KR101758614B1 - Novel Polycyclic Fused Ring Derivatives, Organic Dye Sensitizers Containing The Same for Highly Efficient Dye-sensitized Solar Cells And Dye-sensitized Solar Cells Containing The Same - Google Patents
Novel Polycyclic Fused Ring Derivatives, Organic Dye Sensitizers Containing The Same for Highly Efficient Dye-sensitized Solar Cells And Dye-sensitized Solar Cells Containing The Same Download PDFInfo
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- KR101758614B1 KR101758614B1 KR1020150071439A KR20150071439A KR101758614B1 KR 101758614 B1 KR101758614 B1 KR 101758614B1 KR 1020150071439 A KR1020150071439 A KR 1020150071439A KR 20150071439 A KR20150071439 A KR 20150071439A KR 101758614 B1 KR101758614 B1 KR 101758614B1
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- South Korea
- Prior art keywords
- dye
- sensitized solar
- fused ring
- solar cell
- polycyclic fused
- Prior art date
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 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
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- -1 thiadiazol-4-yl Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- 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
- C09B57/00—Other synthetic dyes of known constitution
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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
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Abstract
The present invention relates to a novel polycyclic fused ring derivative, an organic dye for a dye-sensitized solar cell comprising the same, and a dye-sensitized solar cell comprising the organic dye. More specifically, a polycyclic fused ring derivative represented by the following formula The chromophore has a polycyclic fused ring series chromophore consisting of a large number of 5-membered rings including a group 4, group 5 or group 6 element and a benzene ring, which not only has excellent light conversion efficiency but also has long-term stability And can be used as an organic dye for a new high-efficiency dye-sensitized solar cell having improved long-term stability and energy conversion efficiency. In addition, a dye-sensitized solar cell with high efficiency can be produced by using the dye containing the polycyclic fused ring derivative of the present invention.
[Chemical Formula 1]
(2)
(Wherein R 1 , R 2 , L 1 , L 2 , A 1 , A 2 , B, X 1 to X 3 and m are as described in the description of the invention)
Description
The present invention relates to a novel polycyclic fused ring derivative, an organic dye for a dye-sensitized solar cell comprising the same, and a dye-sensitized solar cell comprising the organic dye. More particularly, the present invention relates to a dye- sensitized solar cell comprising a group 4, 5 or 6 element And a polycyclic fused ring series chromophore composed of a large number of 5-membered rings and benzene rings, and thus has excellent long-term stability and long-term stability and energy conversion efficiency. To a novel high-efficiency dye-sensitized solar cell having improved long-term stability and energy conversion efficiency, and a dye-sensitized solar cell comprising the organic dye.
In recent years, various researches have been carried out to replace existing fossil dyes in order to reduce the amount of carbon dioxide emission, which is regarded as a main cause of global warming, and to solve the energy problem faced.
Extensive research to utilize natural energy sources such as wind power, nuclear power, and solar power has been conducted to replace petroleum resources that will be depleted in the near future. Among them, solar cells using solar energy are the most environmentally friendly, Unlike other energy sources, our resources are infinite if we develop the right method.
Since the solar cell using selenium (Se) was developed in 1983, the silicon solar cell is in the spotlight in recent years, but it is very expensive in terms of production cost, so there is a limit in practical use and battery efficiency is still insufficient.
A dye-sensitized solar cell instead of the electric energy used in the driving mechanism of the organic electroluminescent display (OLED) is a mechanism for absorbing the light energy of the visible light to generate an electron-hole pair, Is a photoelectrochemical solar cell having a transition metal oxide as a main constituent material.
A dye-sensitized solar cell using titanium oxide nanoparticles developed by the research team of Michael Graetzel of the Swiss Federal Institute of Technology (Lausanne) (EPFL) in 1991 is a representative example of conventional dye-sensitized solar cells. The dye-sensitized solar cell using the ruthenium-based complex as a dye has advantages in that it can be applied to a glass window of a building or a glass greenhouse due to a transparent electrode. The manufacturing cost is lower than that of a conventional silicon solar cell, Has attracted considerable attention from academia due to its energy conversion efficiency, but it has a disadvantage in that it has low photoelectric conversion efficiency and low stability, which is the biggest problem of a complex dye, and has yet to be commercialized due to the limit of manufacturing cost.
Therefore, in this field, research for replacing organic dyes with photoelectric conversion efficiency with much lower cost is being actively carried out. For example, Korean Patent Laid-Open No. 10-2010-0136931 discloses a dye-sensitized solar cell (DSSC) which is used as a dye-sensitized photoelectric conversion element and has an improved molar extinction coefficient, Jsc Density) and photoelectric conversion efficiency, thereby greatly improving the efficiency of the solar cell. However, the above conventional techniques have a problem in long-term stability of the dye, and when the organic metal dye is used as a photosensor, the solar cell can not exhibit sufficient power conversion efficiency.
Accordingly, the inventors of the present invention have conducted extensive research to develop a novel organic compound dye for dye-sensitized solar cells which can overcome the above-mentioned problems. Among them, a number of 5-membered rings including 4, 5 or 6 elements and benzene Derivatives having a chromophore group of a ring polycyclic fused ring series have excellent photoconversion efficiency as well as excellent long-term stability and can produce a dye-sensitized solar cell device with high efficiency by using the dye containing the chromophore group. And completed the present invention.
The object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a dye-sensitized solar cell which not only has a high photoelectric conversion rate but also solves the difficulties in application of a device due to lack of long- And a polycyclic fused ring derivative comprising a plurality of 5-membered rings and benzene rings including a novel group 4, 5 or 6 element capable of overcoming the above-mentioned problems.
Still another object of the present invention is to provide a dye for a dye-sensitized solar cell having improved long-term stability and energy conversion efficiency including a novel polycyclic fused ring derivative according to the present invention, and a dye-sensitized solar cell comprising the dye have.
In order to accomplish the above object, the present invention provides a polycyclic fused ring derivative comprising a plurality of 5-membered rings and benzene rings each containing a Group 4, 5 or 6 element, The polycyclic fused ring derivative is represented by the following formula (1) or (2)
[Chemical Formula 1]
(2)
In the
R 1 and R 2 are each independently hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;
L 1 and L 2 are each independently (C 6 -C 20) arylene, and the arylene may be further substituted with at least one selected from (C 1 -C 20) alkoxy and (C 1 -C 20) alkyl;
R 3 and R 4 are each independently (C 1 -C 20) alkoxy or (C 6 -C 20) aryl substituted by one or more (C 1 -C 20) alkoxy;
A 1 and A 2 are each independently selected from the following structures;
R 5 is substituted by hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or (C1-C20) alkyl and (C1-C20) one or more selected from alkoxy (C6- C20) aryl;
m is an integer of 0 or 1;
X 1 to X 3 are each independently CR a R b , S, O, NR c , SiR d R e or Se;
R a , R b , R c , R d and R e are each independently hydrogen or (C 1 -C 20) alkyl;
B is
The present invention also provides an organic dye for a dye-sensitized solar cell comprising a polycyclic fused ring derivative represented by the above formula (1) or (2).
The present invention also provides a dye-sensitized solar cell comprising the organic dye for the dye-sensitized solar cell.
The polycyclic fused ring derivative of the present invention is a chromophore having a polycyclic fused ring series chromophore composed of a plurality of 5-membered rings including a group 4 element, a group 5 element or a group 6 element and a benzene ring, Can be used as a new high-efficiency organic dye for dye-sensitized solar cells having long-term stability and energy conversion efficiency as well as long-term stability. In addition, a dye-sensitized solar cell with high efficiency can be produced by using the dye containing the polycyclic fused ring derivative of the present invention.
1 and 2 are UV absorption and PL spectra of polycyclic fused ring compounds (SGT-130, SGT-131, SGT-126 and SGT-121) obtained in Examples 1 to 4.
FIG. 3 is a graph showing the results of photocatalysis of a solar cell using the polycyclic fused ring compounds (SGT-130, SGT-131, SGT-126, SGT-121, SGT-136 and SGT-137) obtained in Examples 1 to 6 as dyes Current density-voltage.
The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.
The present invention relates to a polycyclic fused ring composed of a plurality of 5-membered rings and benzene rings each containing a group 4, group 5 or group 6 element, specifically a polycyclic fused ring derivative represented by the following general formula (1) or (2) Lt; / RTI >
[Chemical Formula 1]
(2)
In the
R 1 and R 2 are each independently hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;
L 1 and L 2 are each independently (C 6 -C 20) arylene, and the arylene may be further substituted with at least one selected from (C 1 -C 20) alkoxy and (C 1 -C 20) alkyl;
R 3 and R 4 are each independently (C 1 -C 20) alkoxy or (C 6 -C 20) aryl substituted by one or more (C 1 -C 20) alkoxy;
A 1 and A 2 are each independently selected from the following structures;
R 5 is substituted by hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or (C1-C20) alkyl and (C1-C20) one or more selected from alkoxy (C6- C20) aryl;
m is an integer of 0 or 1;
X 1 to X 3 are each independently CR a R b , S, O, NR c , SiR d R e or Se;
R a , R b , R c , R d and R e are each independently hydrogen or (C 1 -C 20) alkyl;
B is
The polycyclic fused ring derivative according to the present invention overcomes difficulties in application due to lack of long-term stability, which is a problem of conventional dyes, and overcomes the low efficiency of solar cells using conventional dyes, A solar cell using a junction ring derivative exhibits long-term stability even in an external environment and has a merit that a high energy conversion efficiency can be obtained by securing a wide absorption region band from a visible ray to a near-infrared region.
In one embodiment of the present invention, the polycyclic fused ring derivative includes a polycyclic fused ring derivative represented by the following general formula (3), (4) or (5)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
Wherein R 1 , R 2 , X 1 to X 3 , A 1 , A 2, and B are the same as defined in Formula 1,
Wherein R < 11 > is (C1-C20) alkyl or (C1-C20) alkoxy; R 'is (C1-C20) alkyl; X is an integer of 1 or 2;
In one embodiment of the present invention, X 1 to X 3 are each independently S, O, NR c or Se in Formula 3, Formula 4 or Formula 5, and R c is (C 1 -C 20) alkyl , And R < 11 > may be (C1-C20) alkoxy.
In one embodiment of the present invention, the polycyclic fused ring derivative can be specifically exemplified by the following structure:
The polycyclic fused ring derivatives of the present invention can be prepared, for example, by the following Reaction Scheme 1. Further details are described in Examples 1 to 6 below. However, the production method is not limited to the following Reaction Scheme 1, but can be synthesized by various methods using a known organic reaction.
[Reaction Scheme 1]
The polycyclic fused ring derivative represented by
The present invention also provides a dye-sensitized solar cell comprising the dye for the dye-sensitized solar cell.
In the present invention, the dye-sensitized solar cell may have the following configuration, but not limited thereto:
A first electrode comprising a conductive transparent substrate;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And
Wherein the electrolyte is located in a space between the first electrode and the second electrode.
The materials constituting the solar cell will be described as follows.
The first electrode including the conductive transparent substrate is formed of a transparent electrode formed of at least one material selected from the group consisting of indium tin oxide, fluorine tin oxide, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and tin oxide Or a plastic substrate.
The light absorbing layer necessarily contains an organic dye for a dye-sensitized solar cell comprising a polycyclic fused ring derivative represented by
The second electrode may be the same as the first electrode, or a conductive layer formed of platinum or the like on the light-transmitting electrode of the first electrode may be used.
Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.
[Preparation Example 1] Preparation of Compound 9
Preparation of Compound (1)
Add bromo (b) thiophene (10.00 g), potassium acetate (33.00 g) and CHCl 3 (150 mL) into a 250 mL flask and slowly add bromine (17.2 mL) at room temperature (23 ° C) And refluxed for 24 hours. Br 2 and CHCl 3 were removed by simple distillation, and CH 2 Cl 2 (100 mL) and a saturated aqueous solution of NaHCO 3 (30 mL) were added to the residue. After stirring for 10 minutes, the organic layer was separated and dried in a separating funnel. Compound 1 was obtained (yield: 17.0 g, 62%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.868 (1 H, s), 7.589 (1 H, d), 7.547
Preparation of
Compound 1 (5.05 g) and THF (120 mL) were added to a 250 mL flask, and the solution was slowly cooled and maintained at -78 ° C. while stirring. 2.5 M n-BuLi (in n-hexane) (6.0 mL) And the mixture was stirred for 1 hour. N-promipiperidine (1.8 mL, 1.85 g) was added to the reaction mixture at -78 ° C, and the mixture was slowly warmed and stirred at 10 ° C for 1 hour. To the reaction mixture was added CH 2 Cl 2 (50 mL) and cold water (40 mL), and after stirring for 1 minute, the reaction mixture solution was layered in a separating funnel. The organic layer was dehydrated with anhydrous MgSO 4 , dried and separated to obtain the desired product, Compound 2 (yield: 1.68 g, 39%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 10.267 (1H, s, CHO), 8.051 (1 H, s), 7.889
Preparation of Compound 3
Compound 2 (1.68 g) and DMF (50 mL) were added to a 100 mL flask, and ethyl thioglycolate (0.8 mL, 0.88 g) and K 2 CO 3 (1.02 g) were added in turn, The mixture was maintained at 60 DEG C and stirred for 24 hours. To the reaction mixture at room temperature is added CH 2 Cl 2 (20 mL) and water (10 mL) and after stirring for 1 minute, the reaction mixture solution is separated in a separatory funnel. The organic layer was dehydrated with anhydrous MgSO 4 , dried and separated to obtain the desired product, Compound 3 (yield: 1.23 g, 69%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 8.002 (1 H, s), 7.996 (1 H, s), 7.75 m, OCH 2), 1.567 ( 3 H, t, CH 3).
Preparation of compound 4
Compound 3 (3.85 g) and THF (100 mL) were placed in a 250 mL flask, and a 10% NaOH aqueous solution (NaOH 2.26 g) and MeOH (30 mL) were sequentially added with stirring and slowly heated to reflux for 5 hours. The reaction mixture was maintained at 10 ° C with an ice bath, and the acidity of the reaction mixture receiving layer was adjusted to pH 1 to 3 while slowly adding c-HCl (concentrated HCl). The resulting solid was filtered off and washed with water and MeOH to give the desired product, Compound 4 (yield: 3.4 g, 96%).
1 H-NMR (300 MHz; DMSO; TMS)? 7.978 (1H, s, CO 2 H), 7.901 (1H, s), 7.73 1 H, d)
Preparation of Compound 5
Compound 4 (1.00 g), Cu (0.19 g) and quinoline (10 mL) were placed in a 25 mL flask, and the mixture was heated to 180 DEG C and stirred for 30 minutes. The reaction mixture was transferred to a 100 mL flask and water (20 mL) and n-hexane (30 mL) were added. The reaction mixture was maintained at 10 DEG C, adjusted to pH 1-3 with HCl, and stirred for 10 minutes. The reaction mixture was transferred to a separatory funnel, and the organic layer was dehydrated with anhydrous MgSO 4 , dried and separated to obtain the desired product, Compound 5 (yield: 0.7 g, 87%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.98 (1 H, s), 7.716 (1 H, d), 7.53 d)
Preparation of Compound 6
Compound 6 was obtained by the same method as in ChemSus Chem 2011, 591.
1 H-NMR (300 MHz; (CDCl 3; TMS) δ 7.415-7.452 (4 H, d, J = 8.4 Hz, Ar-H), 7.153-7.231 (6 H, d, J = 8.7 Hz, Ar- H), 6.545-6.612 (4H d, J = 8.7 Hz, Ar-H), 5.546 (H, Br-S, NH), 3.969-4.032 (8 H, t, -OCH 2), 0.857-2.057 (44 H, m, -CH 2, -CH 3). FT-IR (KBr) [cm -1] 3400 (-NH).
Preparation of Compound 7
Add Pd 2 (dba) 3 (0.02 g) and sodium butoxide (0.08 g) into a 50 mL 2-neck round-bottom flask using a glove box and add a condenser Respectively. Under a stream of nitrogen, distilled toluene (20 mL) was poured, t-butylphosphine (0.01 mL) was poured therein, and the mixture was reacted at 110 DEG C under reflux and stirring. After the reaction, the temperature was lowered, extracted with dichloromethane and water, the organic layer was separated and the solvent was evaporated. The residue was purified by column chromatography (eluent hexane: MC = 2: 1) to obtain Compound 7 as a yellow oil (yield: 0.37 g, 73%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.72 (1 H, d), 7.614 (1 H, d), 7.457-424 7.246 (4 H, m), 7.136 (4 H, d), 6.543 (4 H, m), 4.002-3.934 (8 H, t, -OCH 2), 0.831-1.816 (44 H, m, -
Preparation of
Compound 7 (0.2 g) was dissolved in a chloroform solvent, N-bromosuccinimide (0.04 g) was added thereto, and the mixture was stirred at room temperature. The reaction color changed from yellow to green. When the reaction had disappeared by TLC monitoring, the reaction was terminated and extracted with water and MC, then only the MC layer was separated. The residue was purified by column chromatography (developing solvent n-hex: MC = 3: 1) to obtain Compound 8 (yield: 0.41 g, 94%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.63 (1 H, d), 7.58 (2 H, d), 7.51 25 (2 H, m), 7.16 (4 H, d), 6.547 (4 H, m), 4.008-3.941 (8 H, t, -OCH 2), 0.836-1.824 (44 H, m, -
Preparation of Compound 9
Compound 8 (0.6 g) was placed in a 100 mL round flask, and dry THF (50 mL) was added under a nitrogen stream. While the temperature was lowered to -78 ° C with stirring, n-BuLi (0.38 mL) was slowly added dropwise and stirred for 1 hour. Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.26 mL) was added dropwise, and the mixture was slowly warmed to room temperature. The reaction was terminated and extracted with water and MC. Only the MC layer was separated and purified by column chromatography (developing solvent n-hex: MC = 2: 1) to obtain Compound 9 (yield: 0.27 g, 41%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.74 (1 H, d), 7.65 (2 H, d), 7.61 2 H, m), 7.17 ( 4 H, d), 6.579 (4 H, m), 4.054-3.970 (8 H, t, -OCH 2), 0.877-1.894 (44 H, m, -
[Example 1] Production of polycyclic fused ring compound 11 (SGT-130)
Preparation of
Compound 9 (0.26 g) and 4- (7-bromobenzo [c] [1,2] thiadiazol-4-yl) benzaldehyde (0.075 g) were placed in a 100 mL 2-neck round flak after loading the Pd (PPh 3) 4 (0.01 g), the mixture was refluxed for injecting a solvent in a stream of nitrogen in toluene (20 mL), THF (12 mL), ethanol (4 mL) and water (4 mL). When the reaction was completed, the MC layer was separated only after extraction with water and MC. The residue was purified by column chromatography (developing solvent n-hex: MC = 2: 1) to obtain Compound 10 (yield: 0.25 g, 12%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 10.113 (1 H, s, CHO), 8.498 (1 H, s), 8.18 (2 H, m), 8.019-7.993 (4H, d), 7,754 (2H, d), 7,704 (2H, d) 3.956 (8 H, t, -OCH 2 ), 0.873-1.832 (44 H, m, -CH 2 , -CH 3 ). FT-IR (KBr) [cm- 1 ] 1700.91 (-C = O).
Preparation of Compound 11
Compound 10 (0.12 g), cyanoacetic acid (0.04 g) and piperidine (0.02 g) were added to a 50 mL 2-neck round flask and refluxed under solvent acetonitrile. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. The residue was purified by column chromatography (developing solvent MC: MeOH = 25: 1) to obtain Compound 11 (yield: 0.09 g, 72%).
1 H-NMR (300 MHz; CDCl 3; TMS) δ 12.42 (1 H, s, CO 2 H) 8.52 (1 H, s), 8.23 (2 H, m), 8.10-7.98 (3 H, m) , 7.91 (2H, d), 7.85 (2H, d), 7.52 (4H, d), 7.43 -3.98 (8 H, t, -OCH 2 ), 0.891-1.864 (44 H, m, -CH 2 , -CH 3 ). FT-IR (KBr) [cm- 1 ] 2264.02 (-CN), 1734.66 (-C = O).
[Example 2] Production of polycyclic fused ring compound 13 (SGT-131)
Preparation of
(0.2 g) and butyl 4- (4-bromobenzo [c] [1,2] thiadiazol-7-yl) benzoate (0.07 g) were placed in a 100 mL 2-neck round flak, Pd (PPh 3 ) 4 (0.012 g) was added to the reaction mixture and toluene (20 mL), THF (12 mL), ethanol (4 mL) and water (4 mL) were injected under reflux in a nitrogen stream. When the reaction was completed, the MC layer was separated only after extraction with water and MC. The residue was purified by column chromatography (developing solvent n-hex: MC = 2: 1) to obtain Compound 12 (yield: 0.07 g, 33%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 8.475 (1 H, s), 8.229 (2 H, m), 8.07-04 (3 H, m), 7.988 2 H, d), 7.498 ( 4 H, d), 7.329 (4 H, d), 7.183 (4 H, d), 6.563 (4 H, m), 4.40 (2 H, t, -OCH 2), 4.015-3.956 (8 H, t, -OCH 2), 0.873-1.832 (51 H, m, -
Preparation of Compound 13
Compound 12 (0.07 g) and potassium hydroxide (0.036 g) were placed in a 50 mL 2-neck round flask and refluxed under solvent 2-ethoxyethanol: THF: water = 3: 2: 1. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. The residue was purified by column chromatography (developing solvent Hex: EA = 2: 1) to obtain Compound 13 (yield: 0.03 g, 42%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 10.8 (1 H, s, CO 2 H), 8.46 (1 H, s), 8.23 (1H, d), 7.87 (2H, d), 7.65 (2H, d), 7.35 2 H, t, -OCH 2 ), 3.98 (8 H, t, -OCH 2 ), 0.854-1.87 (51 H, m, -CH 2 , -CH 3 ). FT-IR (KBr) [cm- 1 ] 1730.8 (-C = O).
[Example 3] Preparation of polycyclic fused ring compound 15 (SGT-126)
Preparation of
To a solution of compound 9 (0.3 g) and 5- (4-bromobenzo [c] [1,2] thiadiazol-7-yl) thiophene-2-carbaldehyde ) and the mixture was placed a Pd (PPh 3) 4 (0.018 g) in a glove box, it was in a stream of nitrogen the solvent toluene (20 mL), THF (12 mL) under reflux by injecting ethanol (4 mL) and water (4 mL (Yield: 0.2 g, 66%). The reaction mixture was filtered and the filtrate was concentrated under reduced pressure. .
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 9.985 (1 H, s, CHO), 8.513 (2 H, s), 8.02-7.97 (1H, d), 7.52 (4H, d), 7.32 (4H, d), 7.17 2), 0.711-2.207 (44 H, m, -
Preparation of compound 15
Compound 14 (0.2 g), cyanoacetic acid (0.14 g) and piperidine (0.07 g) were added to a 50 mL 2-neck round flask and refluxed under solvent acetonitrile. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. Purification by column chromatography (developing solvent MC: MeOH = 25: 1) afforded compound 15 (yield: 0.15 g, 71%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 11.57 (1 H, s, CO 2 H), 8.51 (2 H, s), 8.15-8.06 ), 7.95-92 (2 H, d), 7.57 (4 H, d), 7.36 (4 H, d), 7.19 , -OCH 2), 0.865-2.037 (44 H, m, -
[Example 4] Preparation of polycyclic fused ring compound 17 (SGT-121)
Preparation of
100mL 2-neck round flak put in compound 8 (0.1 g) and (5- (1, 3-dioxane turbulence-2-yl) thiophen-2-yl) tree view tilseu taeneon (0.05 g), Pd (PPh 3 ) 2 Cl 2 (0.01 g) was added thereto, followed by refluxing with 20 mL of toluene as a solvent under nitrogen flow. When the reaction was completed, the MC layer was separated only after extraction with water and MC. The residue was purified by column chromatography (developing solvent n-hex: MC = 2: 1) to obtain Compound 16 (yield: 0.05 g, 40%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 9.873 (1 H, s), 7.698 (2 H, d), 7.589 (1 H, d), 7.523 2 H, d), 7.302 ( 4 H, d), 7.19 (4 H, d), 7.183 (4 H, d), 6.558 (4 H, m), 4.06 (8 H, t, -OCH 2), 0.846-1.832 (44 H, m, -
Preparation of Compound 17
Compound 16 (0.05 g), cyanoacetic acid (0.01 g) and piperidine (0.01 g) were added to a 50 mL 2-neck round flask and refluxed under solvent acetonitrile. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. The residue was purified by column chromatography (developing solvent MC: MeOH = 25: 1) to obtain Compound 17 (yield: 0.04 g, 75%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 8.316 (1 H, s), 7.749 (2 H, d), 7.69 2 H, d), 7.491 ( 4 H, d), 7.343 (4 H, d), 7.27 (4 H, d), 6.554 (4 H, m), 4.01 (8 H, t, -OCH 2), 0.865-1.804 (44 H, m, -
[Example 5] Preparation of polycyclic fused ring compound 21 (SGT-136)
Preparation of Compound 19
Pd 2 (dba) 3 (0.02 g) and sodium butoxide (0.08 g) were added to a 50 mL 2-neck round-bottom flask using a glove box and the condenser was charged with the compound 18 (0.11 g) Respectively. Under a stream of nitrogen, distilled toluene (20 mL) was poured, t-butylphosphine (0.01 mL) was poured therein, and the mixture was reacted at 110 DEG C under reflux and stirring. After the reaction, the temperature was lowered, extracted with dichloromethane and water, the organic layer was separated and the solvent was evaporated. The residue was purified by column chromatography (developing solvent: hexane: MC = 3: 1) to obtain Compound 19 as a yellow oil (yield: 0.14 g, 68%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.66 (1 H, d), 7.436-7.407 (4 H, m), 7.330 4 H, d), 7.043 ( 2 H, d), 6.542-6.524 (4 H, m), 4.221 (q, 2 H), 4.004-3.934 (8 H, t, -OCH 2), 0.831-1.816 ( 47 H, m, -CH 2, -CH 3).
Preparation of Compound 20
Compound 19 (0.1 g) was placed in a 50 mL round flask, and dry THF (50 mL) was added under a nitrogen stream. While the temperature was lowered to -78 ° C with stirring, n-BuLi (0.38 mL) was slowly added dropwise and stirred for 1 hour. After that, trivile tilttin chloride was added dropwise, and then slowly warmed to room temperature. After completion of the reaction and extraction with water and MC, only the MC layer was separated, and after vacuum drying without purification, 4- (7-bromobenzo [c] [1,2,5] thiadiazol-4- yl) benzaldehyde 0.053 g) and Pd (PPh 3 ) 2 Cl 2 (0.01 g) were charged, and 20 mL of toluene as a solvent was introduced under reflux in a nitrogen stream. When the reaction was completed, the MC layer was separated only after extraction with water and MC. The residue was purified by column chromatography (developing solvent n-hex: MC = 1: 50) to give compound 20 (yield: 0.05 g, 40%). Yield: 0.27 g, 41%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 10.118 (1 H, s, CHO), 8.414 (1 H, s), 8.20 (1 H, d), 8.105-8.026 7.847 (1H, d), 7.732 (5H, m), 7.692 (1H, s), 7.546 4 H, m), 4.234 (2 H, q), 4.009-3.945 (8 H, t, -OCH 2 ), 0.873-1.832 (47 H, m, -CH 2 , -CH 3 ).
Preparation of Compound 21
Compound 20 (0.053 g), cyanoacetic acid (0.05 g) and piperidine (0.01 g) were added to a 50 mL 2-neck round flask and refluxed under solvent acetonitrile. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. The residue was purified by column chromatography (developing solvent MC: MeOH = 10: 1) to obtain Compound 21 (yield: 12 mg, 71%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 8.414 (1 H, d), 8.20 (1 H, d), 8.105-8.026 (3 H, m), 7.847 5H, m), 7.692 (1H, s), 7.546 (2H, d), 7.465 , q), 4.009-3.945 (8 H , t, -OCH 2), 0.873-1.832 (47 H, m, -
[Example 6] Preparation of polycyclic fused ring compound 25 (SGT-137)
Preparation of Compound 23
Add Pd 2 (dba) 3 (0.02 g) and sodium butoxide (0.08 g) into a 50 mL 2-neck round-bottom flask using a glove box and add a condenser Respectively. Under a stream of nitrogen, distilled toluene (20 mL) was poured, t-butylphosphine (0.01 mL) was poured therein, and the mixture was reacted at 110 DEG C under reflux and stirring. After the reaction, the temperature was lowered, extracted with dichloromethane and water, the organic layer was separated and the solvent was evaporated. The residue was purified by column chromatography (developing solvent: hexane: MC = 3: 1) to obtain Compound 23 as a yellow oil (yield: 0.13 g, 73%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 7.66 (1 H, d), 7.44 (4 H, m), 7.322 , d), 7.047 (2 H , d), 6.549-6.520 (4 H, m), 4.142 (q, 2 H), 4.009-3.938 (8 H, t, -OCH 2), 0798-1.826 (55 H , m, -CH 2, -CH 3 ).
Preparation of Compound 24
Compound 23 (0.11 g) was placed in a 50 mL round flask, and dry THF (50 mL) was added under a nitrogen stream. While the temperature was lowered to -78 ° C with stirring, n-BuLi (0.38 mL) was slowly added dropwise and stirred for 1 hour. After that, trivile tilttin chloride was added dropwise, and then slowly warmed to room temperature. After completion of the reaction and extraction with water and MC, only the MC layer was separated, and after vacuum drying without purification, 4- (7-bromobenzo [c] [1,2,5] thiadiazol-4- yl) benzaldehyde 0.04 g) and Pd (PPh 3 ) 2 Cl 2 (0.01 g) were charged. Then, 20 mL of toluene as a solvent was introduced under reflux in a nitrogen stream. When the reaction was completed, the MC layer was separated only after extraction with water and MC. The residue was purified by column chromatography (developing solvent n-hex: MC = 1: 50) to obtain Compound 24 (yield: 0.04 g, 34%). Yield: 0.27 g, 41%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 10.118 (1 H, s, CHO), 8.391 (1 H, s), 8.20 (1 H, d), 8.108-8.021 D), 7.207 (2H, d), 6.553 (1H, d), 7.70 (1H, 4 H, m), 4.293 ( 2 H, q), 4.009-3.945 (8 H, t, -OCH 2), 0.873-1.832 (55 H, m, -
Preparation of Compound 25
Compound 20 (0.042 g), cyanoacetic acid (0.05 g) and piperidine (0.01 g) were added to a 50 mL 2-neck round flask and refluxed under solvent acetonitrile. When the reactants disappeared, the reaction was terminated and acid treatment was carried out. After the acid treatment, it was extracted with water and MC, and then only the MC layer was separated. The residue was purified by column chromatography (developing solvent MC: MeOH = 10: 1) to obtain Compound 25 (yield: 2.2 mg, 64%).
1 H-NMR (300 MHz; CDCl 3 ; TMS)? 8.391 (1 H, s), 8.20 (1 H, d), 8.108-8.021 (3 H, m), 7.847 (2H, d), 6.553 (4H, m), 4.293 (2H, d) , q), 4.009-3.945 (8 H , t, -OCH 2), 0.873-1.832 (55 H, m, -
Evaluation of spectroscopic characteristics
UV absorption and PL spectra of the polycyclic fused ring compounds (SGT-130, SGT-131, SGT-126 and SGT-121) obtained in Examples 1 to 4 are shown in FIGS.
Characterization of dye-sensitized solar cell
The dye-sensitized solar cell using the polycyclic fused ring compounds (SGT-130, SGT-131, SGT-126, SGT-121, SGT-136 and SGT-137) obtained in Examples 1 to 6, .
A dispersion of titanium oxide particles having an average particle diameter of 20 nm in particle size was applied on the conductive film made of ITO of the first electrode to a surface area of 0.25
Then, the resultant was held at 80 ° C, and the resultant was added to the polycyclic fused ring compound (SGT-130, SGT-131, SGT-126, SGT-121, SGT-136, SGT-137 ) Were immersed in a 0.3 mM dye dispersion in ethanol, and dye adsorption treatment was carried out for 2 hours.
Thereafter, the dye-adsorbed porous membrane was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorbing layer.
Separately, the second electrode was formed by depositing a second conductive film made of Pt on a first conductive film made of ITO by sputtering, and using a drill having a diameter of 0.75 mm for injecting an electrolyte, a fine hole was formed.
Thereafter, a support made of a thermoplastic polymer film having a thickness of 25 탆 was bonded between the first and second electrodes having the porous film formed thereon at 80 캜 for 16 seconds to bond the two electrodes. Then, the electrolyte was injected through the micropores formed in the second electrode, and the micropores were sealed using a cover glass and a thermoplastic polymer film to prepare a dye-sensitized solar cell. At this time, the electrolyte used is of 0.22M [Co (bpy) 3] 2+, a [Co (bpy) 3] 3+ , 4-t- butyl pyridine of LiClO 4 and 1.0M of a 0.05M 0.05M CH 3 CN.
The voltage-current density of the cell was measured under illumination conditions of 1 sun (100 mW / cm) using the dye-sensitized solar cell prepared above, and the result is shown in FIG.
[mA cm -2 ]
[mV]
(%)
(%)
The polycyclic fused ring compound of the present invention has excellent photoconversion efficiency and absorbs a wide range of light and thus has excellent properties as a dye for a dye-sensitized solar cell.
Claims (6)
(3)
R 1 and R 2 are each independently hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy;
Wherein R < 11 > is (C1-C20) alkyl or (C1-C20) alkoxy; R 'is (C1-C20) alkyl; X is an integer of 1 or 2;
A 2 is
X 1 and X 2 are each independently S, O, NR c , SiR d R e or Se;
R c , R d and R e are each independently hydrogen or (C 1 -C 20) alkyl;
B is
A polycyclic fused ring derivative selected from the following structures:
The dye-sensitized solar cell
A first electrode comprising a conductive transparent substrate;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And
And an electrolyte located in a space between the first electrode and the second electrode.
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