KR100893608B1 - Fluorescent Gel of Silver-Complex and Process of Preparation thereof - Google Patents
Fluorescent Gel of Silver-Complex and Process of Preparation thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 3
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- 239000003446 ligand Substances 0.000 claims abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 17
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical class N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960004592 isopropanol Drugs 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract 3
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
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- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 7
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 1
- 229940100890 silver compound Drugs 0.000 abstract 1
- 150000003379 silver compounds Chemical class 0.000 abstract 1
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 14
- 239000000499 gel Substances 0.000 description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical group 0.000 description 10
- -1 silver ions Chemical class 0.000 description 8
- 238000001879 gelation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
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- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
본 발명은 은-결합 모노덴테이트 리간드로서의 역할을 하는 새로운 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체에 관한 것이다. 이 유도체는 하기 반응식 (1)∼(3)에 의하여 합성된다.The present invention relates to novel pyridine-containing trifluoromethyl-based cyanostilbene derivatives that serve as silver-bonded monodentate ligands. This derivative is synthesize | combined by following Reaction Formula (1)-(3).
상기 식(1)은 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 톨루엔/이소-프로판올/물(2N K2CO3) 용액에서 7시간 환류시키고, 상기 식(2)는 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 THF/물(2N K2CO3) 용액에서 12시간 환류시키며, 상기 식(3)은 테트라부틸암모늄 히드록사이드 촉매하에서 t-부틸알콜/THF 50℃ 용액에서 2시간 반응시킨다.Formula (1) was refluxed for 7 hours in a toluene / iso-propanol / water (2N K 2 CO 3 ) solution under a tetrakis (triphenylphosphine) palladium (0) catalyst, and formula (2) was used for tetrakis ( 12 hours reflux in a THF / water (2N K 2 CO 3 ) solution under triphenylphosphine) palladium (0) catalyst, where formula (3) is t-butyl alcohol / THF 50 ° C. under tetrabutylammonium hydroxide catalyst. The solution is reacted for 2 hours.
형광, 겔화 은-착화합물, 은-결합 모노덴테이트 리간드, 공액(conjugated) 분자, 형광센서 Fluorescence, Gelled Silver-Compounds, Silver-Bonded Monodentate Ligands, Conjugated Molecules, Fluorescence Sensors
Description
제1도는 본 발명의 AIEE-활성 리간드와 은 이온 사이에서의 착화합과 자기-조립에 의한 겔화를 나타내는 개략적인 도면 및 사진이다.1 is a schematic drawing and photograph showing gelation by complexation and self-assembly between an AIEE-active ligand and silver ions of the present invention.
제2도는 1,2-DCE/아세토니트릴(10:1)에서 CN-TFMBPPE(1 wt%, 1 eq) 및 AgClO4(0.5 eq)의 은-착화합물로부터 건조된 겔의 SEM 이미지 사진이다.FIG. 2 is an SEM image of a gel dried from a silver complex of CN-TFMBPPE (1 wt%, 1 eq) and AgClO 4 (0.5 eq) in 1,2-DCE / acetonitrile (10: 1).
제3도는 1,2-디클로로에탄(약 10-5M) 내에서 340 ㎚에서 여기된 AIEE-활성 리간드인 CN-TFMBPPE의 UV-vis 흡수(흑색) 및 형광(적색) 스팩트럼이다.3 is the UV-vis absorption (black) and fluorescence (red) spectrum of CN-TFMBPPE, an AIEE-active ligand excited at 340 nm in 1,2-dichloroethane (about 10 -5 M).
제4도는 AM1 방법에 따라 HyperChem 7.0으로부터 계산된 최적화된 CN-TFMBPPE의 기하 구조체 도면이다.4 is a geometry diagram of optimized CN-TFMBPPE calculated from HyperChem 7.0 according to the AM1 method.
제5도는 CN-TFMBPPE 결정체의 SEM 사진이다.5 is an SEM image of CN-TFMBPPE crystals.
제6도는 1,2-DCE에서 CN-TFMBPPE(1 wt%, 1 eq)의 PL 스팩트럼이다.FIG. 6 is the PL spectrum of CN-TFMBPPE (1 wt%, 1 eq) in 1,2-DCE.
제7도는 0.5 당량의 AgClO4를 갖는 은-착화합물 겔의 PLE 스팩트럼이다.7 is the PLE spectrum of a silver-complexed gel having 0.5 equivalents of AgClO 4 .
제8도는 은-착화합물에 테트라부틸암모늄 플루오라이드(TBAF)를 부가한 후, 은-착화합물을 분해하는 과정을 도시한 도면 및 사진이다.8 is a view and a photograph showing a process of decomposing a silver complex after adding tetrabutylammonium fluoride (TBAF) to the silver complex.
발명의 분야Field of invention
본 발명은 π-공액(conjugated) 분자인 은-착화합물에 관한 것이다. 보다 구체적으로, 본 발명은 겔(gel)을 이루고 형광이 증진되어 형광센서로 사용할 수 있는 은-착화합물 구조체 및 그 제조방법에 관한 것이다.The present invention relates to a silver complex which is a π-conjugated molecule. More specifically, the present invention relates to a silver complex compound structure that can be used as a fluorescent sensor by forming a gel (gel) and enhanced fluorescence and a method of manufacturing the same.
발명의 배경Background of the Invention
금속-초분자(超分子: metallo-supramolecules)는 금속과 리간드 사이의 강한 방향적 복합성이 자기 구조 나노구조체 형성을 위한 중요한 하나의 원동력이고 금속 종류에 따라 제어된 특정 기능을 부여하기 때문에 초분자 화학분야에서 집중적으로 연구되고 있다. 특히, 금속을 갖고 두개의 피리딘 단위에 기초한 비스-모노덴테이트(bis-monodentate) 리간드의 선형 배위 기하 구조는 1차원 초분자 구조물 속으로 연장된 고분자 체인을 제공할 수 있다(H.-J. Kim et al. Angew. Chem. Int. Ed. 2005, 44, 5810). 보다 구체적인 2차 나노구조물 속으로 은-착화합물을 형성시킨 금속-초분자 고분자도 보고되었다(H.-J. Kim et al. J. Am. Chem. Soc. 2004, 126, 7009). 최근에는, 금속-리간드 또는 친금속성 작용에 의한 칼라-변색 발광 자 극-응답 초분자가 소개되기도 하였다(W. Weng et al. J. Am. Chem. Soc. 2006, 128, 11663). 이러한 배위 구조는 그 구조 및 특성에 있어서 트리거(triggered) 변화를 갖는 새로운 자기-조립 물질을 생성시키기 때문에 특별한 관심을 끌어왔다.Metallo-supramolecules (metallo-supramolecules) are used in the supramolecular chemistry because the strong directional complexes between metals and ligands are an important driving force for the formation of self-structured nanostructures and confer specific functions controlled by the type of metal. Intensive research. In particular, the linear coordination geometry of bis-monodentate ligands with metals and based on two pyridine units can provide a polymer chain extending into the one-dimensional supramolecular structure (H.-J. Kim). et al. Angew. Chem. Int. Ed. 2005, 44 , 5810). Metal-supermolecular polymers that form silver complexes into more specific secondary nanostructures have also been reported (H.-J. Kim et al. J. Am. Chem. Soc. 2004, 126 , 7009). Recently, color-chromic luminescence stimulation-responsive supramolecules by metal-ligand or electrometallic action have been introduced (W. Weng et al. J. Am. Chem. Soc. 2006, 128 , 11663). This coordination structure has been of particular interest because it creates a new self-assembled material with a triggered change in its structure and properties.
센서나 디스플레이와 같이 보다 실용적인 응용을 목표로 할 때, 자기-조립 블록(block)을 형성하는 것과 같이 기능성 리간드 속에 복잡한 π-공액 방향족 물질을 결합하는 것은 매우 중요하다. 본 발명자들은 전에도 높은 형광을 갖는 유기겔(organogel)을 형성하기 위한 형광 트리플루오로메틸-기재 시아노스틸벤 유도체(CN-TFMBE)을 개발하였는데, 이는 강한 로드형 방향족 세그먼트(segment)에 의한 강한 π-π 작용뿐만 아니라 주변의 4개의 CF3 기에 의한 보조적인 분자간 작용에 의하여 생성됨을 밝힌 바 있다.(S. Y. Park et al. J. Am. Chem. Soc. 2004, 126, 10232). When targeting more practical applications such as sensors and displays, it is very important to combine complex π-conjugated aromatic materials into functional ligands, such as to form self-assembled blocks. The inventors have previously developed a fluorescent trifluoromethyl-based cyanostilbene derivative (CN-TFMBE) for forming an organogel with high fluorescence, which is strong by a strong rod-type aromatic segment. In addition to the π-π action, it has been shown to be produced by the supportive intermolecular action of the surrounding four CF 3 groups (SY Park et al. J. Am. Chem. Soc. 2004, 126 , 10232).
이러한 종류의 형광체는 독특한 집합체-유도 증진 발광(aggregation-induced enhanced emission: AIEE) 현상을 나타내는데, 이는 평면 구조 분자들로부터의 J-타입 적층과 같은 특이한 분자 패킹(packing)과 관련이 있고, 반면 분리 용액에서는 시아노스틸벤 부분에 있어 비평면화된 꼬인 구조가 에너지적으로 안정하며 이러한 구조적 요인은 비방사성 감소에 의한 실제적인 형광을 억제한다. 따라서 이러한 큰 형광 조절 특징은 매우 중요한데, 특히 광 응용분야에서 중요하다.This kind of phosphor exhibits a unique aggregation-induced enhanced emission (AIEE) phenomenon, which is associated with unusual molecular packing, such as J-type deposition from planar structural molecules, while separation In solution, the non-planar twisted structure in the cyanostilbene portion is energetically stable and this structural factor inhibits the actual fluorescence due to the non-radioactive decrease. Thus, this large fluorescence control feature is very important, especially for optical applications.
이러한 관점에서, 본 발명자들은 은-결합 모노덴테이트 리간드로서의 역할을 하는 새로운 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체를 개발하기 에 이른 것이다. 본 발명은 은-착화합물의 자기-조립에 의한 형광 작동 유기겔 시스템에 관한 것이다.In this regard, the inventors have begun to develop new pyridine-containing trifluoromethyl-based cyanostilbene derivatives that serve as silver-bonded monodentate ligands. The present invention relates to a fluorescent actuated organogel system by self-assembly of silver complex compounds.
본 발명의 목적은 겔을 이루고 형광이 증진되어 형광 센서로 응용할 수 있는 은-착화합물 구조체를 제공하기 위한 것이다.An object of the present invention is to provide a silver complex compound structure that can be applied as a fluorescent sensor by forming a gel and enhanced fluorescence.
본 발명의 다른 목적은 형광 센서로 응용할 수 있는 은-착화합물 구조체를 형성하기 위한 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체 및 그 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a pyridine-containing trifluoromethyl-based cyanostilbene derivative for forming a silver complex compound structure that can be applied as a fluorescent sensor, and a method of manufacturing the same.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
발명의 요약Summary of the Invention
본 발명은 은-결합 모노덴테이트 리간드로서의 역할을 하는 새로운 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체에 관한 것이다. 이 유도체는 하기 반응식 (1)∼(3)에 의하여 합성된다.The present invention relates to novel pyridine-containing trifluoromethyl-based cyanostilbene derivatives that serve as silver-bonded monodentate ligands. This derivative is synthesize | combined by following Reaction Formula (1)-(3).
상기 식(1)은 Suzuki 반응으로 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 톨루엔/이소-프로판올/물(2N K2CO3) 용액에서 7시간 환류시킨다. 상기 식(2)도 Suzuki 반응으로 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 THF/물(2N K2CO3) 용액에서 12시간 환류시킨다. 상기 식(3)은 Knoevenagel 반응으로 테트라부틸암모늄 히드록사이드 촉매하에서 t-부틸알콜/THF 50℃ 용액에서 2시간 반응시킨다.Equation (1) was refluxed in a toluene / iso-propanol / water (2N K 2 CO 3 ) solution for 7 hours under a Suzuki reaction under a tetrakis (triphenylphosphine) palladium (0) catalyst. Formula (2) was also refluxed in a THF / water (2N K 2 CO 3 ) solution for 12 hours under a tetrakis (triphenylphosphine) palladium (0) catalyst by a Suzuki reaction. Formula (3) was reacted for 2 hours in a t-butyl alcohol /
1,2 DCE/아세토니트릴(10:1)에서 CN-TFMBPPE(1 wt%, 1 eq) 및 AgClO4(0.5 eq)를 반응시켜 은-착화합물을 제조한다. A silver complex is prepared by reacting CN-TFMBPPE (1 wt%, 1 eq) and AgClO 4 (0.5 eq) in 1,2 DCE / acetonitrile (10: 1).
이하 첨부된 도면을 참고로 본 발명의 구체적인 내용을 하기에 상세히 설명한다.Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명은 은-결합 모노덴테이트 리간드로서의 역할을 하는 새로운 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체에 관한 것이다. 이 유도체는 하기 반응식 (1)∼(3)에 의하여 합성된다.The present invention relates to novel pyridine-containing trifluoromethyl-based cyanostilbene derivatives that serve as silver-bonded monodentate ligands. This derivative is synthesize | combined by following Reaction Formula (1)-(3).
상기 식(1)은 Suzuki 반응으로 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 톨루엔/이소-프로판올/물(2N K2CO3) 용액에서 7시간 환류시킨다. 상기 식(2)도 Suzuki 반응으로 테트라키스(트리페닐포스핀) 팔라듐(0) 촉매하에서 THF/물(2N K2CO3) 용액에서 12시간 환류시킨다. 상기 식(3)은 Knoevenagel 반응으로 테트라부틸암모늄 히드록사이드 촉매하에서 t-부틸알콜/THF 50℃ 용액에서 2시간 반응시킨다.Equation (1) was refluxed in a toluene / iso-propanol / water (2N K 2 CO 3 ) solution for 7 hours under a Suzuki reaction under a tetrakis (triphenylphosphine) palladium (0) catalyst. Formula (2) was also refluxed in a THF / water (2N K 2 CO 3 ) solution for 12 hours under a tetrakis (triphenylphosphine) palladium (0) catalyst by a Suzuki reaction. Formula (3) was reacted for 2 hours in a t-butyl alcohol /
상기와 같이, 본 발명에서는 알데히드(1)와 벤질 시아노 유도체(2)를 반응시켜 Knoevenagel 반응에 따라 좋은 수율로 은 이온에 결합할 수 있는 새로운 AIEE-활성 리간드인 2-(3',5'-비스-트리플루오로메틸-비페닐-4-일)-3-(4-피리딘-4-일-페닐)-아크릴로니트릴("CN-TFMBPPE")를 합성한 것이다. 위 반응식(1)에서의 알데히드(1)와 반응식(2)에서의 벤질시아노유도체(2)는 Suzuki 커플링 반응에 의하여 제조된다. 이들의 분자 구조는 1H, NMR, GCMS 및 원소분석법에 의하여 하기 실시예에서 규명되었다.As described above, in the present invention, 2- (3 ', 5'), which is a new AIEE-active ligand capable of reacting aldehyde (1) with benzyl cyano derivative (2) and binding to silver ions in good yield according to Knoevenagel reaction -Bis-trifluoromethyl-biphenyl-4-yl) -3- (4-pyridin-4-yl-phenyl) -acrylonitrile ("CN-TFMBPPE") was synthesized. The aldehyde (1) in the scheme (1) and the benzyl cyano derivative (2) in the scheme (2) are prepared by the Suzuki coupling reaction. Their molecular structures were identified in the examples below by 1 H, NMR, GCMS and elemental analysis.
제1도는 본 발명의 AIEE-활성 리간드와 은 이온 사이에서의 착화합과 자기조립에 의한 겔화를 나타내는 개략적인 도면 및 사진이다.1 is a schematic drawing and photograph showing gelation by complexation and self-assembly between an AIEE-active ligand and silver ions of the present invention.
제2도는 1,2 DCE/아세토니트릴(10:1)에서 CN-TFMBPPE(1 wt%, 1 eq) 및 AgClO4(0.5 eq)의 은-착화합물로부터 건조된 겔의 SEM 이미지 사진이다.2 is an SEM image of gel dried from silver complex of CN-TFMBPPE (1 wt%, 1 eq) and AgClO 4 (0.5 eq) in 1,2 DCE / acetonitrile (10: 1).
제3도는 1,2-디클로로에탄(약 10-5 M) 내에서 340 ㎚에서 여기된 AIEE-활성 리간드인 CN-TFMBPPE의 UV-vis 흡수(흑색) 및 발광(적색) 스팩트럼이다. UV 흡수 최대는 π-π* 전이 때문에 343 ㎚에서 관측된다. PL 형광 밴드는 비교적 약한 강도를 갖는 427 ㎚에 집중된다. 그 형광 양자 수율(QY)은 9,10-DPA와 비교할 때 0.002이다. 이 낮은 형광 수율(QY)는 에너지 측면에서 안정된 꼬인 구조에 기인하는 것으로 생각된다. AM1 방법에 따라 HyperChem 7.0으로부터 계산된 결과에 기초하면, CN-TFMBPPE의 최적화된 분자 기하 구조는 각각의 연결 위치에서 큰 이면각(二面角) 으로 이루어진다. 제4도는 AM1 방법에 따라 HyperChem 7.0으로부터 계산된 최적화된 CN-TFMBPPE의 기하 구조체 도면이다. 이러한 비평면화 꼬인 구조가 비방사 감소를 야기하여 분리 용액 내에서 QY를 감소시키는 것으로 보인다.3 is the UV-vis absorption (black) and luminescence (red) spectrum of CN-TFMBPPE, an AIEE-active ligand excited at 340 nm in 1,2-dichloroethane (about 10 -5 M). UV absorption maximum is observed at 343 nm because of the π-π * transition. The PL fluorescence band is concentrated at 427 nm with relatively weak intensity. The fluorescence quantum yield (QY) is 0.002 as compared to 9,10-DPA. This low fluorescence yield (QY) is thought to be due to the stable structure in terms of energy. Based on the results calculated from HyperChem 7.0 according to the AM1 method, the optimized molecular geometry of CN-TFMBPPE consists of large backside angles at each linking position. 4 is a geometry diagram of optimized CN-TFMBPPE calculated from HyperChem 7.0 according to the AM1 method. This non-planar twisted structure appears to cause non-radiation reduction, reducing QY in the separation solution.
나노입자 또는 나노와이어(nanowires)와 같이, 본 발명에서의 꼬인 구조는 집합 상태에서 고유의 분자간 적용에 의하여 평면 구조로 쉽게 전환될 수 있고, 그 결과 형광을 증진시키게 된다.Like nanoparticles or nanowires, the twisted structures in the present invention can be easily converted to planar structures by inherent intermolecular applications in the aggregated state, resulting in enhanced fluorescence.
본 발명에서는, 강한 형광이 CN-TFMBPPE 결정에서 관측되었는데, 이는 1,2-DCE/아세토니트릴 혼합물을 재결정하여 얻어진다. 그러므로 팽창, 가열, 또는 증기 노출과 같은 특별한 자극이나 분자 작용을 유도하는 환경 매체(용해도 조절)는 자기-조립에 있어서 구조적 특성뿐만 아니라 광학적 특성에 현저한 변화를 일으키는 것으로 추측된다.In the present invention, strong fluorescence was observed in the CN-TFMBPPE crystals, which were obtained by recrystallization of the 1,2-DCE / acetonitrile mixture. Therefore, environmental media (solubility control) that induce special stimulation or molecular action, such as expansion, heating, or vapor exposure, are thought to cause significant changes in optical as well as structural properties in self-assembly.
은이온으로 착화하는 CN-TFMBPPE의 초분자 시스템에서, 겔화 성능은 다음과 같이 검토되었다. 우선 CN-TFMBPPE를 1,2-DCE 용액 (1 wt%)에 완전히 용해시키면, 실질적으로 비형광인 무색상을 나타낸다. 제1도와 같이, AgClO4 0.5 당량을 부가한 후, 상당한 변화가 일어나는데, 겔화가 시작되고, 색상도 노란색으로 변하고, 형광도 크게 증진된다. 제5도와 같이, CN-TFMBPPE가 결정성 형태를 갖는 것을 고려하면, 겔화는 CN-TFMBPPE와 은 이온 사이의 은-착화합물의 자기-조립에 기인하는 것으로 추측된다. 겔화 형성을 위한 구조적인 특성에 관한 연구를 감안할 때, 강한 π-π 적층구조(stacking)를 갖는 견고한 방향족 물질뿐만 아니라 주변의 CF3 기도 장쇄의 알킬기나 스테로이달 기와 같이 분자간 작용을 강화하는데 중요한 역할을 한다.In the supramolecular system of CN-TFMBPPE complexed with silver ions, the gelation performance was examined as follows. First, complete dissolution of CN-TFMBPPE in 1,2-DCE solution (1 wt%) gives a substantially non-fluorescent colorlessness. As shown in Figure 1, after adding 0.5 equivalent of AgClO 4 , a significant change occurs, gelation begins, the color turns yellow, and the fluorescence is greatly enhanced. As shown in FIG. 5, considering that CN-TFMBPPE has a crystalline form, gelation is presumed to be due to self-assembly of the silver complex compound between CN-TFMBPPE and silver ions. Given the study of the structural properties for the formation of gelation, it is important to enhance the intermolecular action, such as alkyl or steroidal groups of long chains of CF 3 as well as solid aromatics with strong π-π stacking. Play a role.
본 발명의 은-착화합물의 양단에 4개의 CF3 기가 존재하는 것은 겔화에 중요한 것으로 생각된다. 예측한 바와 같이, 한쪽 단부에만 CF3 기를 갖는 CN-TFMBPPE는 1,2-DCE에서 겔화되지 않고 좋은 용해도를 보여주지만, 4개의 CF3를 양쪽 단부에 갖는 은-매개 견고한 방향족 물질로 이루어진 은-착화합물은 효율적인 겔화 성능을 보여준다.The presence of four CF 3 groups at both ends of the silver complex of the present invention is believed to be important for gelation. As expected, CN-TFMBPPE with CF 3 groups on only one end shows good solubility without gelling at 1,2-DCE, but silver-consisting of silver-mediated solid aromatics with 4 CF 3 at both ends The complex shows efficient gelling performance.
제2도에 도시된 바와 같이, 본 발명의 은-착화합물은 섬유상이 서로 엉킨 그물망 구조를 나타내어, 겔이 형성됨을 알 수 있다. 동시에, 형광이 171배까지 현저하게 증폭된다(제6도). 나아가 PL 발광 밴드가 약 50㎚ 레드-시프트된다. 이는 은이 착화된 후에 CN-TFMBPPE 리간드의 AIEE의 독특한 특성에 기인한 것이다. 제7도에 도시된 광발광 여기(photoluminescence excitation: PLE) 스팩트럼에서 보듯이, 440 ㎚-집중 밴드가 겔화 후에 새롭게 관찰되고, 레드-시프트 되는데, 이는 J-타입 집합체의 형성을 의미한다.As shown in FIG. 2, the silver complex compound of the present invention exhibits a network structure in which fibrous entangled with each other, thereby forming a gel. At the same time, fluorescence is significantly amplified by 171 times (Fig. 6). Furthermore the PL emission band is about 50 nm red-shifted. This is due to the unique properties of AIEE of CN-TFMBPPE ligand after silver complexes. As shown in the photoluminescence excitation (PLE) spectrum shown in FIG. 7, a 440 nm-focused band is newly observed after gelling and red-shifted, indicating the formation of J-type aggregates.
제6도는 은 이온을 부가시킴에 따라 형성되는 은-착화합물의 PL 스팩트럼을 도시한 것이다. [Ag]/[CNTFMBPPE]가 0.1인 경우에도, 형광 방사는 크게 증가하고, 그 밴드 최대는 480 ㎚에서 피크를 이룬다. 이는 낮은 은 이온 농도일지라도 은-착화합물이 효율적으로 자기-조립하여 형광 집합체를 형성하는 것으로 생각된다. 은-이온을 부가함에 따라, 480 ㎚에서의 PL 강도는 0.5까지는 비선형적으로 증가하고, 0.5 이상에서는 유지되는데, 이는 제1도에서와 같이 2:1 은-착화합물 형성을 의미한다. 결론적으로, 은-착화합물 자기-조립은 2개의 결합된 리간드의 상호 분자간 작용으로부터 발생되어 평면구조형성과 J-타입 집합을 유도하고, 그 결과 형광이 현저하게 증진되고 레드-시프트된다.6 shows the PL spectrum of silver complex compounds formed by the addition of silver ions. Even when [Ag] / [CNTFMBPPE] is 0.1, the fluorescence emission is greatly increased, and its band maximum peaks at 480 nm. It is believed that even at low silver ion concentrations, the silver complex compounds self-assemble efficiently to form fluorescent aggregates. With the addition of silver-ions, the PL intensity at 480 nm increases nonlinearly to 0.5 and remains above 0.5, which means 2: 1 silver-complex formation, as in FIG. In conclusion, silver-composite self-assembly arises from the intermolecular interaction of two bound ligands, leading to planar formation and J-type aggregation, with the result that fluorescence is significantly enhanced and red-shifted.
한편 은-착화합물은 제8도와 같이 테트라부틸암모늄 플루오라이드(TBAF)를 사용하여 분해하였다. 은-착화합물 겔에 TBAF를 부가하면 Ag+와 F- 이온 사이의 강한 전자기 작용에 의하여 실질적으로 비형광을 갖는 액상의 용액이 된다. 그러므로, 이러한 겔과 졸(sol) 상태에서의 가액 변환은 AIEE-활성 리간드에 은 이온을 착화 또는 분리함으로써 실현될 수 있다.The silver complex was decomposed using tetrabutylammonium fluoride (TBAF) as shown in FIG. Adding TBAF to silver-complex gels results in a liquid solution that is substantially non-fluorescent due to the strong electromagnetic action between Ag + and F − ions. Therefore, the liquefaction conversion in such a gel and sol state can be realized by complexing or separating silver ions to the AIEE-active ligand.
본 발명에 따른 AIEE-활성 리간드와 결합하는 은 이온은 겔을 형성하는 자기-조립 나노 섬유상구조의 집합을 형성하고, 현저하게 향상되고 레드-시프트된 형광을 발현한다.Silver ions that bind to the AIEE-active ligands according to the invention form a collection of self-assembled nanofibrous structures that form a gel and express markedly enhanced and red-shifted fluorescence.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
CN-TFMBPPE의 제조:Preparation of CN-TFMBPPE:
tert-부틸 알콜(30mL)과 THF(2방울) 내의 상기 반응식(1)에서 제조된 알데히 드(1) (0.30g, 1.64mmol)와 상기 반응식(2)에서 제조된 벤질 시아노 유도체(2) (0.54g, 1.64mmol)의 혼합물에 테트라부틸암모늄 히드록시드(TBAH) (메탄올 내의 1M 용액) (0.16mL)를 서서히 적가하였다. 50℃에서 2시간 동안 교반한 후에, 그 반응 혼합물을 물속에 부었다. 침전물을 여과한 후 건조시켰다. 거친 생성물을 칼럼 크로마토그래피(디클로로메탄)하고, 메탄올 내에 침전시켜 연한 노란색 고체(0.5g, 수율 62%, mp 280℃)를 생성하도록 정제하였다.: 1H NMR (300 MHz, CDCl3) d[ppm]: 8.72 (d, 2H, pyridine-H), 8.06 (m, 4H, Ar-H), 7.90 (s, 1H, Ar-H), 7.86 (d, 2H, Ar-H), 7.78 (d, 2H, Ar-H), 7.72 (d, 2H, Ar-H), 7.67 (s, 1H, vinyl), 7.56 (d, 2H, Ar-H); MS(FAB+) (m/z): Calcd for C28H16F6N2: 494, Found: 495 Anal. Calcd for C28H16F6N2: C, 68.02 H, 3.26 N, 5.67. Found: C, 67.89 H, 3.00 N, 5.46.Aldehyde (1) (0.30 g, 1.64 mmol) prepared in Scheme (1) in tert-butyl alcohol (30 mL) and THF (2 drops) and benzyl cyano derivative (2) prepared in Scheme (2) ) (0.54 g, 1.64 mmol) was added slowly dropwise addition of tetrabutylammonium hydroxide (TBAH) (1M solution in methanol) (0.16 mL). After stirring at 50 ° C. for 2 hours, the reaction mixture was poured into water. The precipitate was filtered off and dried. The rough product was purified by column chromatography (dichloromethane) and precipitated in methanol to yield a pale yellow solid (0.5 g, yield 62%, mp 280 ° C.): 1 H NMR (300 MHz, CDCl 3 ) d [ ppm]: 8.72 (d, 2H, pyridine-H), 8.06 (m, 4H, Ar-H), 7.90 (s, 1H, Ar-H), 7.86 (d, 2H, Ar-H), 7.78 (d , 2H, Ar-H), 7.72 (d, 2H, Ar-H), 7.67 (s, 1H, vinyl), 7.56 (d, 2H, Ar-H); MS (FAB +) (m / z): Calcd for C 28 H 16 F 6 N 2 : 494, Found: 495 Anal. Calcd for C 28 H 16 F 6 N 2 : C, 68.02 H, 3.26 N, 5.67. Found: C, 67.89 H, 3.00 N, 5.46.
물성 측정:Physical property measurement:
1H NMR 스팩트럼은 CDCl3 용액에서 JEOL JNM-LA300 (300MHz) 상에 기록되었다. 질량 스팩트럼은 FAB+ 모드로 JMS AX505 WA 상에서 측정되었다. 원소 분석은 CE 기구인 EA 1110 원소 분석기로 측정되었다. UV-visible 흡수 및 형광 스팩트럼은 HP 8452-A 및 Shimadzu RF-500 스펙트로플루오로포토미터로 각각 기록되었다. FE-SEM 이미지는 JSM-6330F (JEOL)로 얻었다. DSC(Differential scanning calorimetry)는 20℃/분의 가열속도로 Perkin Elmer DSC 7에서 행해졌다. 1 H NMR spectrum was recorded on JEOL JNM-LA300 (300 MHz) in CDCl 3 solution. Mass spectrum was measured on JMS AX505 WA in FAB + mode. Elemental analysis was measured with the CE instrument EA 1110 Elemental Analyzer. UV-visible absorption and fluorescence spectra were recorded with HP 8452-A and Shimadzu RF-500 spectrofluorophotometers, respectively. FE-SEM images were obtained with JSM-6330F (JEOL). Differential scanning calorimetry (DSC) was performed on a Perkin Elmer DSC 7 at a heating rate of 20 ° C./min.
은-착화하물의 분해실험:Decomposition test of silver complexes:
1,2-DCE (1 mL)내에 CN-TFMBPPE (1 wt%, 1 eq) 및 AgClO4(0.5 eq)를 포함하는 겔 시약병에, THF(50 μL)내의 테트라부틸암모늄 플루오라이드 (2.5 eq)를 부가하고 7시간 동안 교반하였다. 서서히, 겔은 졸 상태로 변하고, 색상도 변하였는데, 이는 TBAF의 갈색과 형성된 염에 기인한 것으로 추측된다. In a gel reagent bottle containing CN-TFMBPPE (1 wt%, 1 eq) and AgClO 4 (0.5 eq) in 1,2-DCE (1 mL), tetrabutylammonium fluoride (2.5 eq) in THF (50 μL) Was added and stirred for 7 hours. Gradually, the gel changed to a sol state and changed color, presumably due to the brown and formed salt of TBAF.
본 발명은 겔을 이루고 형광이 증진되어 형광 센서로 응용할 수 있는 은-착화합물 구조체를 제공하고, 이 은-착화합물 구조체를 형성하기 위한 피리딘-함유 트리플루오로메틸-기재 시아노스틸벤 유도체 및 그 제조방법을 제공하는 발명의 효과를 갖는다. The present invention provides a silver complex compound structure that can be formed as a gel and enhanced fluorescence to be applied as a fluorescence sensor, and pyridine-containing trifluoromethyl-based cyanostilbene derivative for producing the silver complex compound and its preparation It has the effect of the invention providing a method.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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