KR101882394B1 - Novel organic dye and preparation thereof - Google Patents
Novel organic dye and preparation thereof Download PDFInfo
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- KR101882394B1 KR101882394B1 KR1020100131967A KR20100131967A KR101882394B1 KR 101882394 B1 KR101882394 B1 KR 101882394B1 KR 1020100131967 A KR1020100131967 A KR 1020100131967A KR 20100131967 A KR20100131967 A KR 20100131967A KR 101882394 B1 KR101882394 B1 KR 101882394B1
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- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims description 48
- 239000004065 semiconductor Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 37
- 230000008033 biological extinction Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 125000006850 spacer group Chemical group 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007824 aliphatic compounds Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 238000000434 field desorption mass spectrometry Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- YYXZQUOJBJOARI-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;iodide Chemical compound [I-].CCCCCCN1C=C[N+](C)=C1C YYXZQUOJBJOARI-UHFFFAOYSA-M 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- -1 5-oxothiophen- - boronic acid Chemical compound 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- SFGUXGKXUYYEIR-ONEGZZNKSA-N [(e)-(5-oxothiophen-2-ylidene)methyl]boronic acid Chemical compound OB(O)\C=C1\SC(=O)C=C1 SFGUXGKXUYYEIR-ONEGZZNKSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
본 발명은 신규한 유기염료 및 이의 제조방법에 관한 것으로, 전자 공여체로서 특정 지방족 화합물을, 중간 연결부분(스페이서(spacer))에 티오펜계 또는 디하이드로티오펜계 유닛을 갖는 본 발명의 염료 화합물은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.The present invention relates to a novel organic dye and a process for producing the same, wherein a specific aliphatic compound is used as an electron donor and a dye compound of the present invention having a thiophene- or dihydrothiophene-based unit at an intermediate connecting portion (spacer) Can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar extinction coefficient, J sc (single-line photocurrent density) and photoelectric conversion efficiency over conventional dyes, , The purification can be performed without using an expensive column, and the cost of dye synthesis can be remarkably lowered.
Description
본 발명은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되는 신규한 염료 및 이의 제조방법에 관한 것이다.
The present invention relates to a novel dye used in a dye-sensitized solar cell (DSSC) and a method of producing the same.
1991년도 스위스 국립 로잔 고등기술원(EPFL)의 마이클 그라첼(Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 효율이 높고 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀(hole) 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Much research has been done in this area since the development of dye-sensitized nanoparticle titanium dioxide solar cells by Michael Gratzel of the Swiss National Lozan Institute for Technology (EPFL) in 1991. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because they have higher efficiency and lower manufacturing costs than conventional silicon solar cells. Unlike silicon solar cells, dye-sensitized solar cells have the potential to replace visible silicon A dye molecule capable of absorbing and generating an electron-hole pair, and a transition metal oxide transmitting the generated electrons as main constituent materials.
염료감응태양전지에 사용되는 염료로서 높은 광전기 전환효율을 나타내는 루테늄 금속 착체가 널리 사용되어 왔는데, 이 루테늄 금속 착체는 가격이 너무 비싸다는 단점이 있었다.Ruthenium metal complexes exhibiting high photoelectric conversion efficiency have been widely used as dyes for dye-sensitized solar cells, and these ruthenium metal complexes have been disadvantageous in that they are too expensive.
최근, 흡광효율, 산화환원 반응 안정성 및 분자내 전하-전달(charge-transfer, CT)계 흡수의 측면에서 우수한 물성을 나타내는, 금속을 함유하지 않은 유기염료가, 고가의 루테늄 금속 착체를 대체할 수 있는 태양전지용 염료로서 사용될 수 있음이 발견되어, 금속이 결여된 유기염료에 대한 연구가 중점적으로 이루어지고 있다.Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of absorption efficiency, redox stability and intramolecular charge-transfer (CT) absorption, can replace expensive ruthenium metal complexes It has been found that the dye can be used as a dye for a solar cell, and studies on an organic dye lacking a metal have been focused on.
유기염료는 일반적으로 π-결합 유닛에 의해 연결되는 전자 공여체(electron donor)-전자 수용체(electron acceptor) 잔기의 구조를 갖는다. 대부분의 유기염료에서, 아민 유도체가 전자 공여체의 역할을 하고, 2-시아노아크릴산 또는 로다닌 잔기가 전자 수용체의 역할을 하며, 이 두 부위는 메타인 유닛 또는 티오펜 체인과 같은 π-결합 시스템에 의해 연결된다.Organic dyes generally have a structure of electron donor-electron acceptor moieties connected by a pi-bonding unit. In most organic dyes, the amine derivative serves as an electron donor, and the 2-cyanoacrylic acid or rhodanine residue serves as an electron acceptor, and these two moieties are linked by a π-bond system such as a methine unit or thiophene chain Lt; / RTI >
일반적으로, 전자 공여체인 아민 유닛의 구조적 변화는 전자 특성의 변화, 예를 들어 청색 쪽으로 쉬프트(shift)된 흡광 스펙트럼을 가져오고, π-결합 길이를 변화시켜 흡광 스펙트럼과 산화환원 전위(redox potential)를 조절할 수 있다.In general, the structural change of the amine unit, which is an electron donor, leads to a change in the electron characteristics, for example, an absorption spectrum shifted to the blue side, and changes the? -Bond length to change the absorption spectrum and the redox potential, Can be adjusted.
그러나, 이제까지 알려진 대부분의 유기염료는 루테늄 금속 착체 염료에 비해 낮은 변환효율과 낮은 구동 안정성을 나타내므로, 이러한 전자 공여체와 수용체의 종류 또는 π-결합 길이를 변화시킴으로써, 기존의 유기염료 화합물들에 비해 향상된 몰흡광계수를 가지며 높은 광전기 변환효율을 나타내는 새로운 염료를 개발하려는 노력이 지속되고 있는 실정이다.
However, since most of the organic dyes known so far exhibit lower conversion efficiency and lower driving stability than ruthenium metal complex dyes, by changing the kind or? -Bond length of such electron donors and acceptors, Efforts have been made to develop new dyes having improved molar extinction coefficient and high photoelectric conversion efficiency.
따라서, 본 발명은 종래의 염료보다 향상된 몰흡광계수 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있는 유기염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, it is an object of the present invention to provide an organic dye capable of significantly improving the efficiency of a solar cell by showing a molar extinction coefficient and photoelectric conversion efficiency higher than those of conventional dyes, and a method for producing the same.
또한 본 발명은 상기 염료를 포함하여 현저히 향상된 광전기 변환효율을 나타내며, Jsc(단회로 광전류 밀도, short circuit photocurrent density)와 몰흡광계수가 우수한 염료증감 광전변환소자, 및 효율이 현저히 향상된 태양전지를 제공하는 것을 목적으로 한다.
The present invention also provides a dye-sensitized photoelectric conversion device which exhibits remarkably improved photoelectric conversion efficiency including the dye and has excellent J sc (short circuit photocurrent density) and molar extinction coefficient, and a solar cell with remarkably improved efficiency The purpose is to provide.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1 내지 4 중 어느 하나로 표시되는 유기염료를 제공한다.In order to accomplish the above object, the present invention provides an organic dye represented by any one of the following formulas (1) to (4).
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
상기 식에서,In this formula,
Ar1, Ar2, Ar3 는 각각 독립적으로 치환되거나 비치환된 C6 -12 아릴이고;Ar 1, Ar 2, Ar 3 are each independently a substituted or unsubstituted C 6 -12 aryl;
A는 
B는 
C는 C is
R1 내지 R4는 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이고;R 1 to R 4 are each independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl;
n은 1 내지 5의 정수이다.
n is an integer of 1 to 5;
또한 본 발명은 하기 화학식 5 또는 화학식 15로 표시되는 화합물과 상기 화학식 1 내지 4에서 정의한 A, B, A와 B, 또는 B와 A의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 C를 결합하여 제조되는 화학식 1 내지 4 중 어느 하나로 표시되는 염료의 제조방법을 제공한다.The present invention also relates to a process for preparing a compound represented by the following general formula (5) or (15) and a precursor compound of A, B, A and B or B and A defined in the above general formulas (1) to (4).
[화학식 5][Chemical Formula 5]
[화학식 15][Chemical Formula 15]
또한 본 발명은 상기 화학식 1 내지 4 중 어느 하나로 표시되는 화합물을 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.
The present invention also provides a dye-sensitized photoelectric conversion device comprising oxide semiconductor microparticles on which a compound represented by any one of Chemical Formulas 1 to 4 is supported.
또한 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
본 발명의 염료 화합물은 염료감응태양전지(DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.
INDUSTRIAL APPLICABILITY The dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar extinction coefficient, J sc (single-line photocurrent density) and photoelectric conversion efficiency, Purification can be performed without using an expensive column, and the cost of dye synthesis can be remarkably lowered.
본 발명자들은, 특정 지방족 화합물을 전자 공여체로서 사용하고, 중간 연결부분(스페이서(spacer))에는 몰흡광계수를 증가시키고 소자의 안정성을 증가시키기 위한 티오펜계 또는 디하이드로티오펜계 유닛을 도입하되, 단일 방향으로 존재하던 스페이서 및 고정체(anchoring group)를 양 방향으로 도입하는 등 새로운 유기염료 구조를 갖는 화학식 1 내지 4 중 어느 하나로 표시되는 화합물을 산화물 반도체 미립자에 담지시켜 염료감응태양전지를 제조할 경우 광전기 변환효율, Jsc(단회로 광전류 밀도) 및 몰흡광계수가 높아 기존 염료감응태양전지보다 우수한 효율을 나타냄을 확인하고 본 발명을 완성하게 되었다.The present inventors have found that a thiophene-based or dihydrothiophene-based unit is used for the purpose of increasing the molar extinction coefficient and increasing the stability of the device, by using a specific aliphatic compound as an electron donor and an intermediate connecting portion (spacer) , A compound represented by any one of formulas (1) to (4) having a novel organic dye structure such as introducing a spacer and an anchoring group existing in a single direction in both directions is supported on oxide semiconductor fine particles to prepare a dye- It was confirmed that the photovoltaic conversion efficiency, Jsc (single photocurrent density) and molar extinction coefficient were higher than those of the conventional dye-sensitized solar cell, and the present invention was completed.
본 발명의 유기염료는 하기 화학식 1 내지 4 중 어느 하나로 표시되는 것을 특징으로 한다.The organic dye of the present invention is characterized by being represented by any of the following formulas (1) to (4).
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
상기 식에서, Ar1, Ar2, Ar3, A, B, C, R1 내지 R4, 및 n은 상기에서 정의한 바와 같다.Wherein Ar 1 , Ar 2 , Ar 3 , A, B, C, R 1 to R 4 , and n are as defined above.
본 발명의 화학식 1의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula (1) of the present invention can preferably be represented by one of the following formulas:
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
[화학식 1-6][Chemical Formula 1-6]
[화학식 1-7][Chemical Formula 1-7]
[화학식 1-8][Chemical Formula 1-8]
[화학식 1-9][Chemical Formula 1-9]
[화학식 1-10][Chemical Formula 1-10]
[화학식 1-11][Formula 1-11]
[화학식 1-12][Formula 1-12]
[화학식 1-13][Formula 1-13]
상기 식에서, R은 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이다.Wherein each R is independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl.
본 발명의 화학식 2의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula (2) of the present invention may preferably be represented by one of the following formulas:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Chemical Formula 2-4]
[화학식 2-5][Chemical Formula 2-5]
[화학식 2-6][Chemical Formula 2-6]
[화학식 2-7][Chemical Formula 2-7]
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
본 발명의 화학식 3의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula (III) of the present invention may preferably be represented by one of the following formulas:
[화학식 3-1][Formula 3-1]
[화학식 3-2][Formula 3-2]
[화학식 3-3][Formula 3-3]
[화학식 3-4][Chemical Formula 3-4]
[화학식 3-5][Formula 3-5]
상기 식에서, R은 상기에서 정의한 바와 같다.Wherein R is as defined above.
본 발명의 화학식 4의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다:The dye compound of formula (IV) of the present invention may preferably be represented by any one of the following formulas:
[화학식 4-1][Formula 4-1]
[화학식 4-2][Formula 4-2]
[화학식 4-3][Formula 4-3]
[화학식 4-4][Formula 4-4]
[화학식 4-5][Formula 4-5]
상기 식에서, R은 상기에서 정의한 바와 같다.
Wherein R is as defined above.
또한 본 발명의 화학식 1 내지 4 중 어느 하나로 표시되는 염료는 하기 화학식 5 또는 화학식 15로 표시되는 화합물과 상기 화학식 1 내지 4에서 정의한 A, B, A와 B, 또는 B와 A의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 C를 결합하여 제조할 수 있다.The dyes represented by any one of formulas (1) to (4) of the present invention may be prepared by reacting a compound represented by the following formula (5) or (15) with the precursor compounds of A, B, A and B, or B and A defined in the above formulas And then reacting the resulting compound with C at the terminal of the obtained compound.
[화학식 5][Chemical Formula 5]
[화학식 15][Chemical Formula 15]
구체적으로 본 발명에 따른 화학식 1의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 7의 화합물을 제조하고, (2) 화학식 7의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 1로서 나타낼 수 있다.Specifically, the compound of formula (1) according to the present invention can be prepared by, for example, (1) reacting a compound of formula (5) the compound in the presence piperidine in CH 3 CN can be prepared by reacting the cyanoacetic acid. A specific example thereof can be shown as the following Reaction Scheme 1.
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
상기 식에서, B는 상기에서 정의한 바와 같다.Wherein B is as defined above.
[반응식 1][Reaction Scheme 1]
본 발명에 따른 화학식 2의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 8의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 9의 화합물을 제조하고, (2) 화학식 9의 화합물을 테트라하이드로퓨란(THF) 중에서 트리플루오로아세트산과 반응시켜 하기 화학식 10의 화합물을 제조하고, (3) 화학식 10의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 2로서 나타낼 수 있다.(1) reacting a compound of the following formula (5) with a compound of the following formula (8) by a Suzuki coupling reaction to prepare a compound of the formula (9), (2) With trifluoroacetic acid in tetrahydrofuran (THF) to produce a compound of formula 10, and (3) reacting the compound of formula 10 with cyanoacetic acid in the presence of piperidine in CH 3 CN . A specific example thereof can be shown as the following reaction formula (2).
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Chemical formula 10]
상기 식에서, A 및 B는 상기에서 정의한 바와 같다.Wherein A and B are as defined above.
[반응식 2][Reaction Scheme 2]
본 발명에 따른 화학식 3의 화합물은 예를 들어, (1) 하기 화학식 5의 화합물을 하기 화학식 11의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 12의 화합물을 제조하고, (2) 화학식 12의 화합물을 N-브로모숙신이미드와 반응시켜 하기 화학식 13의 화합물을 제조하고, (3) 화학식 13의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 14의 화합물을 제조하고, (4) 화학식 14의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 3으로서 나타낼 수 있다.(1) a compound of the following formula (5) is subjected to a Suzuki coupling reaction with a compound of the following formula (11) to prepare a compound of the following formula (12), (2) (3) reacting a compound of formula (13) with a compound of formula (6) to produce a compound of formula (14), (4) reacting a compound of formula a compound of formula 14 under the piperidine present in CH 3 CN can be prepared by reacting the cyanoacetic acid. A specific example thereof can be shown as the following reaction formula (3).
[화학식 5][Chemical Formula 5]
[화학식 11](11)
(HO)2B - A(HO) 2 B - A
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
[화학식 6][Chemical Formula 6]
[화학식 14][Chemical Formula 14]
상기 식에서, A 및 B는 상기에서 정의한 바와 같다.Wherein A and B are as defined above.
[반응식 3][Reaction Scheme 3]
본 발명에 따른 화학식 4의 화합물은 예를 들어, (1) 하기 화학식 15의 화합물을 하기 화학식 16의 화합물과 테트라하이드로퓨란(THF) 중에서 칼륨 t-부톡시드 존재 하에 반응시켜 하기 화학식 17의 화합물을 제조하고, (2) 화학식 17의 화합물을 N-브로모숙신이미드와 반응시켜 하기 화학식 18의 화합물을 제조하고, (3) 화학식 18의 화합물을 하기 화학식 6의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 19의 화합물을 제조하고, (4) 화학식 19의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 시아노아세트산과 반응시킴으로써 제조될 수 있다. 그 구체적인 일례는 하기 반응식 4로서 나타낼 수 있다.(1) reacting a compound of the following formula (15) with a compound of the formula (16) in the presence of potassium t-butoxide in tetrahydrofuran (THF) to obtain a compound of the formula (17) (2) reacting the compound of formula (17) with N-bromosuccinimide to prepare a compound of formula (18), and (3) subjecting the compound of formula (18) to Suzuki coupling reaction with a compound of formula preparing a compound of formula (19), and (4) can be prepared by reacting cyanoacetic acid with a compound of formula 19 under the piperidine present in CH 3 CN. A specific example thereof can be represented by the following reaction formula (4).
[화학식 15][Chemical Formula 15]
[화학식 16][Chemical Formula 16]
OHC - AOHC - A
[화학식 17][Chemical Formula 17]
[화학식 18][Chemical Formula 18]
[화학식 6][Chemical Formula 6]
[화학식 19][Chemical Formula 19]
상기 식에서, A 및 B는 상기에서 정의한 바와 같다.Wherein A and B are as defined above.
[반응식 4][Reaction Scheme 4]
또한 본 발명은 염료증감 광전변환소자를 제공하는 바, 상기 염료증감 광전변환소자는 산화물 반도체 미립자에 상기 화학식 1 내지 4 중 어느 하나로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명은 염료증감 광전변환소자는 상기 화학식 1 내지 4 중 어느 하나로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 구체적인 일예로 대한민국공개특허공보 제10-2009-38377호(출원인 동진쎄미켐(주))에 기재된 방법들이 적용될 수 있으며, 바람직하게는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.
Further, the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye-sensitized photoelectric conversion element is characterized in that the dye represented by any one of Chemical Formulas 1 to 4 is supported on the oxide semiconductor fine particles. The dye-sensitized photoelectric conversion device of the present invention can be applied not only to the dye represented by any one of the formulas (1) to (4), but also to a method for producing a dye-sensitized photoelectric conversion device for a solar cell using conventional dyes. For example, the methods described in Korean Patent Publication No. 10-2009-38377 (Applicant, Dongjin Semichem Co., Ltd.) can be applied. Preferably, the dye-sensitized photoelectric conversion element of the present invention is formed by using oxide semiconductor microparticles It is preferable that a thin film of an oxide semiconductor is produced and then the dye of the present invention is carried on the thin film.
이하에서 본 발명을 실시예에 의거하여 보다 구체적으로 설명한다. 단, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.
실시예 1 Example 1
3,6-dibromo-N,N-bis(4-methoxyphenyl)-10-phenylanthracen-9-amine 과 (E)-(5-oxothiophen-2(5H)-ylidene) methylboronic acid, Pd(PPh3)4 및 2M K2CO3 수용액을 디메틸포름아미드(DMF) 중에서 혼합한 후 12시간 동안 환류하였다. 결과로 수득된 반응 용액을 냉각시키고, 물(30ml)과 염수를 첨가한 후, 유기층을 분리 및 정제하여 중간체를 얻었다.(E) - (5-oxothiophen-2 (5H) -ylidene) methylboronic acid, Pd (PPh 3 ) 4 and N-bis (4-methoxyphenyl) And 2M K 2 CO 3 aqueous solution were mixed in dimethylformamide (DMF) and refluxed for 12 hours. The resulting reaction solution was cooled, water (30 ml) and brine were added, and the organic layer was separated and purified to give an intermediate.
상기에서 제조된 중간체와 시아노아세트산을 혼합하여 제조한 혼합물을 진공건조한 후, MeCN 및 피페리딘와 혼합하고, 6시간 동안 환류하였다. 결과로 수득된 반응용액을 냉각시킨 후 유기층을 진공 하에서 제거하였다. 결과로 수득된 고형물을 실리카 겔 크로마토그래피 정제하여 하기 화합물 1을 얻었다. 얻은 화합물 1에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C50H33N3O6S2=836 에 대하여 m/z(측정치)=835 임을 확인했다.The mixture prepared by mixing the intermediate prepared above and cyanoacetic acid was vacuum dried, mixed with MeCN and piperidine, and refluxed for 6 hours. The resulting reaction solution was cooled and the organic layer was removed under vacuum. The resulting solid was purified by silica gel chromatography to give the following compound 1. The obtained Compound 1 was subjected to Field Desorption Mass Spectrometry (FD-MS). As a result, it was confirmed that m / z (measured value) was 835 for C 50 H 33 N 3 O 6 S 2 = 836.
[화합물 1][Compound 1]
실시예 2 :Example 2:
상기 실시예 1에서 (E)-(5-oxothiophen-2(5H)-ylidene)methylboronic acid 대신에 (E)-(5-oxothieno[3,2-b]thiophen-2(5H)-ylidene)methyl- boronic acid를 사용하는 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화합물 2를 얻었다. 상기 화합물 2에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C54H33N3O6S4=948 에 대하여 m/z(측정치)=947 임을 확인했다.(E) - (5-oxothieno [3,2-b] thiophen-2 (5H) -ylidene) methyl ester was obtained in the same manner as in Example 1, except that (E) - (5-oxothiophen- - boronic acid was used in the same manner as in Example 1, to thereby give the following compound 2. Field desorption mass spectrometry (FD-MS) was carried out on Compound 2 to find that m / z (measured value) = 947 for C 54 H 33 N 3 O 6 S 4 = 948.
[화합물 2][Compound 2]
실시예 3 Example 3
상기 실시예 1에서 (E)-(5-oxothiophen-2(5H)-ylidene)methylboronic acid 대신에 (E)-(7-oxo-2,3-dihydrothieno[3,4-b][1,4]dioxin-5(7H) -ylidene)methylboronic acid를 사용하는 것을 제외하고는 실시예 1에서와 동일한 방법을 순차적으로 실시하여 하기 화합물 3을 얻었다. 상기 화합물에 대해 FD-MS(Field desorption mass spectrum)을 수행한 결과 C54H37N3O10S2=952 에 대하여 m/z(측정치)=951 임을 확인했다.(E) - (7-oxo-2,3-dihydrothieno [3,4-b] [1,4] thiophene was obtained in the same manner as in Example 1, ] dioxin-5 (7H) -ylidene) methylboronic acid was used in the same manner as in Example 1, to thereby give the following compound 3. Field desorption mass spectrum (FD-MS) was performed on the compound. As a result, it was confirmed that m / z (measured value) = 951 for C 54 H 37 N 3 O 10 S 2 = 952.
[화합물 3][Compound 3]
염료감응태양전지의 제조Manufacture of dye-sensitized solar cell
본 발명에 따른 염료의 전류-전압 특성을 평가하기 위해, 13+10 ㎛ TiO2 투명층을 이용하여 염료감응태양전지를 제조하였다. In order to evaluate the current-voltage characteristics of the dye according to the present invention, a dye-sensitized solar cell was fabricated using a 13 + 10 탆 TiO 2 transparent layer.
상세하게는 세척된 FTO(Pilkington, 8 Ωsq-1) 유리기판을 40 mM TiCl4 수용액 중에 함침시켰다. TiO2 페이스트(Solaronix, 13 nm 아나타제)를 스크린 프린팅하여 13 ㎛ 두께의 제1 TiO2 층을 제조하고, 광산란을 위해 다른 페이스트(CCIC, HWP-400)로 10 ㎛ 두께의 제2 TiO2 산란층을 제조하였다. 제조된 TiO2 전극을 본 발명에 따른 염료의 용액 (10mM의 3a,7a-디히드록시-5b-콜산 함유 에탄올 중에 상기 실시예 1-3에서 제조된 화합물 1-3을 각각 0.3 mM로 용해시킴)에 함침시킨 후, 실온에서 18시간 동안 방치하였다. FTO 기판 상에 H2PtCl6 용액(에탄올 1 mL 중에 Pt 2 mg 함유)을 코팅하여 대전극을 제조하였다. 이어, 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M LiI, 0.05 M 구아니디움 티오시아네이트 및 0.28 M tert-부틸피리딘을 용해시킨 전해질을 전지에 주입하여 염료감응태양전지를 제조하였다. 염료감응태양전지의 광전지 성능은 1000W 크세논 광원을 사용하여 측정하였으며, 그 결과를 하기 표 1에 나타내었다.Specifically, the washed FTO (Pilkington, 8 Ωsq-1 ) the glass substrate was immersed in 40 mM aqueous solution of TiCl 4. TiO 2 paste (Solaronix, 13 nm anatase) a screen-printed by 13 ㎛ thickness of Claim 1 TiO preparing the second layer, and the other paste for the light scattering (CCIC, HWP-400) of claim 2, TiO of 10 ㎛ thickness of 2 scattering layer . The prepared TiO 2 electrode was dissolved in a solution of the dye according to the present invention (0.3 mM each of the compounds 1-3 prepared in Example 1-3) in ethanol containing 10 mM of 3a, 7a-dihydroxy-5b-cholic acid ), And then allowed to stand at room temperature for 18 hours. A counter electrode was prepared by coating a solution of H 2 PtCl 6 (containing 2 mg of Pt in 1 mL of ethanol) on the FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodide, 0.04 MI 2 , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine were dissolved in acetonitrile was used as a battery To prepare a dye-sensitized solar cell. The photovoltaic performance of the dye-sensitized solar cell was measured using a 1000 W xenon light source, and the results are shown in Table 1 below.
상기 표 1에서 나타난 바와 같이 본 발명의 신규 염료는 우수한 광전기 변환효율을 나타내었다. 따라서 본 발명의 신규한 염료화합물은 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.As shown in Table 1, the novel dyes of the present invention exhibited excellent photoelectric conversion efficiency. Therefore, the novel dye compound of the present invention can greatly improve the efficiency of a solar cell, and can be refined without using an expensive column, thereby dramatically lowering the dye synthesis cost.
Claims (5)
[화학식 1-1]
[화학식 1-2]
[화학식 1-3]
[화학식 1-4]
[화학식 1-5]
[화학식 1-6]
[화학식 1-7]
[화학식 1-8]
[화학식 1-9]
[화학식 1-10]
[화학식 1-11]
[화학식 1-12]
[화학식 1-13]
[화학식 2-1]
[화학식 2-2]
[화학식 2-3]
[화학식 2-4]
[화학식 2-5]
[화학식 2-6]
[화학식 2-7]
[화학식 3-1]
[화학식 3-2]
[화학식 3-3]
[화학식 3-4]
[화학식 3-5]
[화학식 4-1]
[화학식 4-2]
[화학식 4-3]
[화학식 4-4]
[화학식 4-5]
상기 식에서, R은 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이다.An organic dye characterized by being one of the following structural formulas:
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
[Formula 1-5]
[Chemical Formula 1-6]
[Chemical Formula 1-7]
[Chemical Formula 1-8]
[Chemical Formula 1-9]
[Chemical Formula 1-10]
[Formula 1-11]
[Formula 1-12]
[Formula 1-13]
[Formula 2-1]
[Formula 2-2]
[Formula 2-3]
[Chemical Formula 2-4]
[Chemical Formula 2-5]
[Chemical Formula 2-6]
[Chemical Formula 2-7]
[Formula 3-1]
[Formula 3-2]
[Formula 3-3]
[Chemical Formula 3-4]
[Formula 3-5]
[Formula 4-1]
[Formula 4-2]
[Formula 4-3]
[Formula 4-4]
[Formula 4-5]
Wherein each R is independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl.
[화학식 5]
[화학식 15]
A는
B는
C는
R1 내지 R4는 각각 독립적으로 수소, C1-12 알킬 또는 치환되거나 비치환된 C6-12 아릴이고;
n은 1 내지 5의 정수이다.The preparation of the organic dye according to claim 1 produced by sequentially reacting a compound represented by the formula (5) or (15) with a precursor compound of the following formula A, B, A and B or B and A, Way:
[Chemical Formula 5]
[Chemical Formula 15]
A is
B is
C is
R 1 to R 4 are each independently hydrogen, C 1-12 alkyl or substituted or unsubstituted C 6-12 aryl;
n is an integer of 1 to 5;
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