention, B is the C of " divalence " 4～C 20Heterocyclic radical, the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (containing two kinds), the heteroatoms number is 1～4 integer;
Preferred B is the C of " divalence " 4～C 10Heterocyclic radical, the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (containing two kinds), the heteroatoms number is 1～4 integer;
Best B is selected from: a kind of in the following groups:
Figure BSA00000325773100032
Wherein the curve place represents to replace the position.
Description of drawings
The uv-absorbing spectrogram of compound (Compound I-1) in chloroformic solution that Fig. 1 embodiment 1 is prepared;
The prepared compound (Compound I-5) of Fig. 2 embodiment 5 is as the all-solid-state dye-sensitized solar cell I-V curve of sensitizing agent.
Fig. 3 Compound I-1 is as the dye sensitization solar battery I-V curve of sensitizing agent.
Concrete preparation method
Terminological interpretation: related its implication of " divalence " group of preamble is meant: the remainder after certain organism is replaced by two.
Previously described (a) introduces the step of substituted benzene in compound shown in the formula III; Can adopt following synthesis strategy:
To have R 3, R 4, aldehyde radical (CHO) and/or compound shown in the halogeno-benzene of halogen (F, Cl, Br or I) and formula III reaction, thus reach the purpose of in compound shown in the formula III, introducing substituted benzene.
Previously described (b) introduces R in by step (a) gained compound 5Step; Can adopt and comprise following synthesis strategy:
(i) will contain acetylene compound (methylbutynol etc.) and the compound reaction that has halogen (F, Cl, Br or I) by step (a) gained, or by B-CH 2-PPh 3 +Br -(implication of B is described identical with preamble) with have aldehyde radical (CHO) by step (a) gained compound, thereby reach in compound shown in the formula III purpose (implication of A is described identical with preamble) of introducing A;
(ii) by the B that has boric acid functional group (B-B (OH) 2) and have reacting by step (a) gained compound of halogen (F, Cl, Br or I), thereby reach the purpose (implication of B is described identical with preamble) of in compound shown in the formula III, introducing B;
(iii) by compound shown in the formula IV with by the resultant compound that contains ethynyl of synthesis strategy (i), or with have (the B (OH) of boric acid functional group 2) can get the target compound (compound shown in the formula I) of y ≠ 0 by compound [this compound is by having being got by the compound conversion of step (a) gained of halogen (F, Cl, Br or the I)] reaction of step (a) gained.
Among the formula IV, X is halogen (F, Cl, Br or I).
Previously described (c) introduces R in by step (a) gained compound 1And R 2Step, its synthesis strategy comprises: earlier will be by the halogenation of step (a) gained compound, and then and R 1'-H and/or R 2'-H reaction is introduced R thereby reach in by step (a) gained compound 1And R 2Purpose;
R wherein 1' and R 2' independently be selected from respectively: C 1～C 18Alkyl, C 1～C 12Alkoxyl group, amino, C 5～C 20Cyclic hydrocarbon radical or aromatic ring yl or C 4～C 20A kind of in the heterocyclic radical, wherein the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds (containing two kinds), the heteroatoms number is 1～3 integer.
Above-mentioned synthesis strategy can use separately, also can carry out appropriate combination and use, and its order also can suitably exchange according to the needs of target compound.
The triphenylamine compounds of the present invention's design and preparation can be used as the sensitizing agent of dye sensitization solar battery.
Below by embodiment the present invention is further elaborated, its purpose only is to understand better content of the present invention.Therefore, the cited case should not be considered as limiting the scope of the invention.
In addition, the compound that does not provide concrete synthetic method in an embodiment is to synthesize by the synthetic method that existing document or supplier provide, and said room temperature is meant among the embodiment: 15 ℃～25 ℃
Embodiment 1
Figure BSA00000325773100051
In the single port bottle of 250ml, add 50ml Hydrogen bromide and 13.1g triphenyl phosphorus, under the argon shield, be heated to 70 ℃, kept 5 minutes.Cooling has solid to separate out, and uses a small amount of washed with dichloromethane, and drying obtains faint yellow solid powder 16.3g, compound a, productive rate 95%.
Figure BSA00000325773100052
In 100ml single port bottle, add thiophene aldehyde and the 30ml methyl alcohol of 5.6g, to stir, the ice bath protection adds the 2.0g sodium borohydride down, reacts 30 minutes.Reactant is poured in the water, uses dichloromethane extraction, be spin-dried for, obtain 5.4g yellow liquid, compound 1, yield 95%.
Figure BSA00000325773100053
In 100ml single port bottle, add 5.7g compound 1,17.2g compound a and 30ml methylene dichloride, argon shield refluxed 3 hours down.Behind the cool to room temperature, there are a large amount of white solids to separate out, filter, use washed with dichloromethane, get compound 2, yield 80%.
In the 100ml there-necked flask, add 1.93g compound III, 3.48g to benzaldehyde iodine, 0.32g copper powder, 2.07g salt of wormwood, 40mg crown ether and 40ml orthodichlorobenzene, reflux is 40 hours under the argon shield, and solvent is removed in underpressure distillation.Residuum extracts with hot toluene, filters.Filtrate obtains thick product after revolving steaming, uses ethyl alcohol recrystallization, obtains compound 4, yield 62%.
1H-NMR(CDCl 3)：δ9.69(s，1H)，7.51(m，8H)，7.41(m，2H)，6.86(s，2H)，6.35(d，2H).
Figure BSA00000325773100061
In 100ml single port bottle, add 10g compound 4,14.6g compound 2,9.1g salt of wormwood, 0.5g crown ether and 50ml dimethyl formamide, stirring at room 5 hours.Pouring into has a large amount of faint yellow solids to separate out in the water, suction filtration obtains thick product, uses ethyl alcohol recrystallization, obtains compound 5, yield 75%.
1H-NMR(DMSO)：δ7.57(m，6H)，7.45(m，2H)，7.34(d，1H)，7.19(d，2H)，7.07(dd，2H)，6.99(dd，1H)，6.93(s，2H)，6.74(d，1H)，6.10(d，2H).
Figure BSA00000325773100062
In the 100ml there-necked flask, add 3.77g compound 5 and 15ml dimethyl formamide, stir, be heated to dissolving.Under the ice bath, in there-necked flask, slowly drip the 0.5g phosphorus oxychloride.Remove ice bath, be heated to 80 ℃, reacted 6 hours.After being cooled to normal temperature, pour in the frozen water, be neutralized to neutrality with potassium hydroxide, have yellow solid to separate out, suction filtration gets thick product, uses ethyl alcohol recrystallization, gets compound 6, yield 80%.
1H-NMR(DMSO)：δ9.82(s，1H)，7.87(t，1H)，7.56(dd，6H)，7.46(t，2H)，7.29(d，3H)，7.11(m，2H)，6.93(s，2H)，6.13(d，2H).
Figure BSA00000325773100063
In 100ml single port bottle, add 4.03g compound 6,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 7, yield 80%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.52(m，11H)，7.22(d，1H)，7.09(d，1H)，6.96(s，2H)，6.13(d，2H). 13C-NMR(DMSO)：δ163.87，153.32，149.14，146.30，141.77，141.52，135.63，133.07，132.91，130.50，130.31，130.12，129.78，128.10，127.60，126.05，125.83，116.80，116.74，111.56，96.74.HRMS(ESI，m/z)：[M-H] -calcd?for(C 30H 19N 2O 2S)，471.1167；found，471.1153。
Embodiment 2
Figure BSA00000325773100071
In the 100ml there-necked flask, add 1.93g compound III, 2.36g paradibromobenzene, 0.32g copper powder, 2.07g salt of wormwood, 40mg crown ether and 40ml orthodichlorobenzene, reflux is 40 hours under the argon shield, and solvent is removed in underpressure distillation.Residuum extracts with hot toluene, filters.Filtrate obtains thick product after revolving steaming, uses ethyl alcohol recrystallization, obtains compound 8, yield 60%.
1H-NMR(DMSO)：δ7.47(m，6H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.12(d，2H).
Figure BSA00000325773100072
In the 50ml two-mouth bottle, add 3.5g compound 8,1.56g compound 9, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 10, yield 56%.
1H-NMR(DMSO)：δ9.78(s，1H)，7.91(t，1H)，7.56(m，6H)，7.46(t，5H)，6.93(s，2H)，6.18(d，2H).
Figure BSA00000325773100081
In 100ml single port bottle, add 3.79g compound 10,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 11, yield 80%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.52(m，11H)，6.96(s，2H)，6.13(d，2H)。
Embodiment 3
Figure BSA00000325773100082
In the 100ml there-necked flask, add 3.5g compound 8 and 0.48g magnesium rod, under the argon shield, inject the 45ml tetrahydrofuran (THF), and inject the 1ml monobromethane and make initiator, reflux 1 hour.Be cooled to the refrigerator of reaction flask being put into after the room temperature-78 ℃ and stir, add the 3ml trimethyl borate after half an hour,, reaction half an hour, reaction flask is taken out stirred overnight at room temperature from refrigerator.Dripping dilute hydrochloric acid to yellow in bottle disappears.Use dichloromethane extraction, be spin-dried for, dissolve with a small amount of methylene dichloride again, add a large amount of acetonitriles, have solid to separate out, suction filtration gets compound 12, yield 35%.
Figure BSA00000325773100083
In the 50ml two-mouth bottle, add 3.13g compound 12,2.92g compound 13, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=cross post separation (v/v) at 1: 5 gets compound 14, yield 55%.
1H-NMR(DMSO)：δ7.83(d，1H)，7.63(d，1H)，7.47(m，6H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.12(d，2H).
In the 50ml two-mouth bottle, add 3.81g compound 14,1.56g compound 9, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 15, yield 56%.
1H-NMR(DMSO)：δ9.78(s，1H)，7.83(d，1H)，7.63(d，1H)，7.91(t，1H)，7.56(m，6H)，7.46(t，5H)，6.93(s，2H)，6.18(d，2H).
Figure BSA00000325773100092
In 100ml single port bottle, add 5.13g compound 15,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 16, yield 79%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.83(d，1H)，7.63(d，1H)7.52(m，11H)，6.96(s，2H)，6.13(d，2H).
Embodiment 4
Figure BSA00000325773100093
In the there-necked flask of 250ml, add 35g compound 8 and 120ml triethylamine, stirring at room is to all dissolvings.Add the 15ml methylbutynol, stir about 20 minutes, ice bath add catalytic amount cuprous iodide and two (triphenyl phosphorus) palladium chloride down, after stirring closest friend yellow mercury oxide generates, are warming up to 50 ℃, stir 3 hours.Be spin-dried for solvent, the chloroform dissolving, washing, dry organic layer is spin-dried for, and uses the developping agent tetracol phenixin: ethyl acetate=10: 1 (v/v) is crossed the post separation, gets compound 17, yield 50%.
Figure BSA00000325773100101
In 150ml single port bottle, add 3.51g compound 17,2.52g potassium hydroxide and 70ml Virahol, reflux is 4 hours under the argon shield.Reaction is spin-dried for organic layer after finishing, and uses the developping agent methylene dichloride: normal hexane=cross post separation at 1: 3 gets compound 18, yield 83%.
1H-NMR(DMSO)：δ7.47(m，6H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.12(d，2H)，3.54(s，1H).
Figure BSA00000325773100102
In 100ml single port bottle, add 2.93g compound 18,2.91g compound 13, proper catalyst, 50ml triethylamine and 50ml tetrahydrofuran (THF), under the argon shield, reflux 24 hours.Reaction filters out throw out after finishing, and is spin-dried for organic solvent, dissolves after washing with methylene dichloride, and separatory is used the anhydrous magnesium sulfate drying organic layer, is spin-dried for, and uses the developping agent methylene dichloride: sherwood oil=1: 3 (v/v) is crossed post and is separated, and gets compound 19, yield 42%.
1H-NMR(DMSO)：δ7.82(d，1H)，7.61(d，1H)，7.47(m，6H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.12(d，2H).
Figure BSA00000325773100111
In the 50ml two-mouth bottle, add 5.05g compound 19,1.56g compound 9, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 20, yield 55%.
1H-NMR(DMSO)：δ9.76(s，1H)，7.81(d，1H)，7.61(d，1H)，7.90(t，1H)，7.56(m，6H)，7.46(t，5H)，6.93(s，2H)，6.18(d，2H).
Figure BSA00000325773100112
In 100ml single port bottle, add 5.37g compound 20,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 21, yield 80%.
1H-NMR(DMSO)：δ8.41(s，1H)，7.87(d，1H)，7.82(d，1H)，7.62(d，1H)7.52(m，11H)，6.96(s，2H)，6.18(d，2H).
Embodiment 5
Figure BSA00000325773100113
In the 100ml there-necked flask, add 1.93g compound III, 2.17g compound 22,0.32g copper powder, 2.07g salt of wormwood, 40mg crown ether and 40ml orthodichlorobenzene, reflux is 40 hours under the argon shield, and solvent is removed in underpressure distillation.Residuum extracts with hot toluene, filters.Filtrate obtains thick product after revolving steaming, uses ethyl alcohol recrystallization, obtains compound 23, yield 35%.
1H-NMR(DMSO)：δ7.47(m，4H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.67(dd，1H)，6.12(d，2H)，1.80(m，6H).
Figure BSA00000325773100121
In the 100ml there-necked flask, add 3.29g compound 23,1.78gN-bromo-succinimide and 30ml tetracol phenixin, refluxed 7 hours.Suction filtration has a large amount of solids to separate out after the filtrate cooling while hot, uses ethyl alcohol recrystallization, gets compound 24, yield 70%.
1H-NMR(DMSO)：δ7.45(m，4H)，7.32(m，2H)，7.05(d，2H)，6.82(s，2H)，6.10(d，2H)，1.80(m，6H).
Figure BSA00000325773100122
In the 50ml two-mouth bottle, add 4.07g compound 24,1.56g compound 9, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 25, yield 55%.
1H-NMR(DMSO)：δ9.78(s，1H)，7.91(t，1H)，7.56(m，4H)，7.46(t，5H)，6.93(s，2H)，6.18(d，2H)，1.81(m，6H)
In 100ml single port bottle, add 4.39g compound 25,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 26, yield 78%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.52(m，9H)，6.96(s，2H)，6.13(d，2H)，1.81(m，6H).
Embodiment 6
Figure BSA00000325773100131
In the 50ml two-mouth bottle, add 3.13g compound 12,2.98g compound 27, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 28, yield 52%.
1H-NMR(DMSO)：δ7.47(m，6H)，7.36(m，2H)，7.05(d，2H)，6.82(s，2H)，6.12(d，2H)，4.34(s，4H).
Figure BSA00000325773100132
In the 50ml two-mouth bottle, add 4.87g compound 28,1.56g compound 9, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 29, yield 50%.
1H-NMR(DMSO)：δ9.78(s，1H)，7.91(t，1H)，7.56(m，6H)，7.46(t，5H)，6.93(s，2H)，6.18(d，2H)，4.34(s，4H).
Figure BSA00000325773100133
In 100ml single port bottle, add 5.19g compound 29,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 30, yield 75%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.52(d，11H)，6.96(s，2H)，6.13(d，2H)，4.34(s，4H)。
Embodiment 7
Figure BSA00000325773100141
In the history Neck bottle of 100ml, add 1g compound b and 30ml tetrahydrofuran (THF), be cooled to-78 ℃, slowly drip the 1.6M n-Butyl Lithium of 4.8ml, add 1ml exsiccant N again, dinethylformamide, stirring at normal temperature is spent the night.Reaction solution is poured in the dilute hydrochloric acid solution, had precipitation to generate, filter drying.Throw out and 1.02gN-bromo-succinimide are dissolved in 20mlN, and in the dinethylformamide, stirring at room 2 hours is poured in the frozen water, suction filtration, and drying obtains compound d, productive rate 90%.
Figure BSA00000325773100142
In the 50ml two-mouth bottle, add 3.13g compound 12,2.48g compound d, proper catalyst four-triphenyl phosphorus palladium, 20ml tetrahydrofuran (THF) and 5ml2M sodium carbonate solution, under the argon shield, 80 ℃ were reacted 24 hours down.Use the dichloromethane extraction organic layer, be spin-dried for yellow solid.Use the developping agent methylene dichloride: sherwood oil=1: 5 (v/v) is crossed post and is separated, and gets compound 31, yield 58%.
1H-NMR(DMSO)：δ9.78(s，1H)，7.51(m，8H)，7.41(m，2H)，6.86(s，2H)，6.35(d，2H)，4.34(s，4H).
Figure BSA00000325773100143
In 100ml single port bottle, add 4.37g compound 31,0.85g cyanoacetic acid, 3 piperidines and 50ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 32, yield 77%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.51(m，8H)，7.41(m，2H)，6.86(s，2H)，6.35(d，2H)，4.34(s，4H).
Embodiment 8
Figure BSA00000325773100151
In the 250ml there-necked flask, add 2.97g compound 4,2.48g potassiumiodide, 100ml Glacial acetic acid and 10ml water, after the mixture heating up to 80 ℃, add the 2.22g Potassium Iodate, reacted 4 hours.After the reaction end, pour in the big water gaging, use ethyl acetate extraction three times, merge organic phase, be spin-dried for, use the developping agent methylene dichloride: sherwood oil=2: 1 (v/v) is crossed post and is separated, and gets compound 33, yield 88%.
Figure BSA00000325773100152
In the 100ml there-necked flask, add 5.49g compound 33,3.68g compound 3,0.32g copper powder, 2.07g salt of wormwood, 40mg crown ether and 40ml orthodichlorobenzene, reflux is 40 hours under the argon shield, and solvent is removed in underpressure distillation.Residuum extracts with hot toluene, filters.Filtrate obtains thick product after revolving steaming, uses ethyl alcohol recrystallization, obtains compound 34, yield 60%.
1H-NMR(CDCl 3)：δ9.69(s，1H)，7.53(m，18H)，7.41(m，4H)，6.86(s，4H)，6.13(m，6H).
Figure BSA00000325773100161
In 100ml single port bottle, add 6.82g compound 34,4.38g compound 2,2.3g salt of wormwood, 0.2g crown ether and 50ml dimethyl formamide, stirring at room 5 hours.Pouring into has a large amount of faint yellow solids to separate out in the water, suction filtration obtains thick product, uses ethyl alcohol recrystallization, obtains compound 35, yield 75%.
1H-NMR(DMSO)：δ7.57(m，18H)，7.45(m，4H)，7.34(d，1H)，7.19(d，2H)，7.07(dd，2H)，6.99(dd，1H)，6.93(s，2H)，6.74(d，1H)，6.10(d，6H).
In the 100ml there-necked flask, add 7.59g compound 35 and 15ml dimethyl formamide, stir, be heated to dissolving.Under the ice bath, in there-necked flask, slowly drip the 0.5g phosphorus oxychloride.Remove ice bath, be heated to 80 ℃, reacted 6 hours.After being cooled to normal temperature, pour in the frozen water, be neutralized to neutrality with potassium hydroxide, have yellow solid to separate out, suction filtration gets thick product, uses ethyl alcohol recrystallization, gets compound 36, yield 82%.
1H-NMR(DMSO)：δ9.82(s，1H)，7.87(t，1H)，7.56(dd，18H)，7.46(m，4H)，7.29(d，3H)，7.11(m，2H)，6.93(s，2H)，6.13(d，6H).
Figure BSA00000325773100171
In 100ml single port bottle, add 0.78g compound 36,0.11g cyanoacetic acid, 3 piperidines and 30ml tetrahydrofuran (THF), reflux 18 hours.Have dark red solid to separate out after cold the going, suction filtration gets thick product, with chloroform and normal hexane recrystallization, gets compound 37, yield 82%.
1H-NMR(DMSO)：δ8.40(s，1H)，7.88(d，1H)，7.52(m，25H)，7.22(d，1H)，7.09(d，1H)，6.96(s，2H)，6.13(d，6H)。
Embodiment 9
Make solid-state dye sensitized solar cell device with Compound I-3 as photosensitizer: with after the burned nano titanium oxide heated by electrodes to 80 ℃, in 3 * 10 of Compound I-3 preparation -4Soak sensitization 12 hours in the mol acetonitrile solution.Sensitization is taken out after finishing, and rinses out unabsorbed dyestuff with dehydrated alcohol, dries up.Vacuum evaporation one deck hole mobile material spiro-OMe-TAD and gold-plated glass resistor are formed dye sensitization solar battery and are measured on this sensitization electrode.Under the irradiation of AM1.5 standard light source, measuring its open circuit voltage is 0.592V, short-circuit current 6.83mA cm -2, packing factor 0.68, electricity conversion 2.77%.Its photoelectric current and photovoltage curve are seen Fig. 2.
Embodiment 10
Make liquid electrolyte dye sensitization solar battery device with Compound I-1～I-8 as photosensitizer: after will burned nano titanium oxide heated by electrodes to 80 ℃, Compound I-1～I-8 prepare 3 * 10 -4Soak sensitization 12 hours in the mol acetonitrile solution.Sensitization is taken out after finishing, and rinses out unabsorbed dyestuff with dehydrated alcohol, dries up.This sensitization electrode and platinized glass electrode and liquid electrolyte are formed dye sensitization solar battery and measure that (liquid electrolyte consists of: with methoxypropionitrile and acetonitrile as solvent, 3-methyl isophthalic acid-butyl imidazole the iodine that adds 0.3 mol, 0.1 the lithium iodide of mol, 1.2 the iodine of mol, the tert .-butylpyridine of 0.6 mol).Under the irradiation of AM1.5 standard light source, measure battery performance parameter and list in table 1.
The photoelectric properties of the dye sensitization solar battery of table 1 cyclo triphenylamine radical dye sensitization
Figure BSA00000325773100181

Claims (9)

1. triphenylamine compounds, it has structure shown in the formula I:
Figure FSA00000325773000011
Among the formula I: R 1, R 2, R 3And R 4Independently be selected from respectively: H, C 1～C 18Alkyl, C 1～C 12Alkoxyl group, amino, C 5～C 20Cyclic hydrocarbon radical or aromatic ring yl or C 4～C 20A kind of in the heterocyclic radical, wherein the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds, the heteroatoms number is 1～3 integer; R 5Be group shown in the formula II:
Figure FSA00000325773000012
Among the formula II, A is-CH=CH-or-C ≡ C-; B is the C of " divalence " 6～C 20Aromatic ring yl or C 4～C 20Heterocyclic radical; R 6For H or-CN; R 7A kind of for H, metallic cation or non-metal cations; X is 0 or 1; Y is 0 or 1; Z is 0 or 1;
Wherein, the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds, the heteroatoms number is 1～4 integer.
2. triphenylamine compounds as claimed in claim 1 is characterized in that, wherein R 1, R 2, R 3And R 4Independently be selected from respectively: H, C 1～C 6Alkyl, C 1～C 6Alkoxyl group, C 5～C 10Cycloalkyl or aromatic ring yl or C 4～C 15A kind of in the heterocyclic radical.
3. triphenylamine compounds as claimed in claim 2 is characterized in that, wherein R 1, R 2, R 3And R 4Independently be selected from respectively: H, C 1～C 3Alkyl, C 1～C 3Alkoxyl group or C 5～C 15Contain in the N heterocyclic radical a kind of.
4. triphenylamine compounds as claimed in claim 3 is characterized in that, wherein R 1, R 2, R 3And R 4Independently be selected from respectively: H, methoxyl group or
Figure FSA00000325773000013
In a kind of, wherein the curve place represents to replace the position.
5. triphenylamine compounds as claimed in claim 1 is characterized in that, wherein B is the C of " divalence " 4～C 20Heterocyclic radical, the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds, the heteroatoms number is 1～4 integer.
6. triphenylamine compounds as claimed in claim 5 is characterized in that, wherein B is the C of " divalence " 4～C 10Heterocyclic radical, the heteroatoms of said heterocyclic radical is selected from: among N, S or the O one or two or more kinds, the heteroatoms number is 1～4 integer.
7. triphenylamine compounds as claimed in claim 6 is characterized in that wherein B is selected from: a kind of in the following groups:
Figure FSA00000325773000021
Wherein the curve place represents to replace the position.
8. as claim 4 or 7 described triphenylamine compounds, it is characterized in that described triphenylamine compounds is a compound shown in formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, formula I-7 or the formula I-8:
Figure FSA00000325773000022
Figure FSA00000325773000031
9. as the application of any described triphenylamine compounds in the claim 1～8 in the sensitizing agent of preparation dye sensitization solar battery.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604415A (en) * 2012-02-28 2012-07-25 大连理工大学 Preparation method of thiophene pyrazine dye and application thereof in dye sensitization solar battery
WO2013068588A1 (en) * 2011-11-10 2013-05-16 Commissariat à l'énergie atomique et aux énergies alternatives Organic colourant and uses thereof in photovoltaic cells
CN103130797A (en) * 2013-02-01 2013-06-05 中国科学院宁波材料技术与工程研究所 Triphenylamine line type materials modified by electron drawing group and preparation method and purpose thereof
JP2013181108A (en) * 2012-03-01 2013-09-12 Kanto Natural Gas Development Co Ltd Highly-active complete organic dye compound for dye-sensitized photoelectric conversion element, and photoelectric conversion element using the same
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CN110204693A (en) * 2019-06-11 2019-09-06 百合花集团股份有限公司 Macromolecule covalent organic framework polymer and preparation method and application based on triphenylamine derivative

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101362863A (en) * 2008-09-12 2009-02-11 南开大学 Triphenyl amine dyes for dye-sensitized solar cells
CN101497746A (en) * 2009-03-05 2009-08-05 中国科学院长春应用化学研究所 Organic dye containing thiophen ethylene and dye sensitization solar cell prepared thereby
CN101866757A (en) * 2009-04-15 2010-10-20 柯尼卡美能达商用科技株式会社 Photo-electric conversion element and solar cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101362863A (en) * 2008-09-12 2009-02-11 南开大学 Triphenyl amine dyes for dye-sensitized solar cells
CN101497746A (en) * 2009-03-05 2009-08-05 中国科学院长春应用化学研究所 Organic dye containing thiophen ethylene and dye sensitization solar cell prepared thereby
CN101866757A (en) * 2009-04-15 2010-10-20 柯尼卡美能达商用科技株式会社 Photo-electric conversion element and solar cell

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US9171676B2 (en) 2011-11-10 2015-10-27 COMMISSARIAT {dot over (A)} L'ĖNERGIE ATOMIQUE ET AUX ÉNERGIES ALTERNATIVES Organic colourant and uses thereof in photovoltaic cells
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