CN110317471B - Aggregation-free dye with spiro structure auxiliary unit and synthesis method thereof - Google Patents
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 125000003003 spiro group Chemical group 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 2
- 230000004931 aggregating effect Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 27
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002950 deficient Effects 0.000 abstract description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 abstract description 3
- 125000002541 furyl group Chemical group 0.000 abstract description 2
- 125000001544 thienyl group Chemical group 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000003595 spectral effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- JUWYQISLQJRRNT-UHFFFAOYSA-N (5-formylfuran-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)O1 JUWYQISLQJRRNT-UHFFFAOYSA-N 0.000 description 1
- 101100326595 Arabidopsis thaliana CAD6 gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical group C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a non-aggregation dye with a spiro structure auxiliary unit and a synthesis method thereof. The invention introduces an electron-deficient quinoxaline unit as an auxiliary electron acceptor on the basis of the traditional D-pi-A type dye, so that an electron donor part and a conjugated pi-bridge are separated, a series of D-A-pi-A type dyes based on quinoxaline are designed and synthesized by changing the conjugated pi-bridge, namely taking furyl, thienyl and phenyl as the pi-bridge respectively, the dye not only promotes the transmission of charges in molecules from the donor side to the acceptor side, but also regulates the molecular energy level gap of compounds, increases the spectral response of dye molecules to light, thereby obviously enhancing the efficiency of a solar cell.
Description
Technical Field
The invention belongs to the field of synthesis and application of dye-sensitized solar cell sensitizers, and particularly relates to a non-aggregation dye with a spiral structure auxiliary unit and a synthesis method thereof.
Background
With the rapid growth of global population and economic development, the demand for energy is increasing, and the search for clean renewable energy has become a global general concern. Among various renewable energy sources, solar energy has the least pollution to the environment, the widest sources and the easiest availability compared with geothermal energy, wind energy and hydroelectric power generation, and therefore, the development and utilization of solar energy are increasingly emphasized. Initially, lab-prepared higher efficiency dye-sensitized solar cells were based on ruthenium complexes and black dye etc. as dye sensitizers. However, as rare metals, ruthenium is stored in the earth in a small amount and the extraction cost is high, which affects the large-scale development of the dye sensitizer containing the ruthenium complex, and the pure organic sensitizing dye has the advantages of high molar extinction coefficient, easy structure design, simple preparation and purification, low cost, easy operation of battery cycle, and the like, so the research on the pure organic sensitizing dye is receiving very extensive attention.
The common dye molecules are adsorbed on the surface of a nano-crystal semiconductor to generate intermolecular aggregation, the dye molecules in the aggregate are quickly deactivated due to the intermolecular interaction, the electron injection efficiency is reduced, and a co-adsorbent (CDCA) is required to be added into a dye solution to prevent the dye from being adsorbed on TiO2Surface ofThereby improving the photoelectric conversion efficiency.
Disclosure of Invention
The invention aims to provide an aggregation-free dye with a spiro structure auxiliary unit and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: the non-aggregation dye with the auxiliary unit of the spiral structure has the following structural general formula:
wherein: r1Selected from one of the following groups: triphenylamine, coumarin, tetrahydroquinoline, indoline, phenothiazine and the like,
ar is selected from one of the following groups: furan, benzene rings.
Preferably, R1Is triphenylamine.
The invention provides a synthesis method of the target compound, which comprises the following steps:
(1) a step of generating an intermediate product c by the Suzuki reaction of the compound a and the compound b in the presence of sodium carbonate
(2) A step of reacting the compound c with cyanoacetic acid in the presence of ammonium acetate to generate a target product d,
further, in the step (1), the catalyst of the reaction system is Pd (PPh)3)4(ii) a Compound a and catalyst Pd (PPh)3)4Is 1: 0.06.
Further, in the step (1), the solvent of the reaction system is a mixed solution of water and tetrahydrofuran in a volume ratio of 1: 1.5.
Further, in the step (1), the molar ratio of the compound a to the compound b is 1:1.2, and the molar ratio of the compound a to the sodium carbonate is 1: 3.
Further, in the step (1), the reaction temperature is 50-60 ℃.
Further, in the step (2), the solvent of the reaction system is a mixed solution of glacial acetic acid and toluene in a volume ratio of 1: 3.
Further, in the step (2), the molar ratio of the compound c to the cyanoacetic acid is 1:3, and the molar ratio of the compound c to the ammonium acetate is preferably 1: 0.4.
Compared with the prior art, the invention has the following advantages:
the invention introduces an electron-deficient quinoxaline unit (derivative) as an auxiliary electron acceptor on the basis of the traditional D-pi-A type dye, so that an electron donor part and a conjugated pi-bridge are separated, and a series of D-A-pi-A type dyes based on quinoxaline are designed and synthesized by changing the conjugated pi-bridge (namely, furyl, thienyl and phenyl are respectively used as the pi-bridge).
Detailed Description
On the basis of the traditional D-Pi-A type dye, an electron-deficient quinoxaline unit (derivative) is introduced as an auxiliary electron acceptor, a triphenylamine unit, a coumarin unit, tetrahydroquinoline, indoline and phenothiazine are used as electron donors, a cyanoacrylate group is used as an electron acceptor, and a series of novel D-A-Pi-A type structural dyes are synthesized by changing the design of a conjugated Pi-bridge. The spiro structure designed by the invention has a geometric framework with two mutually perpendicular surfaces, can effectively inhibit the action between strong molecules through the spiro structure, can effectively inhibit dye aggregation under the condition of not needing a co-adsorbent (CADA), reduces the non-radiative transition of a luminescent material, and improves the luminous efficiency.
The design and synthesis route of the dye of this example is as follows:
the molecular structural formula of the target compound of the present invention is preferably F1, F2 shown below:
example (b):
all reactions were carried out under nitrogen atmosphere unless otherwise indicated.
Example 1
Preparation of Compound F1
Compound F1 was obtained according to scheme 1 below:
scheme 1
Synthesis of intermediate 1
Adding the intermediate a (1mmol), 5-formyl-2-furanboronic acid (1.2mmol), palladium (6 mol%) and sodium carbonate (3mmol) into a two-neck flask, adding tetrahydrofuran (45mL) and water (30mL), and reacting at 60 ℃ overnight under the protection of nitrogen. After the reaction is finished, adding saturated NH into the reaction system4Cl solution with CH2Cl2Extraction, drying of the organic phase over anhydrous magnesium sulphate, filtration, spin drying, PE/DCM as eluent, column chromatography gave intermediate 1 (dark red solid) in 77% yield. The intermediate product 1 is prepared by1H NMR(500MHz,CDCl3) Characterisation, the following spectra were obtained: 9.74(s,1H),8.68(d, J-8.0 Hz,1H),8.44(d, J-7.5 Hz,1H),8.29(d, J-7.5H)Hz,1H),8.03(d,J＝8.0Hz,1H),7.99(d,J＝3.5Hz,1H),7.81(d,J＝8.5Hz,2H),7.75(d,J＝8.0Hz,2H),7.49(t,J＝7.0Hz,1H),7.40(d,J＝3.5Hz,1H),7.38-7.15(m,19H),7.05(t,J＝7.0Hz,4H),6.77(br.s,2H).。
Synthesis of Compound F1
Intermediate 1(1mmol) and cyanoacetic acid (3mmol), ammonium acetate (30mg) were added to a two-necked flask, glacial acetic acid (16.7mL) and toluene (50mL) were added, and the reaction was refluxed overnight under a nitrogen blanket. After the reaction is finished, adding saturated NH into the reaction system4Cl solution with CH2Cl2Extraction and drying of the organic phase over anhydrous magnesium sulphate, filtration, spin-drying, eluting with DCM/MeOH (i.e. dichloromethane/methanol), column chromatography gave the title compound F1 (dark red solid, 242mg) in 95% yield.
The compound F1 is prepared by1H NMR (500MHz, DMSO) characterization, obtained the following spectra: 13.77(br.s,1H),8.62(d, J ═ 7.5Hz,1H),8.33(t, J ═ 8.0Hz,2H),8.14-8.16(m,2H),8.00(s,1H),7.96(d, J ═ 6.5Hz,2H),7.88(d, J ═ 8.0Hz,2H),7.60-7.63(m,2H),7.27-7.42(m,9H),7.08-7.16(m,12H),6.63(br.s,2H).
Example 2
Preparation of Compound F2
Compound F2 was obtained according to scheme 2 below:
scheme 2
Synthesis of intermediate 2
Adding the intermediate a (1mmol), 4-formylphenylboronic acid (1.2mmol), palladium (6 mol%) triphenylphosphine and sodium carbonate (3mmol) into a two-neck flask, adding tetrahydrofuran (45mL) and water (30mL), and reacting at 60 ℃ overnight under the protection of nitrogen. After the reaction is finished, adding saturated N into the reaction systemH4Cl solution with CH2Cl2Extraction and drying of the organic phase over anhydrous magnesium sulphate, filtration and spin-drying with PE/DCM as eluent gave intermediate 2 (orange solid, 270mg) in 85.2% yield by column chromatography.
The intermediate product 2 is obtained by1H NMR(500MHz,CDCl3) Characterisation, the following spectra were obtained: 10.10(s,1H),8.37(d, J ═ 8.0Hz,1H),8.21(d, J ═ 7.5Hz,1H),8.08(d, J ═ 8.0Hz,2H),8.02(s,2H),8.01(d, J ═ 8.5Hz,2H),7.81(d, J ═ 8.5Hz,2H),7.73(d, J ═ 7.5Hz,2H),7.26-7.37(m,8H),7.14-7.22(m,10H),7.05(t, J ═ 7.0Hz,4H),6.79(br.s,2H).
Synthesis of Compound F2
Intermediate 2(1mmol) and cyanoacetic acid (3mmol), ammonium acetate (30mg) were added to a two-necked flask, glacial acetic acid (16.7mL) and toluene (50mL) were added, and the reaction was refluxed overnight under a nitrogen blanket. After the reaction is finished, adding saturated NH into the reaction system4Cl solution with CH2Cl2Extraction, drying of the organic phase over anhydrous magnesium sulphate, filtration, spin-drying, elution with DCM/MeOH, column chromatography gave the title compound F2 (orange powder) in 80% yield.
The compound F2 is prepared by1H NMR (500MHz, DMSO) characterization, obtained the following spectra: 13.97(br.s,1H),8.42(s,1H),8.34(d, J ═ 7.5Hz,1H),8.28(d, J ═ 8.0Hz,1H),8.21(d, J ═ 8.5Hz,2H),8.19(d, J ═ 8.0Hz,1H),8.13-8.15(m,3H),7.95(d, J ═ 7.5Hz,2H),7.89(d, J ═ 8.5Hz,2H),7.44(t, J ═ 7.5Hz,2H),7.37-7.39(m,2H),7.34(t, J ═ 8.0Hz,4H),7.26-7.30(m,2H),7.07-7.14(m,12H),6.6 (br.6, 2H).
Example 3
Determination of the photovoltaic Properties of Compounds F1, F2
Photoelectrode chemistry corresponding to F1 and F2: short circuit current density (Jsc), open circuit voltage (Voc), Fill Factor (FF) and power conversion efficiency (η) data are listed in table 1.
In many cases, the addition of CDCA willImprove photovoltaic performance because CDCA assists in hindering TiO2Aggregation between dye molecules on the membrane. From a comparative analysis of the above data, the observed effect of DSSC on photovoltaic performance was different based on F1 and F2 after addition of CDCA. DSSCs based on F1 show little change with or without the addition of CDCA. For the F2-based DSSC, the power conversion efficiency dropped from 3.72% to 3.43% after the CDCA was added. Therefore, the quinoxaline-based organic dye having a spiro structural auxiliary unit can effectively inhibit dye aggregation without a co-adsorbent.
Claims (9)
1. The aggregation-free dye with the spiral structure auxiliary unit is characterized in that the spiral structure auxiliary unit has two mutually perpendicular geometrical skeletons, and the structural general formula is as follows:
wherein R is1Selected from one of the following groups: triphenylamine, coumarin, tetrahydroquinoline, indoline, phenothiazine; ar is selected from one of the following groups: furan, benzene rings.
2. The non-aggregating dye of claim 1, wherein R is1Is triphenylamine.
3. The method of synthesizing an aggregation-free dye having a spiro structural assist unit as set forth in claim 1, comprising the steps of:
(1) a step of carrying out Suzuki reaction on the compound a and the compound b in the presence of sodium carbonate to generate an intermediate product c,
(2) a step of reacting the compound c with cyanoacetic acid in the presence of ammonium acetate to generate a target product d,
4. the synthesis method according to claim 3, wherein in the step (1), the catalyst of the reaction system is Pd (PPh)3)4(ii) a Compound a and catalyst Pd (PPh)3)4Is 1: 0.06.
5. The method according to claim 3, wherein in the step (1), the solvent of the reaction system is a mixture of tetrahydrofuran and water.
6. The synthesis method according to claim 3, wherein in step (1), the molar ratio of the compound a to the compound b is 1:1.2, and the molar ratio of the compound a to sodium carbonate is 1: 3.
7. The synthesis method according to claim 3, wherein in the step (1), the reaction temperature is 50-60 ℃.
8. The synthesis method according to claim 3, wherein in the step (2), the solvent of the reaction system is a mixture of glacial acetic acid and toluene.
9. The method of claim 3, wherein in step (2), the molar ratio of compound c to cyanoacetic acid is 1:3 and the molar ratio of compound c to ammonium acetate is 1: 0.4.
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| CN106674204B (en) * | 2017-01-05 | 2018-12-25 | 浙江工业大学上虞研究院有限公司 | The carbazole compound of the azophenlyene containing dibenzo, preparation method and applications |
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