KR20040005261A - Novel quinolinic compounds showing a feature of excited-state intramolecular proton transfer (esipt) - Google Patents
Novel quinolinic compounds showing a feature of excited-state intramolecular proton transfer (esipt) Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
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Abstract
Description
본 발명의 목적은 발광재료로서 퀴놀린 단위를 가지는 단량체, 덴드리머 및 중합체를 합성하며, 이들의 다양한 발광색 조절, 레이징 (lasing) 및 소자 제작 시 열안정성을 구현하기 위하여 새로운 구조를 도입하여 고체상태 및 용액상태로 그성능을 구현하는 데에 있다.An object of the present invention is to synthesize monomers, dendrimers and polymers having a quinoline unit as a light emitting material, and to introduce a new structure in order to realize a variety of emission color control, lasing and thermal stability during device fabrication, The solution is to realize its performance.
최근에 유기 전기발광 (EL) 소자는 고휘도의 평판 디스플레이용 후보로서 주목을 받고 있다. 이러한 경향에 따라, 이에 대한 많은 연구 및 개발이 활발히 진행되고 있다. 유기 EL 소자는 발광층이 두 전극 사이에 삽입되어 있는 구조를 갖는다. 양극으로 주입되는 정공(hole) 및 음극으로부터 주입되는 전자는 발광층 내에서 재결합하여 발광한다. 고분자량 및 저분자량 재료 모두가 유기 EL 소자의 제조에 사용될 수 있으며, 양쪽 모두 고휘도의 유기 EL 소자를 제공하는 것으로 입증되었다.Recently, organic electroluminescent (EL) devices have attracted attention as candidates for high brightness flat panel displays. According to this tendency, many researches and developments about this are actively progressed. The organic EL device has a structure in which a light emitting layer is inserted between two electrodes. Holes injected into the anode and electrons injected from the cathode recombine and emit light in the emission layer. Both high molecular weight and low molecular weight materials can be used in the manufacture of organic EL devices, both of which have been demonstrated to provide high brightness organic EL devices.
유기 EL 소자는 두 유형으로 나누어진다. 한 유형은 형광색소가 첨가된 전하 수송재료를 이용하여 발광층을 형성하는 것이고 (Journal of the Applied Physics, 65, 3610, 1989), 다른 유형은 형광색소 자체를 발광층으로 사용하는 것이다 (Japanese Journal of the Applied Physics, 27, L269, 1988)Organic EL devices are divided into two types. One type is to form a light emitting layer by using a charge transport material to which fluorescent dye is added (Journal of the Applied Physics, 65, 3610, 1989), and the other type is to use the fluorescent color itself as a light emitting layer (Japanese Journal of the Applied Physics, 27, L269, 1988)
형광색소 자체를 발광층으로 이용하는 유기 EL 소자는 추가로 다음의 세 가지 유형으로 구분된다. 첫번째는 발광층이 정공수송층 및 전자수송층 사이에 삽입된 삼층소자이고, 두번째는 정공수송층과 발광층이 다른 하나에 적층되어 있는 이층 소자이며, 세번째는 전자수송층과 발광층이 다른 하나에 적층되어 있는 이층소자이다. 그래서, 유기 EL 소자는 이층 또는 삼층구조를 갖는 경우 향상된 발광효율을 나타내는 것으로 알려져 있다.The organic EL device using the fluorescent dye itself as a light emitting layer is further divided into the following three types. The first is a three-layer device in which the light emitting layer is interposed between the hole transport layer and the electron transport layer, the second is a two-layer device in which the hole transport layer and the light emitting layer are stacked on the other one, and the third is a two-layer device in which the electron transport layer and the light emitting layer are stacked on the other one. . Therefore, it is known that an organic EL device exhibits improved luminous efficiency when it has a two-layer or three-layer structure.
전술한 유기 EL 소자에서, 전자수송층은 전자전달 화합물을 함유하고, 음극으로부터 주입되는 전자를 발광층으로 전달하는 기능을 갖는다. 정공주입층 및 정공수송층 모두는 정공전달 화합물을 함유하고, 양극으로부터 주입된 정공을 발광층으로 전달하는 기능을 갖는다. 정공주입층이 양극과 발광층 사이에 삽입된 경우, 증가된 수의 정공을 저전계에서 발광층에 주입할 수 있고, 또한 음극 또는 전자 주입층으로부터 주입된 전자를 발광층 내에 한정시킬 수 있어 발광효율을 향상시킬 수 있기 때문에, 우수한 발광성능을 갖는 유기 EL 소자를 실현시킬 수 있다.In the above organic EL device, the electron transport layer contains an electron transport compound and has a function of transferring electrons injected from the cathode to the light emitting layer. Both the hole injection layer and the hole transport layer contain a hole transport compound and have a function of transferring holes injected from the anode to the light emitting layer. When the hole injection layer is inserted between the anode and the light emitting layer, an increased number of holes can be injected into the light emitting layer at a low electric field, and electrons injected from the cathode or the electron injection layer can be limited in the light emitting layer, thereby improving luminous efficiency. In this way, an organic EL device having excellent light emission performance can be realized.
종래에 사용되던 트리페닐아민 유도체에 집중된 다양한 재료가 이러한 유기 EL 소자에 사용되는 재료로서 많이 알려져 있으나 아직 매우 적은 수의 재료만이 실제 사용에 적합하다. 예로서, N,N'-디페닐-N,N'-디(3-메틸페닐)-4,4'-디아미노페닐 (TPD) (Applied Physics Letter, Vol.57, No.6, 531, 1990)이 알려져 있는데 이 화합물은 열적으로 불안정하고, 생성된 소자의 수명에서 문제점을 갖는다. 많은 기타 트리페닐아민 유도체들이 알려져 있는데 (미국특허 제 5047686호, 제 4047948호 및 제 4536457호, 일본특허공보(공고) 제 6-32307호 및 일본특허출원공개 제 5-234681호, 제 5-239455호, 제8-87122호 및 제 8-259940호) 이들 중 대부분이 특성면에서 만족스럽지 못하다.Various materials concentrated on triphenylamine derivatives used in the prior art are widely known as materials used in such organic EL devices, but only a very small number of materials are suitable for practical use. For example, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminophenyl (TPD) (Applied Physics Letter, Vol. 57, No. 6, 531, 1990 Are known to be thermally unstable and have problems with the lifetime of the resulting device. Many other triphenylamine derivatives are known (US Pat. Nos. 5047686, 4047948 and 4536457, Japanese Patent Publications 6-32307 and Japanese Patent Application Publication Nos. 5-234681, 5-239455). Nos. 8-87122 and 8-259940) Most of these are not satisfactory in character.
일본특허출원공개 제 4-308688호 또는 제 6-1972호 또는 Advanced Material, Vol.6, 577, 1994에 개시되어 있는 스타버스트 (star-burst) 아민유도체는 실제로는 유기 EL 소자에 필수적인 요건, 즉, 고 발광효율 및 긴 수명을 충족시키지 못하고, 일본특허출원공개 제 7-126226호, 제 7-126615호, 제 7-331238호, 제 7-97355호, 제 8-48656호 및 제 8-100172호 및 Journal of the Chemical Society Chemical Communication, p2175, 1996에 개시되어 있는 각각의 화합물들도 충족시키지 못한다.The star-burst amine derivatives disclosed in Japanese Patent Application Laid-Open No. 4-308688 or 6-1972 or Advanced Material, Vol. 6, 577, 1994, are actually essential requirements for organic EL devices, namely , Japanese Patent Application Publication Nos. 7-126226, 7-126615, 7-331238, 7-97355, 8-48656 and 8-100172 And the individual compounds disclosed in the Journal of the Chemical Society Chemical Communication, p2175, 1996.
Advanced Material Vol.9, 720, 1997에 개시되어 있는 티오펜고리를 갖는 화합물은 장파장의 광을 발산하는 단점을 갖는다.Compounds having a thiophene ring disclosed in Advanced Material Vol. 9, 720, 1997 have the disadvantage of emitting long wavelengths of light.
전술한 바와 같이, 통상의 유기 EL 소자에서 사용하는 재료들은 여전히 향상된 성능이 요구되며, 따라서 유기 EL 소자의 발광성능을 향상시킬 수 있는 우수한 재료가 요구되고 있다.As described above, materials used in conventional organic EL devices still require improved performance, and therefore, excellent materials capable of improving the light emitting performance of organic EL devices are required.
본원발명에 대한 종래기술 (및 그 문제점)에 관한 참조문헌들로는 다음과 같은 것들이 있다:References to the prior art (and problems thereof) to the present invention include the following:
1) Journal of the Applied Physics, 65, 3610, 1989;1) Journal of the Applied Physics, 65, 3610, 1989;
2) Japanese Journal of the Applied Physics, 27, L269, 1988;2) Japanese Journal of the Applied Physics, 27, L269, 1988;
3) Applied Physics Letter, Vol.57, No.6, 531, 1990;3) Applied Physics Letter, Vol. 57, No. 6, 531, 1990;
4) Advanced Material, Vol.6, 577, 1994;4) Advanced Material, Vol. 6, 577, 1994;
5) Journal of the Chemical Society Chemical Communication, p2175, 1996;5) Journal of the Chemical Society Chemical Communication, p2175, 1996;
6) Advanced Material Vol.9, 720, 1997.6) Advanced Material Vol. 9, 720, 1997.
본 발명의 주요 목적은 새로운 구조의 퀴놀린계 단량체, 덴드리머 및 중합체를 합성하여 발광특성을 구현하고 전기발광 디스플레이 (ELD)용 재료 및 레이징용 재료로서 사용하는 데 있다.The main object of the present invention is to synthesize the quinoline-based monomers, dendrimers and polymers of the new structure to implement the luminescence properties and to use as a material for electroluminescent display (ELD) and lasing material.
본 발명의 다른 목적은 퀴놀린 구조내 양자 현상(ESIPT)을 이용하여 다양한 색을 발광하도록 하는 데에 있다.Another object of the present invention is to emit various colors using quantum phenomenon (ESIPT) in quinoline structure.
본 발명의 또 다른 목적은 퀴놀린 구조내에 양자 현상을 안정화할 수 있는 반응기를 도입함으로써 안정적이고 양자효율이 높으며 수명이 긴 발광 특성을 내도록 하는 데에 있다.Another object of the present invention is to introduce a reactor capable of stabilizing quantum phenomena in the quinoline structure to provide stable, high quantum efficiency and long lifespan luminescence properties.
본 발명의 또 다른 목적은 열적 안정성이 우수한 퀴놀린 구조를 발광체에 도입하여 전기발광 디스플레이 공정에 안정하게 사용될 수 있도록 하는 데에 있다.Still another object of the present invention is to introduce a quinoline structure having excellent thermal stability into a light emitter so that it can be stably used in an electroluminescent display process.
도 1은 합성된 새로운 퀴놀린계 유기물의 여기상태 분자내 양자이동 현상 (ESIPT)에 의한 발광현상을 나타낸 도면이다.1 is a view showing the luminescence phenomenon by the excited state intramolecular quantum transfer phenomenon (ESIPT) of the synthesized quinoline-based organic compounds.
도 2는 합성된 퀴놀린계 단량체 MQ와 덴드리머들의 발광 스펙트럼을 나타낸 도면이다.2 is a diagram showing the emission spectrum of the synthesized quinoline monomer MQ and dendrimer.
도 3은 합성된 퀴놀린계 중합체 PQ 및 PQH의 흡광 발광 스펙트럼을 나타낸 도면이다.3 is a graph showing the absorption spectra of the synthesized quinoline-based polymers PQ and PQH.
도 4는 합성된 퀴놀린계 중합체 PQDH의 흡광 발광 스펙트럼을 나타낸 도면이다.FIG. 4 is a diagram showing an absorbance emission spectrum of the synthesized quinoline-based polymer PQDH.
상기의 목적들을 달성하기 위한 본 발명은 퀴놀린 구조를 가지는 단량체, 덴드리머 및 중합체를 제공한다.The present invention for achieving the above objects provides a monomer, dendrimer and polymer having a quinoline structure.
퀴놀린 유도체는 하기 화학식 1과 같이 R1, R2및 R3위치에서 치환될 수 있는 구조를 가지며:The quinoline derivative has a structure that can be substituted at the R 1 , R 2 and R 3 positions as shown in Formula 1 below:
화학식 2는 퀴놀린계 단량체 (MQ)를 나타내고:Formula 2 represents quinoline-based monomers (MQ):
[식 중, X는 -OH 또는 -OCH3임],[Wherein X is -OH or -OCH 3 ],
화학식 3a는 퀴놀린계 덴드리머 (QG1 내지 QG3 및 QG1-t)를 나타내며:Formula 3a represents quinoline-based dendrimers (QG1 to QG3 and QG1-t):
[식 중, X는 하기 화학식 3b 내지 화학식 3d의 기로부터 선택되며,[Wherein X is selected from the group of formulas 3b to 3d,
Y는 -H 또는 화학식 3b의 기임],Y is —H or a group of formula 3b],
화학식 4는 퀴놀린계 중합체 (PQ, PQH, PQDH)를 나타낸다:Formula 4 represents quinoline-based polymers (PQ, PQH, PQDH):
[X 및 Y는 서로 독립적으로 -H 또는 -OH임].[X and Y are, independently from each other, -H or -OH].
상기 퀴놀린계 유기물들은 하기 반응식 1과 같이 비스아미노케톤과 치환된 비스케토메틸렌의 프리들렌더 (Friedlaender) 반응을 통하여 퀴놀린 환을 형성하며 합성된다.The quinoline organics are synthesized by forming a quinoline ring through a Friedlaender reaction of bisaminoketone and substituted bisketomethylene as shown in Scheme 1 below.
구체적으로 화학식 2의 퀴놀린계 단량체 (MQ)는 메타크레졸 및 오산화이인의 혼합물을 가열 후 냉각시키고, 이 혼합물에 비스아미노케톤 및 2-히드록시-4-메톡시아세토페논을 첨가하고 가열하여 프리들렌더 반응을 실시함으로써 제조한다.Specifically, the quinoline-based monomer (MQ) of formula (2) is freed by heating and cooling a mixture of methacresol and diphosphorous pentoxide, and adding bisaminoketone and 2-hydroxy-4-methoxyacetophenone to the mixture and heating. It prepares by performing a render reaction.
그리고, 화학식 3a의 퀴놀린계 덴드리머 (QG1 내지 QG3 및 QG1-t)는 비스아미노케톤 및 2',4'-디히드록시아세토페논을 사용하여 상기 퀴놀린계 단량체 (MQ)의 제조시와 같은 방법으로 합성한 퀴놀린코어를 덴드리틱 벤질브로마이드 (Gn-Br. 화학식 3b 내지 화학식 3d의 기에 -Br이 결합된 화합물)와 함께 용매에 용해시킨 후 칼슘카보네이트 및 크라운에테르(18-crown-6)를 첨가하여 혼합하고, 이를 환류시킨 후 냉각한 다음 메틸렌클로리드에 희석하고 이를 증류 ·정제함으로써 제조한다.In addition, the quinoline dendrimer of the formula (3a) (QG1 to QG3 and QG1-t) using the bisamino ketone and 2 ', 4'- dihydroxyacetophenone in the same manner as in the preparation of the quinoline monomer (MQ) The synthesized quinoline core was dissolved in a solvent with dendritic benzyl bromide (Gn-Br. -Br bonded to a group of Formulas 3b to 3d) and calcium carbonate and crown ether (18-crown-6) were added. The mixture is mixed with the mixture, refluxed, cooled, diluted with methylene chloride, and prepared by distillation and purification.
또한 화학식 4의 퀴놀린계 중합체 (PQ, PQH, PQDH)는 비스아미노케톤 및 히드록시기가 치환된 비스케톤메틸렌 단량체들의 프리들렌더 반응에 의해 제조한다.In addition, quinoline-based polymers of formula (4) (PQ, PQH, PQDH) are prepared by a predender reaction of bisaminoketone and bisketonmethylene monomers substituted with hydroxy groups.
특히 본 발명은 퀴놀린 구조내에 새로운 작용기들을 도입하여 도 1과 같이 여기상태 분자내 양자이동 현상 (ESIPT)을 보이며 새로운 발광특성을 발현하여 발광색 조절 및 여기상태를 상대적으로 안정화하여 발광 효율 증대 및 수명 연장 기술을 제공한다.In particular, the present invention exhibits excited intramolecular quantum transfer phenomenon (ESIPT) by introducing new functional groups into the quinoline structure and expresses new luminescence properties, thereby controlling emission color and stabilizing the excited state to increase luminous efficiency and lifespan. Provide technology.
본 발명에서 제조된 퀴놀린계 화합물들은 필름상태일 경우 자체 흡수 (self-absorption. 발광영역과 흡광영역이 중복되어 발광된 빛을 다시 재흡수 하는 현상)가 일어나지 않아 더 효율적인 발광특성을 보여주고 있다. 단량체, 덴드리머 및 중합체 각각의 흡광 발광 스펙트럼을 도 2 내지 도 4에 나타내었다. 상기 도면에서 도 3 및 도 4 중 PL은 발광 (photoluminescence)를 의미하고, 도 4 중 TCA 및 FA는 각각 테트라클로로에탄 및 포름산을 의미한다. 도면에서 알 수 있듯이 용액상태에서 중복되었던 흡광 발광 영역이 필름상태에서는 중복되지 않음을 알 수 있다. 그 중 단량체들은 전기발광 특성 및 색조절 특성이 우수하며, 덴드리머들은 여기상태 분자내 양자이동현상 (ESIPT) 및 증폭 자발 발광 (Amplified SpontaneousEmission, ASE) 현상을 나타내 레이징 소자로 유용하며, 중합체들은 발광 특성 및 내열성이 우수하여 실제 공정에 적용하기에 적합하다.The quinoline compounds prepared in the present invention do not exhibit self-absorption when the film is in the form of a film. Absorption emission spectra of each of the monomers, dendrimers, and polymers are shown in FIGS. In FIG. 3 and FIG. 4, PL denotes photoluminescence, and in FIG. 4, TCA and FA denote tetrachloroethane and formic acid, respectively. As can be seen in the figure, it can be seen that the absorbing light emitting regions that overlapped in the solution state do not overlap in the film state. Among them, the monomers are excellent in electroluminescence and color control properties, and the dendrimers are useful as rasing devices because they exhibit excited intramolecular quantum shift (ESIPT) and amplified spontaneous emission (ASE) phenomena. Its excellent properties and heat resistance make it suitable for practical applications.
본 발명은 종래의 퀴놀린계 유기물들이 내열성 및 전도성을 주 응용범위로 하는 데에 비하여 발광소재 및 레이징 소재로서 응용된다는 점에서 이전에 알려진 퀴놀린계 유기물과 차이를 갖는다.The present invention differs from the previously known quinoline organics in that conventional quinoline organics are applied as light emitting materials and lasing materials as compared with the main application range of heat resistance and conductivity.
상기 퀴놀린계 단량체 (MQ), 덴드리머 (QG1 내지 QG3 및 QG1-t) 및 중합체 (PQ, PQH, PQDH)의 제조방법은 하기 실시예에 의해 보다 자세히 설명된다. 그러나, 본 발명이 하기 실시예에 한정되는 것은 아니다.The preparation method of the quinoline monomer (MQ), dendrimers (QG1 to QG3 and QG1-t) and polymers (PQ, PQH, PQDH) is described in more detail by the following examples. However, the present invention is not limited to the following examples.
실시예 1Example 1
광 토토머화가 가능한 저분자량 퀴놀린 (Photo-tautomerizable low molecular weight quinoline. MQ)의 합성 (화학식 2, X는 -OCH3임)Synthesis of Photo-tautomerizable low molecular weight quinoline (MQ) (Formula 2, X is -OCH 3 )
3.6ml의 메타크레졸과 1.8g의 오산화이인의 혼합물을 가열한 후 상온이 되면, 0.1g의 비스아미노케톤과 0.07g의 2-히드록시-4-메톡시아세토페논을 투입한 후 다시 가열하여 프리들렌더 반응을 실시하여 MQ를 합성했다. 생성물을 에틸아세테이트와 노르말헥산을 일루언트로 사용하여 컬럼크로마토그래피를 통하여 정제하여 수율 30%의 황색 고체의 MQ를 제조했다.After heating the mixture of 3.6 ml of methacresol and 1.8 g of diphosphorous pentoxide to room temperature, 0.1 g of bisaminoketone and 0.07 g of 2-hydroxy-4-methoxyacetophenone were added and then heated again to free. The renderer reaction was carried out to synthesize MQ. The product was purified by column chromatography using ethyl acetate and normal hexane as an illuminator to give a yield of 30% of a yellow solid MQ.
MQ: mp 98℃, 1H NMR (CDCl3, ppm): 3.84 (s, 6H), 3.87 (s, 6H), 6.51 (dd, J=8.79, 2.66Hz, 2H), 6.60 (d, J=2.66Hz, 2H), 7.00 (d, J=8.79Hz, 4H), 7.40-7.50 (m, 8H), 7.82 (s, 2H), 7.84 (d, J=8.79Hz, 2H), 8.02 (d, J=9.15Hz, 2H).MS(EI) (C46H36N2O7에 대한 계산치 728.79, 실측치 728)MQ: mp 98 ° C., 1 H NMR (CDCl 3, ppm): 3.84 (s, 6H), 3.87 (s, 6H), 6.51 (dd, J = 8.79, 2.66 Hz, 2H), 6.60 (d, J = 2.66 Hz , 2H), 7.00 (d, J = 8.79 Hz, 4H), 7.40-7.50 (m, 8H), 7.82 (s, 2H), 7.84 (d, J = 8.79 Hz, 2H), 8.02 (d, J = 9.15 Hz, 2H) .MS (EI) (calculated for C46H36N2O7 728.79, found 728)
실시예 2Example 2
퀴놀린코어의 합성 (화학식 2, X는 -OH임)Synthesis of quinoline core (Formula 2, X is -OH)
0.59g의 비스아미노케톤과 0.38g의 2',4'-디히드록시아세토페논을 사용하여 실시예 1과 같은 방법으로 수율 48%의 오렌지색 고체의 퀴놀린코어 (Quinoline Core)를 합성했다. 이 퀴놀린코어는 다음 실시예의 퀴놀린계 덴드리머의 합성에 사용되었다.In the same manner as in Example 1, 0.59 g of bisaminoketone and 0.38 g of 2 ', 4'-dihydroxyacetophenone were used to synthesize a quinoline core of 48% yield of an orange solid. This quinoline core was used for the synthesis of the quinoline dendrimer of the following example.
퀴놀린코어: mp 83℃, 1H NMR (CDCl3, ppm): 3.83 (s, 6H), 6.46 (dd, J=8.25, 2.01Hz, 2H), 6.54 (d, J=2.01Hz, 2H), 7.00 (d, J=8.22Hz, 4H), 7.40-7.48 (m, 8H), 7.80 (s, 2H), 7.82 (d, J=8.25Hz, 2H), 8.01 (d, J=9.33Hz, 2H). MS(EI) (C44H32N2O7에 대한 계산치 700.73, 실측치 700)Quinoline core: mp 83 ° C., 1 H NMR (CDCl 3, ppm): 3.83 (s, 6H), 6.46 (dd, J = 8.25, 2.01 Hz, 2H), 6.54 (d, J = 2.01 Hz, 2H), 7.00 ( d, J = 8.22 Hz, 4H), 7.40-7.48 (m, 8H), 7.80 (s, 2H), 7.82 (d, J = 8.25 Hz, 2H), 8.01 (d, J = 9.33 Hz, 2H). MS (EI) (calculated for C44H32N2O7 700.73, found 700)
실시예 3Example 3
퀴놀린코어와 Gn-Br의 커플링 반응을 통한 퀴놀린계 덴드리머(QGn)의 합성 (화학식 3a)Synthesis of quinoline dendrimer (QGn) through coupling reaction between quinoline core and Gn-Br (Formula 3a)
실시예 2에서 합성된 퀴놀린코어 1당량과 덴드리틱 벤질브로마이드 (Gn-Br) 2.1당량을 무수아세톤이나 무수THF에 용해시킨 후 3당량의 칼슘카보네이트와 0.2당량의 크라운에테르(18-crown-6)를 추가했다. 혼합물을 하루 동안 환류시킨 후 상온으로 냉각하고 과량의 메틸렌클로리드에 희석하여 용매를 증류시킨 후 컬럼크로마토그래피로 정제하여 퀴놀린계 덴드리머를 합성했다.One equivalent of quinoline core synthesized in Example 2 and 2.1 equivalents of dendritic benzyl bromide (Gn-Br) were dissolved in anhydrous acetone or anhydrous THF, followed by three equivalents of calcium carbonate and 0.2 equivalents of crown ether (18-crown-6). Added). The mixture was refluxed for one day, cooled to room temperature, diluted with excess methylene chloride, distilled off the solvent, and purified by column chromatography to synthesize a quinoline dendrimer.
QG1 [화학식 3a 중, X는 화학식 3b의 기이고, Y는 -H임]: 수율 28%, Tg 105℃, 1H NMR (CDCl3, ppm): 3.84 (s, 6H), 5.05 (s, 8H), 5.07 (s, 4H), 6.56-6.61 (m, 4H), 6.67 (d, J=2.01, 2H), 6.71 (d, J=2.19, 4H), 7.00 (d, J=8.61, 4H), 7.26-7.49 (m, 28H), 7.82-7.86 (m, 4H), 8.03 (d, J=8.97, 2H). MS(MALDI) (계산치 1305.47, 실측치 1303.21)QG1 [In Formula 3a, X is a group of Formula 3b, Y is -H]: Yield 28%, Tg 105 ° C, 1H NMR (CDCl3, ppm): 3.84 (s, 6H), 5.05 (s, 8H) , 5.07 (s, 4H), 6.56-6.61 (m, 4H), 6.67 (d, J = 2.01, 2H), 6.71 (d, J = 2.19, 4H), 7.00 (d, J = 8.61, 4H), 7.26-7.49 (m, 28H), 7.82-7.86 (m, 4H), 8.03 (d, J = 8.97, 2H). MS (MALDI) (calculated 1305.47, found 1303.21)
QG1-t [화학식 3a 중, X 및 Y는 화학식 3b의 기임]: 수율 19%, Tg 56.7℃, 1H NMR (CDCl3, ppm): 3.81 (s, 6H), 5.02-5.05 (m, 24H), 6.56-6.82 (m, 13H), 6.98 (d, J=8.61, 4H), 7.25-7.51 (m, 38H), 7.80-8.01 (m, 6H). MS(MALDI) (계산치 1607.83, 실측치 1605.33)QG1-t in Formula 3a, X and Y are groups of Formula 3b: yield 19%, Tg 56.7 ° C., 1 H NMR (CDCl 3, ppm): 3.81 (s, 6H), 5.02-5.05 (m, 24H), 6.56-6.82 (m, 13H), 6.98 (d, J = 8.61, 4H), 7.25-7.51 (m, 38H), 7.80-8.01 (m, 6H). MS (MALDI) (calculated 1607.83, found 1605.33)
QG2 [화학식 3a 중, X는 화학식 3c의 기이고, Y는 -H임]: 수율 59%, Tg 53.6℃, 1H NMR (CDCl3, ppm): 3.83 (s, 6H), 4.93-5.13 (m, 28H), 6.55-6.74 (m, 22H), 7.00 (d, J=8.61, 4H), 7.26-7.49 (m, 48H), 7.78-7.82 (m, 4H), 8.01 (d, J=8.97, 2H). MS(MALDI) (계산치 2154.44, 실측치 2152.51)QG2 [In Formula 3a, X is a group of Formula 3c, Y is -H]: Yield 59%, Tg 53.6 ° C., 1H NMR (CDCl 3, ppm): 3.83 (s, 6H), 4.93-5.13 (m, 28H), 6.55-6.74 (m, 22H), 7.00 (d, J = 8.61, 4H), 7.26-7.49 (m, 48H), 7.78-7.82 (m, 4H), 8.01 (d, J = 8.97, 2H ). MS (MALDI) (calculated 2154.44, found 2152.51)
QG3 [화학식 3a 중, X는 화학식 3d의 기이고, Y는 -H임]: 수율 77%, Tg 49.7℃, 1H NMR (CDCl3, ppm): 3.80 (s, 6H), 4.89-5.05 (m, 60H), 6.51-6.69 (m, 46H), 6.97 (d, J=8.61, 4H), 7.24-7.41 (m, 88H), 7.74-7.79 (m, 4H), 8.97 (d, J=8.97, 2H). MS(MALDI) (계산치 3852.39, 실측치 3848.41)QG3 [In Formula 3a, X is a group of Formula 3d, Y is -H]: yield 77%, Tg 49.7 ° C., 1H NMR (CDCl 3, ppm): 3.80 (s, 6H), 4.89-5.05 (m, 60H), 6.51-6.69 (m, 46H), 6.97 (d, J = 8.61, 4H), 7.24-7.41 (m, 88H), 7.74-7.79 (m, 4H), 8.97 (d, J = 8.97, 2H ). MS (MALDI) (calculated 3852.39, found 3848.41)
실시예 4Example 4
퀴놀린계 중합체의 합성 (화학식 4)Synthesis of Quinoline-Based Polymer (Formula 4)
퀴놀린계 중합체들(PQ, PQH, PQDH. PQ는 화학식 4 중 X 및 Y가 -H이고; PQH는 화학식 4 중 X가 -OH, Y가 -H이며; PQDH는 화학식 4 중 X 및 Y가 -OH임)은 비스아미노케톤과 히드록시기가 치환된 비스케톤메틸렌 단량체들의 프리들렌더 반응에 의해서 합성되었다. 특히 합성된 퀴놀린계 중합체들은 230℃ 이상의 높은 유리전이온도(Tg)와 450℃이상의 높은 초기분해온도를 나타내 기존의 전기발광에 사용되는 재료들에 비해 우수한 열적 안정성을 보였다.Quinoline-based polymers (PQ, PQH, PQDH. PQ is X and Y in formula 4 is -H; PQH is X in formula 4 is -OH, Y is -H; PQDH is X and Y in formula 4- OH) was synthesized by a predender reaction of bisaminoketone and bisketonemethylene monomers having hydroxy group substitution. In particular, the synthesized quinoline-based polymers showed a high glass transition temperature (Tg) of more than 230 ℃ and a high initial decomposition temperature of more than 450 ℃ showed excellent thermal stability compared to the materials used for conventional electroluminescence.
본 발명은 화학식 1의 퀴놀린 유도체들을 최초로 전기발광 및 레이징 소자에 적용하는 것이다.The present invention is the first application of quinoline derivatives of formula 1 to electroluminescent and lasing devices.
본 발명은 최초로 전기발광 및 레이징 소자에 퀴놀린 구조를 갖는 단량체, 덴드리머 및 중합체들을 도입한다.The present invention first introduces monomers, dendrimers and polymers with quinoline structures in electroluminescent and lasing devices.
본 발명은 퀴놀린 구조에 새로운 작용기를 도입함으로써 전기발광 시 다양한 색을 구현할 수 있으며, 여기상태 분자내 양자이동 현상 (ESIPT)을 통하여 발광 효율을 높이며 발광 수명을 연장한다.The present invention can implement a variety of colors during electroluminescence by introducing a new functional group in the quinoline structure, and enhances the luminous efficiency and the emission life through the excited state intramolecular quantum transfer phenomenon (ESIPT).
본 발명은 증폭 자발 발광(Amplified Spontaneous Emission, ASE)을 나타내는 퀴놀린계 덴드리머를 사용하여 레이저의 발진 효과를 일으키는 레이징 소자를 제공한다.The present invention provides a rasing device that generates a laser oscillation effect by using a quinoline-based dendrimer that exhibits amplified spontaneous emission (ASE).
본 발명은 발광현상을 나타내는 퀴놀린계 유기물을 단량체, 중합체 및 덴드리머의 형태로 합성하여 물리적 화학적으로 안정하며 용액상태와 큰 차이 없이 발광특성을 나타낼 수 있으며 열적 성질이 매우 우수한 전기발광 필름을 제조한다.The present invention synthesizes a quinoline-based organic material exhibiting a luminescence phenomenon in the form of monomers, polymers and dendrimers to produce an electroluminescent film which is physically and chemically stable, exhibits luminescent properties without significant differences from solution state, and has excellent thermal properties.
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