CN103450700A - Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell - Google Patents

Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell Download PDF

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CN103450700A
CN103450700A CN2013103744803A CN201310374480A CN103450700A CN 103450700 A CN103450700 A CN 103450700A CN 2013103744803 A CN2013103744803 A CN 2013103744803A CN 201310374480 A CN201310374480 A CN 201310374480A CN 103450700 A CN103450700 A CN 103450700A
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carbazole
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dyestuff
dye
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CN103450700B (en
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刘军民
苏成勇
谭礼林
黄剑锋
吴优
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Sun Yat Sen University
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Abstract

The invention discloses tree-based organic dyestuff based on carbazole or triphenylamine derivatives. The chemical general formula of the tree-based organic dyestuff is as shown in the specifications. The invention also discloses an application of the tree-based organic dyestuff based on the carbazole or triphenylamine derivatives in the preparation of a dye-sensitized solar cell. The tree-based structure of the dyestuff can be used for ensuring the bathochromic-shift of absorption spectrums by adding donors and prolonging conjugates and effectively inhibiting the molecular aggregation caused by the dyestuff absorbed on TiO2, and meanwhile, dyestuff molecules contain multiple thiophene or derivatives of the thiophene, so that the light stability and the electron-transport property of the organic dyestuff are enhanced. The organic dyestuff can serve as a photosensitizer to be used for preparing the dye-sensitized solar cell and has high conversion efficiency.

Description

A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative and the application in preparing dye sensitization solar battery thereof
Technical field
The present invention relates to a kind of tree-shaped organic dye based on carbazole or triphenylamine derivative and the application in preparing dye sensitization solar battery thereof.
Background technology
After entering 21 century, the whole world increases gradually to energy demand.What the past people mainly utilized is the Nonrenewable energy resources such as coal, oil, Sweet natural gas, and along with time lapse, this conventional energy resources is approach exhaustion the most at last.And the use of fossil energy also will bring serious problem of environmental pollution.Therefore, the development renewable resources becomes the only way that human future can sustainable development.Sun power is a kind of reproducible, clean energy, remarkable in aspect advantages such as economy, environmental protection, Sustainable developments.And dye sensitization solar battery (DSSCs) due to advantages such as its manufacture craft are simple, cost is low, have good stability, thereby has huge potential using value as a kind of novel solar cell.The sensitizing agent of dye sensitization solar battery mainly contains metal complexes and the large class of pure organic dye two, but because rare metal in metal complexes is expensive, purify loaded down with trivial details, pure organic dye has environmentally friendly, cheap and molar extinction coefficient is higher, synthetic and the relative advantage such as simple of purifying, so organic sun sensitizing dye of seeking the base metal class of superior performance becomes the important content of current research.
Summary of the invention
The object of the present invention is to provide a kind of tree-shaped organic dye based on carbazole or triphenylamine derivative and the application in preparing dye sensitization solar battery thereof.
The technical solution used in the present invention is:
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical general formula is as follows:
Figure 2013103744803100002DEST_PATH_IMAGE001
；
Wherein, the group that the derivative that D1 is one or more aromatic hydrocarbons in thiophene, carbazole, triphenylamine, fluorenyl forms, D2 is carbazyl or trianilino group, the natural number that n is 1～6, the natural number that m is 0～3, R1, R2 are hydrogen atom; Perhaps, straight chained alkyl or branched paraffin that in R1, R2 one is C1～C20, another is hydrogen atom; A is 2-(1 ', 1 '-dicyano) rhodanine or cyanoacetic acid group.
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical general formula is:
Figure 406271DEST_PATH_IMAGE002
；
Wherein, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 2013103744803100002DEST_PATH_IMAGE003
, h, h, h; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
, H,
Figure 2013103744803100002DEST_PATH_IMAGE005
,
Figure 777002DEST_PATH_IMAGE005
; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 152619DEST_PATH_IMAGE004
, n-hexyl,
Figure 749735DEST_PATH_IMAGE005
,
Figure 19042DEST_PATH_IMAGE005
; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 476699DEST_PATH_IMAGE006
, n-hexyl, ,
Figure 734560DEST_PATH_IMAGE005
; And n=2.
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical structural formula is:
Figure 2013103744803100002DEST_PATH_IMAGE007
。
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical structural formula is:
Figure 671423DEST_PATH_IMAGE008
。
A kind of application of tree-shaped organic dye in preparing dye sensitization solar battery based on carbazole or triphenylamine derivative.
The invention has the beneficial effects as follows:
Pure organic dye of the present invention belongs to D-D-π-A structure type, and the derivative of thiophene, carbazole, triphenylamine, fluorenyl or above aromatic hydrocarbons of take is D 1electron donor(ED), with carbazyl, trianilino group is D 2electron donor(ED), with 2-(1 ', 1 '-dicyano) the rhodanine cyanoacetic acid is as electron acceptor(EA), with the conjugation thiophene, the conjugation hexyl thiophene, or (with) conjugation 3, the 4-ethene dioxythiophene is bridging group, its tree structure can, by increasing to the body extension conjugation, make absorption spectrum Einstein shift, and effectively suppress dye adsorption at TiO 2on the molecular aggregates that causes, contain a plurality of thiophene or derivatives thereofs in dye molecule simultaneously, strengthened light stability and the electronic transmission performance of organic dye.
Pure organic dye of the present invention can be used as light-sensitive coloring agent for the preparation of dye sensitization solar battery, has high transformation efficiency.
The accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra figure of pure organic dye in chloroform;
Fig. 2 is electric current and the voltage curve figure of the dye sensitization solar battery that prepared by pure organic dye.
Embodiment
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical general formula is:
Figure 752512DEST_PATH_IMAGE002
Wherein, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 837142DEST_PATH_IMAGE003
, h, h, h; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 301359DEST_PATH_IMAGE004
, H,
Figure 155046DEST_PATH_IMAGE005
,
Figure 16823DEST_PATH_IMAGE005
; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 854329DEST_PATH_IMAGE004
, n-hexyl,
Figure 217177DEST_PATH_IMAGE005
,
Figure 689484DEST_PATH_IMAGE005
; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 253321DEST_PATH_IMAGE006
, n-hexyl,
Figure 578123DEST_PATH_IMAGE005
,
Figure 620028DEST_PATH_IMAGE005
; And n=2.
Specifically, the chemical structural formula of above four kinds of dyestuffs is as follows:
Figure 2013103744803100002DEST_PATH_IMAGE009
The synthetic route of above several dyestuffs is schematically as follows:
Figure 613087DEST_PATH_IMAGE010
In this synthetic route, (1) Suzuki coupling and go Boc reaction, (2) Ullmann reaction, (3) Knoevenagel condensation reaction.
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical structural formula is:
Figure 2013103744803100002DEST_PATH_IMAGE011
。
The synthetic route of this compound is schematically as follows:
A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative, its chemical structural formula is:
Figure 2013103744803100002DEST_PATH_IMAGE013
。
The synthetic route of this compound is as follows:
Figure 596141DEST_PATH_IMAGE014
。
Below the present invention is described further in conjunction with specific embodiments:
embodiment 1:
one, dyestuff D1's is synthetic
1. compound 1a [3,6-di (thiophen-2-yl)-9H-carbazole]
Figure 2013103744803100002DEST_PATH_IMAGE015
Get 100 mL schlenk bottles, repeatedly vacuumize, form the anhydrous and oxygen-free system after logical nitrogen three times.In the situation that keep passing into nitrogen, by I 2bocCz(3 mmol), 2-boric acid thiophene (6.6 mmol), tetrakis triphenylphosphine palladium (0.12 mmol), K 3pO 4(12 mmol) adds in reactor.DMF dewaters after deoxygenation, with syringe, adds 20 mL as reaction solvent.Oil bath is heated to 100 ℃ of stirrings and spends the night (16 h), and reaction solution is cooled to room temperature, with methylene dichloride and water, is extracted, and retains organic phase.After revolving and steaming and to obtain solid, with 10 mL methylene dichloride dissolvings, add trifluoroacetic acid (TFA) 5 mL, methyl-phenoxide 1.5 mL.Under room temperature, water extraction after reaction 2 h, retain organic phase.Obtain thick product after revolving steaming, purify with silicagel column, eluent is sherwood oil: methylene dichloride (volume ratio)=2:1.Obtaining product is white solid, 520 mg, productive rate 53%.
1 (300 MHz, CDCl 3) δ (ppm):8.32 (s, 1H), 8.14-8.11 (m, 0H), 7.70 (d, J=8.4 Hz, 1H), 7.43 (d, J=8.5 Hz, 1H), 7.36 (d, J=3.5 Hz, 1H), 7.28 (s, 0H), 7.11 (t, J=4.3 Hz, 1H). ESI-MS: m/z 330.2([M-H] -)
2. compound 1b [5'-(3,6-di (thiophen-2-yl)-9H-carbazol-9-yl)-[2,2'-bithiophene]-5-carbaldehyde]
Figure 113841DEST_PATH_IMAGE016
Get 50 mL two neck round-bottomed flasks, load onto reflux condensing tube, repeatedly vacuumize, form the anhydrous and oxygen-free system after logical nitrogen three times.In the situation that keep passing into nitrogen, will 1a(0.7 mmol), 5-are bromo-2,2 '-bithiophene-5 '-formaldehyde ( 1c) (0.77 mmol), copper powder (0.42 mmol), K 2cO 3(3.5 mmol), 18-hat-6(0.35 mmol) and orthodichlorobenzene (4 mL) join in flask.Oil bath is heated to 180 ℃ of stirring and refluxing and spends the night (20 h), continues logical nitrogen in process.Reaction solution is cooled to filtering reacting liquid after normal temperature, collects filtrate, and oil bath is outstanding to be evaporated solution and obtain crude product.With silicagel column, purify, eluent is sherwood oil: methylene dichloride (volume ratio)=1:1.Obtaining product is yellow solid, 130 mg, productive rate 33%.
1 (300 MHz, CDCl 3) δ (ppm):9.87 (s, 1H), 8.32 (s, 2H), 7.73 (d, J=1.7 Hz, 1H), 7.71-7.68 (d, 2H), 7.52 (d, J=8.5 Hz, 2H), 7.42 (dd, J=3.9 Hz, 1.0, 1H), 7.37 (d, J=3.6 Hz, 1.1, 2H), 7.29 -7.27 (m, 3H), 7.20(d,1H), 7.19(d, 2H), 7.13-7.09 (m, 2H)。
dyestuff D1
Figure 2013103744803100002DEST_PATH_IMAGE017
Get 50 mL two neck round-bottomed flasks, load onto reflux condensing tube, repeatedly vacuumize, form the anhydrous and oxygen-free system after logical nitrogen three times.In the situation that keep passing into nitrogen, will 1b(0.2 mmol), cyanoacetic acid (1 mmol), piperidines (4 mmol) and acetonitrile (4 mL) and chloroform (4 mL) join in flask.Be heated to 65 ℃ of back flow reaction 6 h, reaction is cooled to room temperature, the hcl acidifying that is 30% by mass concentration after finishing.Use CH 2cl 2reaction solution is extracted, retained organic phase.Outstanding steaming obtains crude product, the silicagel column separating-purifying, and eluent is methylene dichloride: acetic acid (volume ratio)=1:1.Obtaining dyestuff is red powder 100 mg, productive rate 83%.
1 (300 MHz, DMSO) δ (ppm)：8.68 (s, 2H), 8.15 (s, 1H), 7.80 (dd, J=8.6, 1.7 Hz, 2H), 7.75 (d, J=3.9 Hz, 1H), 7.65 (d, J=3.9 Hz, 1H), 7.62 (s, 1H), 7.60-7.55 (m, 4H), 7.53 (d, J=5.1 Hz, 2H), 7.50 (d, J=4.0 Hz, 1H), 7.19-7.15 (m, 2H). 13 C NMR (400 MHz, DMSO) δ (ppm)：144.44, 141.03, 138.28, 135.79, 128.93, 128.13, 126.97, 126.10, 125.82, 125.53, 125.42, 124.20, 123.59, 118.39, 111.40, 55.37, 29.49, 22.69. ESI-MS: m/z 741.102([M-H] -).
two, dyestuff D2's is synthetic
1. compound 2a [3,6-bis (5-hexylthiophen-2-yl)-9H-carbazole]
Reference 1asynthetic method, the first step I 2bocCz(3 mmol), 5-hexyl-2-thienyl boric acid (6.6 mmol), tetrakis triphenylphosphine palladium (0.12 mmol), K 3pO 4(12 mmol), DMF 20 mL.Remove Boc CH 2cl 2(10 mL), trifluoroacetic acid (5 mL), methyl-phenoxide (1.5 mL).Obtain white solid product 770 mg, productive rate 51.5%.
1 (400 MHz, DMSO) δ (ppm): 8.61 (s, 2H), 8.51 (s, 1H), 8.02 (s, 1H), 7.75 (d, J=9.1 Hz, 4H), 7.69 (d, J=3.8 Hz, 2H), 7.61 (d, J=8.5 Hz, 2H), 7.54 (d, J=3.8 Hz, 1H), 7.39 (d, J=3.4 Hz, 2H), 6.89 (s, 2H), 2.86-2.80 (m, 4H), 1.71-1.63 (m, 4H), 1.38 (s, 4H), 1.32 (s, 8H), 0.88 (s, 6H). 13 C NMR (400 MHz, DMSO) δ (ppm): 139.99, 138.11, 134.52, 122.31, 120.26, 119.75, 119.10, 117.03, 112.76, 106.29, 27.05, 26.98, 25.66, 24.19, 17.96, 9.46. ESI-MS: m/z 499.270 ([M-H] +).
2. compound 2b's is synthetic
Reference 1bsynthetic method, 2a(0.7 mmol), 2c(0.64 mmol), copper powder (0.42 mmol), K 2cO 3(3.5 mmol), 18-hat-6(0.35 mmol) and orthodichlorobenzene (4 mL).Obtain reddish-brown solid 130 mg, productive rate 25%.
1 (400 MHz, CDCl 3) δ (ppm): 9.95 (s, 1H), 8.27 (s, J=1.4 Hz, 2H), 7.67 (dd, J=8.5Hz, 1.7, 2H), 7.49-7.48 (m, 2H), 7.44 (dd, J=3.7Hz, 1.0 Hz, 1H), 7.38 (dd, J=5.1 Hz, 1.0 Hz, 1H), 7.19 (d, J=4.0 Hz, 1H), 7.18 (d, J=3.5Hz, 2H), 6.78 (d, J=3.5Hz, 2H), 4.42 (d, J=2.8 Hz, 4H), 2.85 (t, J=7.6 Hz, 4H), 1.73 (dd, J=14.6 Hz, 7.1 Hz, 4H), 1.48-1.40 (m, 4H), 1.34 (dd, J=7.2 Hz, 3.4 Hz, 8H), 0.90 (d, J=7.0 Hz, 6H). ESI-MS: m/z 748.543([M-H] +).
3. dyestuff D2
Figure 935221DEST_PATH_IMAGE020
Reference d1synthetic method, 2b(0.1mmol), cyanoacetic acid (0.5mmol), pyridine (2mmol), acetonitrile (4 mL) and chloroform (4 mL).Obtain reddish black solid 70 mg, productive rate 85%.
1 (400 MHz, CDCl 3) δ (ppm): 8.25 (s,2H), 8.03 (s, 1H), 7.64 (d, J=8.4 Hz, 2H), 7.37 (d, J=8.4 Hz, 2H), 7.15 (d, J=3.3 Hz, 2H), 6.77 (d, J=2.9 Hz, 2H), 2.84 (t, J=7.5 Hz, 4H), 1.79-1.68 (m, 4H), 1.42 (s, 4H), 1.34 (d, J=3.3 Hz, 8H), 0.91 (s, 6H). 13 C NMR (101 MHz, DMSO) δ (ppm): 163.98, 162.77, 146.62, 145.30, 144.70, 141.75, 140.62, 139.02, 134.89, 133.22, 128.43, 126.64, 126.05, 124.97, 124.22, 123.06, 117.80, 116.99, 36.25, 31.59, 31.46, 31.24, 29.97, 28.62, 22.51, 14.41. ESI-MS: m/z 816.084([M-H] -).
three, dyestuff D3's is synthetic
1. compound 3a
Figure 2013103744803100002DEST_PATH_IMAGE021
Reference 1bsynthetic method, 2a(0.7 mmol), 2d '(0.64 mmol), copper powder (0.42 mmol), K 2cO 3(3.5 mmol), 18-hat-6(0.35 mmol) and orthodichlorobenzene (4 mL).Obtain reddish-brown solid 100 mg, productive rate 20.6%.
1 (400 MHz, DMSO) δ (ppm): 9.95(s, 1H), 8.27 (s, 2H), 7,68 (s, 1H), 7.55 (d, J=5.6 Hz , 2H), 7.44 (d, J=8.6 Hz, 2H), 7.36 (d, J=3.5 Hz, 2H), 6.97 (d, J=5.2 Hz, 1H), 6.79 (d, J=3.4 Hz, 2H), 4.48 (d, J=17.7 Hz, 4H), 2.83-2.74 (m, 8H), 1.63 (tt, J=15.8 Hz, 7.7 Hz, 8H), 1.38 (s, 8H), 1.32-1.23 (m, 16H), 0.90-0.82 (m, 12H). 13 C NMR (400 MHz, DMSO) δ (ppm): 164.36, 148.62, 144.60, 144.32, 143.10, 142.39, 141.80, 140.52, 138.32, 134.50, 133.53, 132.45, 132.17, 132.00, 131.47, 131.09, 130.30, 129.59, 128.98, 128.24, 122.98, 120.53, 117.38, 109.98, 94.54, 66.15, 65.42, 31.59, 31.49, 30.63, 30.51, 30.10, 29.98, 29.06, 28.63, 22.47, 14.37. ESI-MS: m/z 833.170 ([M-H] -).
2. dyestuff D3
Figure 375561DEST_PATH_IMAGE022
Reference d1synthetic method, 3b(0.1 mmol), cyanoacetic acid (0.5 mmol), pyridine (2 mmol), acetonitrile (2 mL) and chloroform (2 mL).Obtain reddish black solid 55 mg, productive rate 65%.
1 (400 MHz, DMSO) δ (ppm): 8.55 (s, 2H), 8.19 (s, 1H), 7.68 (d, J=5.6 Hz , 2H), 7.54 (d, J=8.6 Hz, 2H), 7.35 (d, J=3.5 Hz, 2H), 7.07 (d, J=5.2 Hz, 1H), 6.85 (d, J=3.4 Hz, 2H), 4.48 (d, J=17.7 Hz, 4H), 2.83-2.74 (m, 8H), 1.63 (tt, J=15.8 Hz, 7.7 Hz, 8H), 1.38 (s, 8H), 1.32-1.23 (m, 16H), 0.90-0.82 (m, 12H). 13 C NMR (101 MHz, DMSO) δ (ppm): 164.31, 162.77, 149.29, 144.61, 141.78, 140.68, 140.20, 128.27, 126.05, 124.94, 124.22, 123.04, 117.80, 117.44, 66.32, 65.71, 36.25, 31.59, 31.46, 31.24, 29.94, 28.62, 22.52, 14.41. ESI-MS: m/z 901.122([M-H] -).
four, dyestuff D4's is synthetic
1. compound 4a
[4,4'-(9H-carbazole-3,6-diyl)bis(N,N-diphenylaniline)]
Reference 1asynthetic method, but adopted the dibromo carbazole to replace I here 2bocCz, as raw material, can directly obtain product 4a, saved the step of Boc protection.Dibromo carbazole (1.5 mmol), 5-hexyl-2-thienyl boric acid (3.3 mmol), tetrakis triphenylphosphine palladium (0.06 mmol), K 3pO 4(4.5 mmol), DMF 9 mL.
1 (400 MHz, CDCl 3) δ (ppm): 8.35 (s, 2H), 8.12 (s, 1H), 7.71 (dd, J=8.4 Hz, 1.8, 2H), 7.65-7.63 (m, 4H), 7.53 (d, J=8.4 Hz, 2H), 7.32 (dt, J=7.3 Hz, 1.7 Hz, 8H), 7.24-7.22 (m, 4H), 7.20 (dd, J=8.6 Hz, 1.1 Hz, 8H), 7.07 (dd, J=10.4 Hz , 4.2 Hz, 4H). 13 C NMR (101 MHz, DMSO) δ (ppm): 147.87, 146.51, 136.38, 129.27, 127.94, 124.49, 124.23, 122.73, 118.41, 110.87, 58.49, 29.73, 26.95, 18.46. ESI-MS: m/z 652.961 ([M-H] -).
2. compound 4b's is synthetic
7-(5'-(3,6-bis(4-(diphenylamino)phenyl)-9H-carbazol-9-yl)-3',4-dihexyl-[2,2'-bithiophen]-5-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde
Reference 1bsynthetic method, 4a(0.6 mmol), intermediate 2f '(0.66 mmol), copper powder (0.36 mmol), K 2cO 3(3 mmol) and orthodichlorobenzene (2.5 mL).Obtain reddish-brown solid 160 mg, productive rate 43%.
Figure 320121DEST_PATH_IMAGE024
dyestuff D4
(Z)-3-(7-(5'-(3,6-bis(4-(diphenylamino)phenyl)-9H-carbazol-9-yl)-3',4-dihexyl-[2,2'-bithiophen]-5-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-cyanoacrylic acid
Figure DEST_PATH_IMAGE025
Reference d1synthetic method, 4b(0.1 mmol), cyanoacetic acid (0.5 mmol), pyridine (2 mmol), acetonitrile (2 mL) and chloroform (2 mL).Obtain reddish black solid 119 mg, productive rate 91%.
1 (400 MHz, DMSO) δ (ppm): 8.66 (s, 1H), 8.48 (s, 1H), 7.78 (d, J=8.5 Hz, 1H), 7.73 (d, J=8.3 Hz, 2H), 7.65 (d, J=8.0 Hz, 2H), 7.33 (t, J=7.7 Hz, 4H), 7.09 (t, J=9.6 Hz , 8H), 4.48 (d, J=17.7 Hz, 4H), 2.83-2.74 (m, 8H), 1.63 (tt, J=15.8 Hz, 7.7 Hz, 8H), 1.38 (s, 8H), 1.32-1.23 (m, 16H), 0.90-0.82 (m, 12H). 13 C NMR (400 MHz, CDCl 3) δ (ppm): 147.78, 146.74, 141.15, 135.87, 134.00, 129.26, 127.95, 125.59, 124.28, 122.80, 31.71, 31.66, 30.42, 29.24, 29.21, 22.66, 22.60, 14.11, 1.02. ESI-MS:1220.399([M-H] -).
five, dyestuff D5's is synthetic
1. compound 1b '
Figure 529517DEST_PATH_IMAGE026
Carbazole (19.2 mmol), copper powder (6.5 mmol), salt of wormwood (47.8 mmol), and 18 hat 6(1.2 mmol) add successively in reaction flask, then add 50 ml to rouse in advance the orthodichlorobenzene of nitrogen deoxygenation, stir and be heated to backflow.4', 4'', 24 ml o-dichlorobenzene solutions of 4'''-tri-iodo triphenylamines (9.6 mmol) slowly splash into, and then continue stirring and refluxing 24 h.Question response liquid is cooled to room temperature, and by reacting liquid filtering, the solvent in filtrate is removed by revolving to steam, and the thick product obtained carries out the column chromatography chromatogram separation, and developping agent is sherwood oil/methylene dichloride (10:1, v/v), obtains white powder 2.3 g, and productive rate is 34%.
1 H-NMR(400 MHz, DMSO- d6) δ (ppm): 8.25 (d, J = 7.7 Hz, 4H), 7.76 (d, J = 8.8 Hz, 2H), 7.69 (d, J = 8.8 Hz, 2H), 7.62 (d, J = 8.8 Hz, 4H), 7.46-7.41 (m, 8H), 7.30 (ddd, J = 8.0, 5.6, 2.4 Hz, 4H), 7.12 (d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H). 13 C-NMR (100 MHz, DMSO- d6) δ (ppm): 146.7, 145.7, 140.2, 138.5, 138.4, 131.9, 128.1, 126.4, 126.2, 125.1, 122.6, 120.5, 120.0, 109.7. EI-MS: m/z 576.4 ([M-I] +). Elemental Analysis: Calcd for C 42H 28IN 3: C, 71.90; H, 4.02; N, 5.99%. Found: C, 71.66; H, 4.32; N, 6.01%.
2. compound 1c '
Figure DEST_PATH_IMAGE027
Under nitrogen atmosphere, in the Schlenk bottle, add successively 1b '(1.7 mmol), tetramethyl ethylene ketone two boron (2.1 mmol), Potassium ethanoate (5.1 mmol) and Pd (dppf) Cl 2(0.1 mmol), then add the DMSO(50 mL of the deoxygenation that dewaters), reaction 5 h under 100 ℃.Question response liquid is cooled to room temperature, adds ethyl acetate, then adds the water washing organic phase, takes away the DMSO in organic phase, collects organic phase.Use the anhydrous magnesium sulfate drying organic phase.Revolve and steam desolventizing, column chromatography chromatogram separates, and developping agent is that petrol ether/ethyl acetate (5:1, v/v) obtains white solid 1c '900 mg, productive rate 75%.
1 (400 MHz, CDCl 3) δ(ppm): 8.13 (d, J = 7.7 Hz, 4H), 7.83 (d, J = 8.5 Hz, 2H), 7.55 -7.37 (m, 16H), 7.33-7.24 (m, 6H), 1.35 (s, 12H). 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 150.0, 146.3, 140.9, 136.3, 132.7, 128.0, 125.9, 125.4, 123.3, 123.2, 120.3, 119.9, 109.8, 83.7, 24.9.; MALDI-TOF: m/z 701.262 ([M +]); Elemental Analysis: Calcd for C 48H 40BN 3O 2: C, 82.16; H, 5.75; N, 5.99. Found: C, 82.34; H, 5.79; N, 6.05.
3. compound 2c '
Figure 137215DEST_PATH_IMAGE028
Under nitrogen protection, in the Schlenk reaction flask, add 2b '(2.0 mmol), 3-hexyl thiophene-2-pinacol borate (2.6 mmol) and tetrakis triphenylphosphine palladium (0.12 mmol), then add the glycol dimethyl ether (DME, 24 mL) of deoxygenation, adds the 2mol/L Na of deoxygenation under stirring 2cO 3the aqueous solution (1.7 mL), reaction under 90 ℃ after stirring 15 min under room temperature.Thin-layer chromatography (TLC) is followed the tracks of reaction process.Question response liquid is cooled to room temperature, revolves and steams except desolventizing, ethyl acetate/saturated NaCl aqueous solution extraction.Collect organic phase, anhydrous MgSO 4dry organic phase, again revolve and steam except desolventizing, and column chromatography chromatogram separates, and developping agent is petrol ether/ethyl acetate (3:1, v/v), obtains yellow solid 2c '615 mg, productive rate 91%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.93 (s, 1H), 7.34 (d, J = 5.2 Hz, 1H), 6.95 (d, J = 5.2 Hz, 1H), 4.37 (tdd, J = 6.7, 4.1, 2.6 Hz, 5H), 2.81-2.74 (m, 2H), 1.69-1.56 (m, 2H), 1.39-1.26 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.6, 148.3, 142.9, 137.4, 129.7, 126.7, 126.1, 122.6, 116.3, 65.2, 64.6, 31.7, 30.4, 29.8, 29.3, 22.6, 14.1; MALDI-TOF: m/z 336.090 ([M +]); Elemental Analysis: Calcd for C 17H 20O 3S 2: C, 60.68; H, 5.99. Found: C, 60.79; H, 6.23.
3. compound 2d '
Figure DEST_PATH_IMAGE029
In single necked round bottom flask, add 2c '(0.47 mmol), add CHCl 3(10 mL) dissolves it fully, adds NBS(0.47 mmol), stir and spend the night under room temperature.Revolve and steam except desolventizing, column chromatography chromatogram separates, and developping agent is that petrol ether/ethyl acetate (3:1, v/v) obtains nearly colorless solid 2d '177 mg.Productive rate 90%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.92 (s, 1H), 6.91 (s, 1H), 4.44-4.33 (m, 4H), 2.75-2.69 (m, 2H), 1.65-1.52 (m, 2H), 1.41-1.27 (m, 6H), 0.88 (t, J = 6.8 Hz, 3H); 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.6, 148.2, 143.1, 137.6, 132.3, 127.9, 121.2, 116.3, 114.0, 65.2, 64.8, 31.6, 30.2, 30.0, 29.2, 22.6, 14.1.; MALDI-TOF: m/z 413.980 ([M +]); Elemental Analysis: Calcd for C 17H 19O 3S 2Br: C, 49.16; H, 4.61. Found: C, 49.35; H, 4.56.
4. compound 2e '
Figure 569246DEST_PATH_IMAGE030
Under nitrogen protection, in the Schlenk reaction flask, add 2d '(1.5 mmol), 3-hexyl thiophene-2-pinacol borate (1.9 mmol) and tetrakis triphenylphosphine palladium (0.088 mmol), then add the glycol dimethyl ether (DME, 18 mL) of deoxygenation, adds the 2mol/L Na of deoxygenation under stirring 2cO 3the aqueous solution (1.3 mL), reaction under 90 ℃ after stirring 15 min under room temperature.Thin-layer chromatography (TLC) is followed the tracks of reaction process.Question response liquid is cooled to room temperature, revolves and steams except desolventizing, ethyl acetate/saturated NaCl aqueous solution extraction.Collect organic phase, anhydrous MgSO 4dry organic phase, again revolve and steam except desolventizing, and column chromatography chromatogram separates, and developping agent is petrol ether/ethyl acetate (5:1, v/v), obtains yellow solid 2e '592 mg, productive rate 80%.
1 (400 MHz, CDCl 3) δ(ppm): 9.94 (s, 1H), 7.18 (d, J = 5.2 Hz, 1H), 6.96 (s, 1H), 6.93 (d, J = 5.2 Hz, 1H), 4.39 (dd, J = 11.1, 5.2 Hz, 4H), 2.78 (dd, J = 16.2, 9.4 Hz, 4H), 1.75-1.58 (m, 4H), 1.44-1.21 (m, 12H), 0.94-0.82 (m, 6H) ; 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.5, 148.3, 143.1, 140.1, 137.4, 137.3, 130.2, 130.1, 128.3, 126.0, 124.1, 122.5, 116.1, 65.2, 64.7, 31.7, 31.6, 30.7, 30.3, 30.1, 29.3, 29.37, 29.2, 22.6, 14.1; MALDI-TOF: m/z 502.147 ([M +]); Elemental Analysis: Calcd for C 27H 34O 3S 3: C, 64.50; H, 6.82. Found: C, 64.79; H, 6.73.
5. compound 2e '
Figure DEST_PATH_IMAGE031
In single necked round bottom flask, add 2e '(0.56 mmol), add CHCl 3(10 mL) dissolves it fully, adds NBS(0.56 mmol), stir and spend the night under room temperature.Revolve and steam except desolventizing, column chromatography chromatogram separates, and developping agent is that petrol ether/ethyl acetate (5:1, v/v) obtains yellow solid 2f '294 mg.Productive rate 90%.
1 (400 MHz, CDCl 3) δ(ppm): 9.94 (s, 1H), 6.90 (s, 1H), 6.89 (s, 1H), 4.40 (dd, J = 11.8, 4.6 Hz, 5H), 2.83-2.74 (m, 2H), 2.74-2.65 (m, 2H), 1.75-1.60 (m, 4H), 1.45-1.18 (m, 12H), 0.88 (M, 6H).; 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.6, 148. 2, 143.1, 140.7, 137.4, 135.9, 132.8, 131.7, 128.6, 126.6, 122.1, 116.3, 110.9, 65.2, 64.7, 31.7, 31.6, 30.5, 30.3, 30.0, 29.3, 29.1, 22.6, 14.1 ; MALDI-TOF: m/z 578.895 ([M +]); Elemental Analysis: Calcd for C 27H 33O 3S 3Br: C, 55.75; H, 5.72. Found: C, 55.86; H, 5.62.
6. Compound D 5 '
Figure 428749DEST_PATH_IMAGE032
Under nitrogen protection, in the Schlenk reaction flask, add 1c '(1.1 mmol), 2f '(0.96 mmol) and tetrakis triphenylphosphine palladium (0.047 mmol), then add the glycol dimethyl ether (DME, 60 mL) of deoxygenation, adds the 2mol/L K of deoxygenation under stirring 2cO 3the aqueous solution (1.3 mL), reaction under 90 ℃ after stirring 15 min under room temperature.Thin-layer chromatography (TLC) is followed the tracks of reaction process.Question response liquid is cooled to room temperature, revolves and steams except desolventizing, ethyl acetate/saturated NaCl aqueous solution extraction.Collect organic phase, anhydrous MgSO 4dry organic phase, again revolve and steam except desolventizing, and column chromatography chromatogram separates, and developping agent is petrol ether/ethyl acetate (3:1, v/v), obtains yellow solid d5 '772 mg, productive rate 75%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.94 (s, 1H), 8.15 (dd, J = 7.0, 5.5 Hz, 8H), 7.60 (d, J = 8.4 Hz, 2H), 7.55-7.40 (m, 8H), 7.37-7.27 (m, 8H), 7.14 (s, 1H), 7.02 (s, 1H), 6.91 (d, J = 8.5 Hz, 2H), 4.40 (d, J = 4.7 Hz, 4H), 2.80 (m, 4H), 1.80-1.64 (m, 12H), 1.33 (s, 4H), 0.93-0.82 (m, 6H).; 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.6, 147.0, 146.3, 141.2, 141.1, 141.0, 132.6, 131.5, 129.4, 128.3, 128.2, 128.0, 128.0, 126.8, 125.9, 125.9, 125.1, 124.9, 123.5, 123.3, 123.2, 120.4, 120.3, 119.9, 119.8, 116.8, 109.8, 65.2, 64.7, 31.7, 31.7, 30.5, 30.3, 30.1, 29.7, 29.3, 29.3, 22.7, 22.6, 14.1; MALDI-TOF: m/z 1075.331 ([M +]); Elemental Analysis: Calcd for C 69H 61N 3O 3S 3: C, 76.99; H, 5.71; N, 3.90. Found: C, 77.10; H, 5.64; N, 3.75.
7. Compound D 5
Figure DEST_PATH_IMAGE033
Under the atmosphere of nitrogen, in the Schlenk reaction flask, add d5 '(0.57 mmol), cyanoacetic acid (2.8 mmol), then add piperidines (5.7 mmol), stirs 15 min after toluene (20 mL) and acetonitrile (40 mL) under room temperature, in 100 ℃ of lower back flow reaction 5 h.Question response liquid is cooled to room temperature, adds 1 mol/L HCl aqueous solution conditioned reaction liquid pH to 2-3.Ethyl acetate/saturated NaCl aqueous solution extraction, collect organic phase, anhydrous MgSO 4dry organic phase.Again revolve and steam except desolventizing, column chromatography chromatogram separates, and developping agent is methylene dichloride/acetic acid (80:1, v/v), obtains dark red solid d5522 mg, productive rate 80%.
1 (400 MHz, DMF- d 7 ) δ(ppm): 8.34 (s, 1H), 8.30 (d, J = 7.8 Hz, 3H), 7.83 (d, J = 8.5 Hz, 2H), 7.72 (d, J = 8.6 Hz, 4H), 7.62-7.46 (m, 15H), 7.42(d, J = 8.5 Hz, 2H)，7.37-7.26 (m, 4H), 4.61 (dd, J = 17.5, 4.3 Hz, 4H), 2.99- 2.84 (m, 4H), 1.86-1.64 (m, 4H), 1.54-1.19 (m, 12H), 0.89 (t, J = 6.7 Hz, 6H); 13 C-NMR (100 MHz, DMF- d 7 ) δ(ppm): 166.0, 164.4, 149.0, 147.2, 146.6, 144.0, 142.1, 142.0, 141.1, 140.3, 138.2, 137.6, 132.7, 129.1, 128.9, 128.6, 127.1, 126.9, 126.4, 126.2, 125.7, 124.9, 123.4, 120.9, 120.7, 120.2, 117.4, 110.1, 108.0, 94.5, 66.3, 65.5, 31.73, 31.65, 30.7, 30.4, 24.4, 22.64, 22.63, 13.8.; MALDI-TOF: m/z 1142.328([M +]); Elemental Analysis: Calcd for C 72H 62N 4O 4S 3: C, 75.63; H, 5.47; N, 4.90. Found: C, 75.36; H, 5.39; N, 4.86.
six, dyestuff D6's is synthetic
1. compound 2g '
Figure 381399DEST_PATH_IMAGE034
Under nitrogen protection, in the Schlenk reaction flask, add 2f '(3.0 mmol), 3-hexyl thiophene-2-pinacol borate (3.3 mmol) and tetrakis triphenylphosphine palladium (0.18 mmol), then add the glycol dimethyl ether (DME, 50 mL) of deoxygenation, adds the 2mol/L Na of deoxygenation under stirring 2cO 3the aqueous solution (5.0 mL), reaction under 90 ℃ after stirring 15 min under room temperature.Thin-layer chromatography (TLC) is followed the tracks of reaction process.Question response liquid is cooled to room temperature, revolves and steams except desolventizing, ethyl acetate/saturated NaCl aqueous solution extraction.Collect organic phase, anhydrous MgSO 4dry organic phase, again revolve and steam except desolventizing, and column chromatography chromatogram separates, and developping agent is petrol ether/ethyl acetate (5:1, v/v), obtains yellow solid 2g '1.6 g, productive rate 80%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.94 (s, 1H), 7.16 (d, J = 5.2 Hz, 1H), 6.99 (s, 1H), 6.94 (s, 1H), 6.93 (d, J = 5.2 Hz, 1H), 4.41 (dd, J = 10.5, 5.3 Hz, 4H), 2.86-2.72 (m, 6H), 1.78-1.60 (m, 6H), 1.48-1.28 (m, 18H), 0.97-0.81 (m, 9H); 13 C-NMR (100 MHz, CDCl 3) δ(ppm): 179.5, 148.3, 143.2, 140.3, 139.8, 137.3, 137.1, 134.7, 130.4, 130.1, 129.9, 128.8, 128.1, 126.1, 123.7, 122.6, 116.1, 65.2, 64.7, 31.7, 31.7, 31.7, 30.6, 30.5, 30.3, 30.1, 29.5, 29.3, 29.3, 29.24, 29.21, 22.64, 22.63, 14.1.; MALDI-TOF: m/z 668.200 ([M +]); Elemental Analysis: Calcd for C 37H 48O 3S 4: C, 66.42; H, 7.23. Found: C, 66.26; H, 7.35 .
2. compound 2h '
Figure DEST_PATH_IMAGE035
In single necked round bottom flask, add 2g '(1.9 mmol), add CHCl 3(40 mL) dissolves it fully, adds NBS(1.9 mmol), stir and spend the night under room temperature.Revolve and steam except desolventizing, column chromatography chromatogram separates, and developping agent is that petrol ether/ethyl acetate (5:1, v/v) obtains yellow solid 2h '1.3 g.Productive rate 90%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.94 (s, 1H), 6.98 (s, 1H), 6.90-6.86 (m, 2H), 4.40 (dd, J = 10.4, 5.2 Hz, 4H), 2.85-2.65 (m, 6H), 1.73 -1.53 (m, 6H), 1.46-1.23 (m, 21H), 0.94-0.84 (m, 9H); 13 C-NMR (100 MHz, CDCl 3) δ(ppm) 179.5, 148.3, 143.2, 140.4, 140.3, 137.3, 136.7, 133.3, 132.8, 131.9, 130.5, 129.2, 128.2, 126.3, 122.4, 116.2, 110.5, 65.2, 64.7, 31.7, 31.6, 31.6, 30.5, 30.3, 30.1, 29.4, 29.3, 29.2, 29.2, 29.1, 22.63, 22.62, 22.60, 14.1; MALDI-TOF: m/z 746.120 ([M +]); Elemental Analysis: Calcd for C 37H 47O 3S 4Br: C, 59.42; H, 6.33. Found: C, 59.26; H, 6.50.
3. Compound D 6 '
Under nitrogen protection, in the Schlenk reaction flask, add 1c '(1.9 mmol), 2h '(1.60 mmol) and tetrakis triphenylphosphine palladium (0.096mmol), then add the glycol dimethyl ether (DME, 40 mL) of deoxygenation, adds the 2mol/L K of deoxygenation under stirring 2cO 3the aqueous solution (4.4 mL), reaction under 90 ℃ after stirring 15 min under room temperature.Thin-layer chromatography (TLC) is followed the tracks of reaction process.Question response liquid is cooled to room temperature, revolves and steams except desolventizing, ethyl acetate/saturated NaCl aqueous solution extraction.Collect organic phase, anhydrous MgSO 4dry organic phase, again revolve and steam except desolventizing, and column chromatography chromatogram separates, and developping agent is petrol ether/ethyl acetate (3:1, v/v), obtains yellow solid d6 '1.4 g, productive rate 70%.
1 H-NMR (400 MHz, CDCl 3) δ(ppm): 9.87 (s, 1H), 8.09 (d, J = 7.7 Hz, 4H), 7.54 (d, J = 8.1 Hz, 2H), 7.49-7.31 (m, 16H), 7.24-7.16 (m, 6H), 7.07 (s, 1H), 6.93 (m, 2H), 4.33 (dd, J = 9.6, 4.8 Hz, 4H), 2.78-2.68 (m, 6H), 1.69-1.56 (m, 6H), 1.42-1.20 (m, 18H), 0.83 (s, 9H); 13C-NMR (100 MHz, CDCl 3) δ(ppm): 179.6, 148.4, 146.8, 146.5, 143.4, 141.5, 141.1, 140.9, 140.6, 137.4, 137.2, 134.8, 132.7, 130.0, 129.8, 129.6, 128.7, 128.3, 128.3, 126.9, 126.2, 126.1, 126.0, 125.2, 125.0, 123.5, 122.7, 120.5, 120.1, 116.3, 110.0, 65.3, 64.9, 53.6, 31.8, 31.8, 30.7, 30.5, 30.2, 29.8, 29.7, 29.4, 29.4, 22.8, 22.8, 14.3, 14.2; MALDI-TOF: m/z 1241.449 ([M] +); Elemental Analysis: Calcd for C 79H 75N 3O 3S 4: C, 76.35; H, 6.08; N, 3.38. Found: C, 76.24; H, 6.00; N, 3.56.
4. Compound D 6
Under nitrogen atmosphere, add d6 '(0.25 mmol) and 2i '(0.25 mmol), triethylamine (0.2 mL) and anhydrous CaCl 2(0.019 mmol), in toluene (3 mL) with except reflux 48 h in water-ethanol (15 mL) mixed solvent.Reaction solution is cooled to room temperature, revolves and steams except desolventizing, and thick product separates with column chromatography chromatogram, and developping agent is methylene chloride/methanol (10:1, v/v), can obtain atropurpureus pressed powder d6225 mg, productive rate 65%.
1 (400 MHz, DMF- d 7 ) δ(ppm): 8.30 (d, J = 7.5 Hz, 4H), 7.82 (d, J = 6.1 Hz, 2H), 7.71 (s, 5H), 7.60 – 7.45 (m, 14H), 7.41 (d, J = 7.4 Hz, 2H), 7.36 – 7.28 (m, 4H), 7.25 (s, 2H), 4.51 (m, 4H), 3.69 – 3.31 (m, 6H), 2.90-2.82 (m, 6H), 1.84-1.61 (m, 6H), 1.52-1.23 (m, 18H), 0.96-0.78 (m, 9H); 13 C-NMR (100 MHz, DMF- d 7 ) δ(ppm): 181.1, 178.910, 147.5, 147.0, 143.5, 142.5, 141.8, 141.7, 141.4, 141.1, 141.1, 135.5, 134.6, 133.0, 130.4, 129.6, 129.2, 128.9, 128.9, 127.6, 127.6, 127.3, 127.2, 126.7, 126.0, 125.3, 123.7, 121.0, 120.6, 118.7, 118.7, 117.3, 117.3, 116.2, 114.5, 114.3, 110.3, 65.9, 65.8, 32.1, 32.0, 31.0, 30.8, 30.8, 23.0, 22.9, 14.2, 14.2; MALDI-TOF: m/z 1388.428 ([M +]); Elemental Analysis: Calcd for C 85H 76N 6O 3S 5: C, 73.45; H, 5.51; N, 6.05. Found: C, 73.55; H, 5.64; N, 6.35.
Organic dye of the present invention can be used for preparing dye sensitization solar battery, prepares the method for dye sensitization solar battery described in patent 200810151310.8.
The dyestuff that embodiment is synthetic makes 1 * 10 -5the ethanolic soln of mol/L, but adopt Shimadzu UV-1700 ultraviolet spectrophotometer to carry out the test of absorption spectrum.
As Fig. 1 is the uv-visible absorption spectra figure of pure organic dye in chloroform;
As Fig. 2 is electric current and the voltage curve figure of the dye sensitization solar battery that prepared by pure organic dye.
Be below the DSSCs basic parameter value of six dyestuffs:
the DSSCs basic parameter value of six dyestuffs of table 1
Figure DEST_PATH_IMAGE039

Claims (5)

1. the tree-shaped organic dye based on carbazole or triphenylamine derivative, it is characterized in that: its chemical general formula is as follows:
Figure 2013103744803100001DEST_PATH_IMAGE002
；
Wherein, D 1for the group that the derivative of one or more aromatic hydrocarbons in thiophene, carbazole, triphenylamine, fluorenyl forms, D 2for carbazyl or trianilino group, the natural number that n is 1～6, the natural number that m is 0～3, R 1, R 2for hydrogen atom; Perhaps, R 1, R 2in one be C 1～C 20straight chained alkyl or branched paraffin, another is hydrogen atom; A is 2-(1 ', 1 '-dicyano) rhodanine or cyanoacetic acid group.
2. a kind of tree-shaped organic dye based on carbazole or triphenylamine derivative according to claim 1, it is characterized in that: its chemical general formula is:
Figure 2013103744803100001DEST_PATH_IMAGE004
；
Wherein, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 2013103744803100001DEST_PATH_IMAGE006
, H, H, H; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
, H,
Figure 2013103744803100001DEST_PATH_IMAGE010
,
Figure 756085DEST_PATH_IMAGE010
; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 469963DEST_PATH_IMAGE008
, n-hexyl,
Figure 250417DEST_PATH_IMAGE010
, ; And n=1;
Perhaps, R 1, R 2, R 3, R 4be followed successively by respectively a kind of in following groups:
Figure 2013103744803100001DEST_PATH_IMAGE012
, n-hexyl,
Figure 335365DEST_PATH_IMAGE010
,
Figure 829931DEST_PATH_IMAGE010
; And n=2.
3. a kind of tree-shaped organic dye based on carbazole or triphenylamine derivative according to claim 1, it is characterized in that: its chemical structural formula is:
。
4. a kind of tree-shaped organic dye based on carbazole or triphenylamine derivative according to claim 1, it is characterized in that: its chemical structural formula is:
Figure DEST_PATH_IMAGE016
。
5. the described a kind of application of tree-shaped organic dye in preparing dye sensitization solar battery based on carbazole or triphenylamine derivative of any one in claim 1-4.
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