KR100332495B1 - Octupolar Molecules for Nonlinear Optics and the Method Producing Thereof - Google Patents
Octupolar Molecules for Nonlinear Optics and the Method Producing Thereof Download PDFInfo
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- KR100332495B1 KR100332495B1 KR1019990054553A KR19990054553A KR100332495B1 KR 100332495 B1 KR100332495 B1 KR 100332495B1 KR 1019990054553 A KR1019990054553 A KR 1019990054553A KR 19990054553 A KR19990054553 A KR 19990054553A KR 100332495 B1 KR100332495 B1 KR 100332495B1
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- nonlinear optical
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- benzene
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- 238000000034 method Methods 0.000 title claims description 14
- 230000003287 optical effect Effects 0.000 claims abstract description 63
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 101150065749 Churc1 gene Proteins 0.000 claims abstract description 6
- 102100038239 Protein Churchill Human genes 0.000 claims abstract description 6
- 125000002757 morpholinyl group Chemical group 0.000 claims abstract description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims abstract description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 22
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
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- MDIOQISHQLPGRU-UHFFFAOYSA-N 1-[4-[2-[2,4,6-trinitro-3,5-bis[2-(4-piperidin-1-ylphenyl)ethynyl]phenyl]ethynyl]phenyl]piperidine Chemical compound [O-][N+](=O)c1c(C#Cc2ccc(cc2)N2CCCCC2)c(c(C#Cc2ccc(cc2)N2CCCCC2)c(c1C#Cc1ccc(cc1)N1CCCCC1)[N+]([O-])=O)[N+]([O-])=O MDIOQISHQLPGRU-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LZMONXBJUOXABQ-UHFFFAOYSA-N 1,3,5-trichloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1Cl LZMONXBJUOXABQ-UHFFFAOYSA-N 0.000 claims description 5
- YVJCXMCIFPUNDO-UHFFFAOYSA-N 1,3,5-trimethyl-2,4,6-trinitrobenzene Chemical compound CC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C(C)=C1[N+]([O-])=O YVJCXMCIFPUNDO-UHFFFAOYSA-N 0.000 claims description 5
- WURVTDKUHZJPJX-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3,5-tricarbonitrile Chemical compound CC1=C(C#N)C(C)=C(C#N)C(C)=C1C#N WURVTDKUHZJPJX-UHFFFAOYSA-N 0.000 claims description 5
- GONRGFIAQSFRAT-UHFFFAOYSA-N 1,3,5-tris[2-(4-methoxyphenyl)ethenyl]-2,4,6-trinitrobenzene Chemical compound [N+](=O)([O-])C1=C(C(=C(C(=C1C=CC1=CC=C(C=C1)OC)[N+](=O)[O-])C=CC1=CC=C(C=C1)OC)[N+](=O)[O-])C=CC1=CC=C(C=C1)OC GONRGFIAQSFRAT-UHFFFAOYSA-N 0.000 claims description 4
- YKJDKKAIOPYIMC-UHFFFAOYSA-N 1,3,5-tris[2-(4-methoxyphenyl)ethynyl]-2,4,6-trinitrobenzene Chemical compound COc1ccc(cc1)C#Cc1c(c(C#Cc2ccc(OC)cc2)c(c(C#Cc2ccc(OC)cc2)c1[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O YKJDKKAIOPYIMC-UHFFFAOYSA-N 0.000 claims description 4
- FFOUHDOHPMJNCS-UHFFFAOYSA-N 1-[4-[2-[2,4,6-trinitro-3,5-bis[2-(4-piperidin-1-ylphenyl)ethenyl]phenyl]ethenyl]phenyl]piperidine Chemical compound [N+](=O)([O-])C1=C(C(=C(C(=C1C=CC1=CC=C(C=C1)N1CCCCC1)[N+](=O)[O-])C=CC1=CC=C(C=C1)N1CCCCC1)[N+](=O)[O-])C=CC1=CC=C(C=C1)N1CCCCC1 FFOUHDOHPMJNCS-UHFFFAOYSA-N 0.000 claims description 4
- TVBUJCBKCSCNDJ-UHFFFAOYSA-N 2,4,6-tris[2-(4-methoxyphenyl)ethenyl]benzene-1,3,5-tricarbonitrile Chemical compound C1=CC(OC)=CC=C1C=CC1=C(C#N)C(C=CC=2C=CC(OC)=CC=2)=C(C#N)C(C=CC=2C=CC(OC)=CC=2)=C1C#N TVBUJCBKCSCNDJ-UHFFFAOYSA-N 0.000 claims description 4
- BAZAVZKRVDZQGZ-UHFFFAOYSA-N 2,4,6-tris[2-(4-piperidin-1-ylphenyl)ethenyl]benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=C(C=CC=2C=CC(=CC=2)N2CCCCC2)C(C#N)=C(C=CC=2C=CC(=CC=2)N2CCCCC2)C(C#N)=C1C=CC(C=C1)=CC=C1N1CCCCC1 BAZAVZKRVDZQGZ-UHFFFAOYSA-N 0.000 claims description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 2
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000001491 hyper Rayleigh scattering spectroscopy Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 2
- MNFZZNNFORDXSV-UHFFFAOYSA-N 4-(diethylamino)benzaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C=C1 MNFZZNNFORDXSV-UHFFFAOYSA-N 0.000 description 2
- ILJVPSVCFVQUAD-UHFFFAOYSA-N 4-piperidin-1-ylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1N1CCCCC1 ILJVPSVCFVQUAD-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- LHPONFOTSDFRFA-UHFFFAOYSA-N 1,3,5-trinitro-2,4,6-tris(2-phenylethenyl)benzene Chemical class [N+](=O)([O-])C1=C(C(=C(C(=C1C=CC1=CC=CC=C1)[N+](=O)[O-])C=CC1=CC=CC=C1)[N+](=O)[O-])C=CC1=CC=CC=C1 LHPONFOTSDFRFA-UHFFFAOYSA-N 0.000 description 1
- BMDQWHKNDCOKNM-UHFFFAOYSA-N 1,3,5-trinitro-2,4,6-tris(2-phenylethynyl)benzene Chemical class C1=CC=C(C=C1)C#CC2=C(C(=C(C(=C2[N+](=O)[O-])C#CC3=CC=CC=C3)[N+](=O)[O-])C#CC4=CC=CC=C4)[N+](=O)[O-] BMDQWHKNDCOKNM-UHFFFAOYSA-N 0.000 description 1
- HSVTWKBBVMEXGW-UHFFFAOYSA-N 1-(4-ethynylphenyl)piperidine Chemical group C1=CC(C#C)=CC=C1N1CCCCC1 HSVTWKBBVMEXGW-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- JFQCQELTUDXMQH-UHFFFAOYSA-N 2,4,6-tribromobenzene-1,3,5-tricarbonitrile Chemical compound BrC1=C(C#N)C(Br)=C(C#N)C(Br)=C1C#N JFQCQELTUDXMQH-UHFFFAOYSA-N 0.000 description 1
- RPPZWMSEJVBNBH-UHFFFAOYSA-N 2,4,6-tris(2-phenylethenyl)benzene-1,3,5-tricarbonitrile Chemical class N#CC1=C(C=CC=2C=CC=CC=2)C(C#N)=C(C=CC=2C=CC=CC=2)C(C#N)=C1C=CC1=CC=CC=C1 RPPZWMSEJVBNBH-UHFFFAOYSA-N 0.000 description 1
- JLAKCHGEEBPDQI-UHFFFAOYSA-N 4-(4-fluorobenzyl)piperidine Chemical compound C1=CC(F)=CC=C1CC1CCNCC1 JLAKCHGEEBPDQI-UHFFFAOYSA-N 0.000 description 1
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- CBCACOCJKPPSMS-UHFFFAOYSA-N n,n-diethyl-4-ethynylaniline Chemical group CCN(CC)C1=CC=C(C#C)C=C1 CBCACOCJKPPSMS-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
- C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
본 발명은 신규한 유기 비선형 광학물질에 관한 것으로서, 구체적으로는 하기 일반식 (Ⅰ) 및 (Ⅱ)와 같은 구조를 가지고 있어서 비선형 광학성질이 매우 크고, 또한 쌍극자 모멘트를 가지고 있지 않아서 분자집합체로서의 비선형 광학성질을 향상시키기가 용이한 팔중극자 비선형 광학물질에 관한 것이다.The present invention relates to a novel organic nonlinear optical material, specifically, having a structure such as the following general formulas (I) and (II), which has a very large nonlinear optical property and does not have a dipole moment. It relates to an octapole nonlinear optical material that is easy to improve optical properties.
여기서, A는 NO2, CN, SO2R, CF3등과 같은 전자 받개이며, D는 R, OR, NR2, piperidinyl, piperazinyl, morpholinyl, NR(CH2)xOH, N[(CH2)xOH]2, NR[(CH2)XO(CH2)y]ZOH, NR[(CH2)XO(CH2)y]ZH, N{[(CH2)XO(CH2)y]ZOH}2, N{[(CH2)XO(CH2)y]ZH}2NR(CH2)XOC(O)CH=CH2, NR(CH2)XOC(O)C(CH3)=CH2, NR(CH2)XOC(O)CH=CHCH3, N[(CH2)XOC(O)CH=CH2]2, N[(CH2)XOC(O)C(CH3)=CH2]2, N[(CH2)xOC(O)CH=CHCH3]2,등과 같은 전자 주개이고, R 은 CmH2m+1, n은 1-5의 정수, m, x, y, 및 z는 각각 1-100의 정수이다.Where A is an electron acceptor such as NO 2 , CN, SO 2 R, CF 3, etc., and D is R, OR, NR 2 , piperidinyl, piperazinyl, morpholinyl, NR (CH 2 ) x OH, N [(CH 2 ) x OH] 2 , NR [(CH 2 ) X O (CH 2 ) y ] Z OH, NR [(CH 2 ) X O (CH 2 ) y ] Z H, N {[(CH 2 ) X O (CH 2 ) y ] Z OH} 2 , N {[(CH 2 ) X O (CH 2 ) y ] Z H} 2 NR (CH 2 ) X OC (O) CH = CH 2 , NR (CH 2 ) X OC (O) C (CH 3 ) = CH 2 , NR (CH 2 ) X OC (O) CH = CHCH 3 , N [(CH 2 ) X OC (O) CH = CH 2 ] 2 , N [(CH 2 ) X OC (O) C (CH 3 ) = CH 2 ] 2 , N [(CH 2 ) xOC (O) CH = CHCH 3 ] 2 , Electron donors such as and the like, R is C m H 2m + 1 , n is an integer of 1-5, and m, x, y, and z are each an integer of 1-100.
Description
비선형 광학 물질은 입사광의 전기장과 작용하여 입사광의 진동수 위상, 진폭 등의 성질을 변화시키기 때문에 광신호를 정류변조, 스위칭하는 특성을 지니고 있으므로 광통신, 광기록 등에 사용되는 핵심 소재이다. 현재 가장 널리 사용되고 있는 비선형 광학 물질은 LiNbO3와 GaAs 등과 같은 무기재료이다. 그러나 이들은 생산 공정의 어려움으로 인하여 21세기의 막대한 정보소자의 수요를 감당하기에는 경제적인 측면에서의 제약이 있다. 반면에 유기 비선형 광학물질은 다양한 합성방법을 사용하여 원하는 전자 및 광학 성질을 가진 분자들을 비교적 쉽게 합성할 수 있고, 광신호 및 전산 정보의 처리에 필수적인 초고속 감응 속도를 가지며, 상대적으로 낮은 유전상수와 굴절률로 인하여 넓은 주파수 영역에서 사용할 수 있고, 가공성이 뛰어난 장점을 가지고 있다.Non-linear optical material is a core material used in optical communication, optical recording, etc. because it has the characteristics of rectifying modulation and switching of optical signals because it changes the properties of frequency, phase, amplitude, etc. of incident light by working with electric field of incident light. The most widely used nonlinear optical materials are inorganic materials such as LiNbO 3 and GaAs. However, they are economically constrained to meet the huge demand for information devices in the 21st century due to the difficulty of the production process. Organic nonlinear optics, on the other hand, can be synthesized relatively easily with molecules of desired electronic and optical properties using a variety of synthesis methods, have very fast response speeds essential for processing optical signals and computational information, and have relatively low dielectric constants. Due to the refractive index, it can be used in a wide frequency range, and has excellent workability.
지금까지 알려진 대부분의 유기 비선형 광학물질은 컨쥬게이션 이중 결합의 양쪽 끝에 전자 주개와 받개가 치환된 이중극자 구조를 가지고 있다 [Prasad, P. N.; William, D. J. Introduction to Nonlinear Optical Effects in Molecules and Polymers, John & Wiley, New York, 1991, Marder, S. R.; Perry, J. W. Adv. Mater. 1993, 804-815, Jen, A. K-Y.; Cai, Y.; Bedworth, P. V.; Marder, S. R. Adv. Mater. 1997, 9,132-135, Morley, J. O. J. Chem. Soc. Faraday Trans. 1991, 87, 3009-3013, P. R. Varanasi, A. K-Y. Jen, J. Chandrasekhar, I. N. N. Namboothiri, and A. Rathna, J. Am. Chem. Soc., 1996, 118, 12443-12448]. 이와 같은 이중극자는 유기 결정, LB필름 및 고분자에 결합시켜 폴링(poling) 시킨 물질 등을 만들어 비선형 광학 소재로 사용한다. 그러나 유기결정은 만들기가 어려우며, 이중극자 분자는 고체상태에서 쌍극자 모멘트가 상쇄되는 방법으로 배치되는 것이 열역학적으로 안정하므로, 시간이 지남에 따라 LB필름이나 폴링된 고분자에 포함된 비선형 광학 발색단의 배열이 점차 이완되어 비선형 광학 성질이 감소하는 등의 문제점을 가지고 있다. 또한 일반적으로 유기분자는 열 안정성이 약하여 비선형 광학 소재의 제작 과정에 수반되는 높은 온도에서 분해하는 단점을 가지고 있다.Most organic nonlinear optics known to date have a dipole structure with electron donors and acceptors substituted at both ends of the conjugated double bond [Prasad, P. N .; William, D. J. Introduction to Nonlinear Optical Effects in Molecules and Polymers, John & Wiley, New York, 1991, Marder, S. R .; Perry, J. W. Adv. Mater. 1993, 804-815, Jen, A. K-Y .; Cai, Y .; Bedworth, P. V .; Marder, S. R. Adv. Mater. 1997, 9,132-135, Morley, J. O. J. Chem. Soc. Faraday Trans. 1991, 87, 3009-3013, P. R. Varanasi, A. K-Y. Jen, J. Chandrasekhar, I. N. N. Namboothiri, and A. Rathna, J. Am. Chem. Soc., 1996, 118, 12443-12448. Such a dipole is bonded to an organic crystal, an LB film, and a polymer to make a polled material and used as a nonlinear optical material. However, organic crystals are difficult to make, and since the dipole molecules are thermodynamically stable in such a way that the dipole moments are offset in the solid state, the arrangement of nonlinear optical chromophores in LB films or polled polymers over time There is a problem such as gradually relaxed to reduce the non-linear optical properties. In addition, organic molecules generally have a weak thermal stability and have a disadvantage in that they decompose at high temperatures accompanying the manufacturing process of nonlinear optical materials.
본 발명자들은 이상과 같은 기존 유기 비선형 광학물질의 문제점을 해결하고자 연구를 수행하여 본 발명을 완성하였다.The present inventors completed the present invention by conducting research to solve the problems of the existing organic nonlinear optical material as described above.
제 1도는 본 발명에 따라 실시예 1에서 제조한 1,3,5-트리니트로-2,4,6-트리스(파라메톡시스티릴)벤젠의 nmr스펙트럼을 나타낸다.Figure 1 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris (paramethoxystyryl) benzene prepared in Example 1 according to the present invention.
제 2도는 본 발명에 따라 실시예 2에서 제조한 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠의 nmr스펙트럼을 나타낸다.2 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris [p- (N-diethylamino) styryl] benzene prepared in Example 2 according to the present invention.
제 3도는 본 발명에 따라 실시예 3에서 제조한 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노스티릴)벤젠의 nmr스펙트럼을 나타낸다.Figure 3 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris (parapiperidinostyryl) benzene prepared in Example 3 according to the present invention.
제 4도는 본 발명에 따라 실시예 4에서 제조한 1,3,5-트리시아노-2,4,6-트리스(파라메톡시스티릴)벤젠의 nmr스펙트럼을 나타낸다.4 shows the nmr spectrum of 1,3,5-tricyano-2,4,6-tris (paramethoxystyryl) benzene prepared in Example 4 according to the present invention.
제 5도는 본 발명에 따라 실시예 5에서 제조한 1,3,5-트리시아노-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠의 nmr스펙트럼을 나타낸다.5 shows the nmr spectrum of 1,3,5-tricyano-2,4,6-tris [p- (N-diethylamino) styryl] benzene prepared in Example 5 in accordance with the present invention.
제 6도는 본 발명에 따라 실시예 6에서 제조한 1,3,5-트리시아노-2,4,6-트리스(파라피페리디노스티릴)벤젠의 nmr스펙트럼을 나타낸다.6 shows the nmr spectrum of 1,3,5-tricyano-2,4,6-tris (parapiperidinostyryl) benzene prepared in Example 6 according to the present invention.
제 7도는 본 발명에 따라 실시예 7에서 제조한 1,3,5-트리니트로-2,4,6-트리스(파라메톡시페닐에티닐)벤젠의 nmr스펙트럼을 나타낸다.FIG. 7 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris (paramethoxyphenylethynyl) benzene prepared in Example 7 in accordance with the present invention.
제 8도는 본 발명에 따라 실시예 8에서 제조한 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)페닐에티닐]벤젠의 nmr스펙트럼을 나타낸다.8 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris [p- (N-diethylamino) phenylethynyl] benzene prepared in Example 8 according to the present invention.
제 9도는 본 발명에 따라 실시예 9에서 제조한 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노페닐에티닐)벤젠의 nmr스펙트럼을 나타낸다.Figure 9 shows the nmr spectrum of 1,3,5-trinitro-2,4,6-tris (parapiperidinophenylethynyl) benzene prepared according to the invention in Example 9.
제 10도는 실시예 10에서 HRS방법에 따라 측정한 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노페닐에티닐)벤젠의 농도에 따른 HRS신호의 세기 변화를 나타낸다.FIG. 10 shows the change in intensity of the HRS signal according to the concentration of 1,3,5-trinitro-2,4,6-tris (parapiperidinophenylethynyl) benzene measured according to the HRS method in Example 10.
본 발명자들은 위에서 설명한 이중극자 비선형광학 물질의 단점을 보완하기위하여, 쌍극자 모멘트는 없으나 비선형 광학성질이 크며, 열안정성이 높은 새로운 비선형 광학물질을 개발하기 위하여 여러 가지 유기화합물들을 검토한 결과 다음의 일반식 (I)-(II)로 나타낼 수 있는 새로운 비선형 광학 팔중극자 분자가 비선형 광학성질이 매우 크고 열적 안정도도 상당히 큼을 발견하고 그 제조방법을 공개한다. 아래 표 1-3에서 보듯이 팔중극자 비선형 광학물질 III, V, VII은 그것에 상응하는 이중극자 물질 IV, VI, VIII에 비해 이차 비선형 광학 성질[β(0)]이 1-22배 정도In order to make up for the shortcomings of the bipolar nonlinear optical materials described above, the present inventors examined various organic compounds to develop new nonlinear optical materials having no dipole moments but high nonlinear optical properties and high thermal stability. The new nonlinear optical octapole molecules, which can be represented by formulas (I)-(II), find that the nonlinear optical properties are very large and the thermal stability is very high and the preparation method is disclosed. As shown in Table 1-3 below, the bipolar nonlinear optical materials III, V, and VII have a second nonlinear optical property [β (0)] by 1-22 times compared to the corresponding dipole materials IV, VI, and VIII.
클 뿐만아니라 고체상태에서 같은 방향으로 배열시키기가 용이하므로 광신호를 정류, 변조 및 스위칭하는 광학 소자로써 뿐만 아니라 초고집적 광 메모리의 제작에 사용할 수 있다.As well as being easy to arrange in the same direction in the solid state, it can be used not only as an optical device for rectifying, modulating and switching optical signals, but also for fabricating ultra-high density optical memories.
여기서, A는 NO2, CN, SO2R, CF3등과 같은 전자 받개이며, D는 R, OR, NR22, piperidinyl, piperazinyl, morpholinyl, NR(CH2)xOH, N[(CH2)xOH]2, NR[(CH2)XO(CH2)y]ZOH, NR[(CH2)XO(CH2)y]ZH, N{[(CH2)XO(CH2)y]ZOH}2, N{[(CH2)XO(CH2)y]ZH}2NR(CH2)XOC(O)CH=CH2, NR(CH2)XOC(O)C(CH3)=CH2,NR(CH2)XOC(O)CH=CHCH3, N[(CH2)XOC(O)CH=CH2]2, N[(CH2)XOC(O)C(CH3)=CH2]2, N[(CH2)XOC(O)CH=CHCH3]2,등과 같은 전자 주개이고, R 은 CmH2m+1, n은 1-5의 정수, m, x, y, 및 z는 각각 1-100의 정수이다.Where A is an electron acceptor such as NO 2 , CN, SO 2 R, CF 3, etc., and D is R, OR, NR 2 2, piperidinyl, piperazinyl, morpholinyl, NR (CH2) xOH, N [(CH 2 ) xOH ] 2 , NR [(CH 2 ) X O (CH 2 ) y ] Z OH, NR [(CH 2 ) X O (CH 2 ) y ] Z H, N {[(CH 2 ) X O (CH 2 ) y ] Z OH} 2 , N {[(CH 2 ) X O (CH 2 ) y ] Z H} 2 NR (CH 2 ) X OC (O) CH = CH 2 , NR (CH 2 ) X OC (O ) C (CH 3 ) = CH 2 , NR (CH 2 ) X OC (O) CH = CHCH 3 , N [(CH 2 ) X OC (O) CH = CH 2 ] 2 , N [(CH 2 ) X OC (O) C (CH 3 ) = CH 2 ] 2 , N [(CH 2 ) X OC (O) CH = CHCH 3 ] 2 , Electron donors such as and the like, R is C m H 2m + 1 , n is an integer of 1-5, and m, x, y, and z are each an integer of 1-100.
화합물 I은 1,3,5-트리니트로-2,4,6-트리메틸벤젠 또는 1,3,5-트리시아노-2,4,6-트리메틸벤젠과 파라위치에 치환기를 가진 벤즈알데히드 또는 4'위치에 치환기를 가진 스틸벤카르복시알데히드를 톨루엔에 녹이고 피페리딘을 가하여 3-5일동안 환류시키면 얻을 수 있다. 또한 화합물 II는 1,3,5-트리클로로-2,4,6-트리니트로벤젠 또는 1,3,5-트리브로모-2,4,6-트리시아노벤젠과 파라위치에 치환기를 가진 페닐아세틸렌 또는 4'위치에 치환기를 가진 페닐에티닐페닐아세틸렌을 THF 용액에서 BuLi(Bu: Butyl)과 반응 시켜 합성한다.Compound I is a benzaldehyde having a substituent at 1,3,5-trinitro-2,4,6-trimethylbenzene or 1,3,5-tricyano-2,4,6-trimethylbenzene and in the para position or at the 4 'position. It can be obtained by dissolving stilbencarboxyaldehyde with a substituent in toluene and adding piperidine to reflux for 3-5 days. In addition, compound II is 1,3,5-trichloro-2,4,6-trinitrobenzene or 1,3,5-tribromo-2,4,6-tricyanobenzene and phenylacetylene having a substituent in the para position. Alternatively, phenylethynylphenylacetylene having a substituent at the 4 ′ position is synthesized by reacting with BuLi (Bu: Butyl) in THF solution.
아래의 실시예는 본 발명을 구체적으로 설명하지만 본 발명이 이들 예로만 한정되는 것은 아니다.The following examples illustrate the invention in detail, but the invention is not limited to these examples.
실시예Example
본 발명자들은 이중극자 비선형 광학물질의 대표적인 화합물인 스틸벤 구조가 한 분자 속에 세 개 포함되어 있는 팔중극자 분자를 합성하면 비선형 광학 성질이 뛰어날 뿐만 아니라 분자의 극성이 없어져 광학소자 및 초고집적 메모리 소자로써 응용성이 클 것임에 착안하여, 상기 일반식 (I), (II)로 나타낼 수 있는 화합물을 합성하고 비선형 광학 성질을 측정하였다.The inventors of the present invention synthesized octadipole molecules containing three stilbene structures, which are representative compounds of a dipole nonlinear optical material, in a molecule, which are excellent in nonlinear optical properties and lose the polarity of the molecules. In view of the great applicability, the compounds represented by the general formulas (I) and (II) were synthesized and nonlinear optical properties were measured.
실시예 1 : 1,3,5-트리니트로-2,4,6-트리스(파라메톡시스티릴)벤젠의 합성Example 1 Synthesis of 1,3,5-trinitro-2,4,6-tris (paramethoxystyryl) benzene
1,3,5-트리니트로-2,4,6-트리메틸벤젠 (1.2 g, 4.7 mmol)과 4-메톡시알데히드 (2.1 g, 16 mmol)를 에탄올/벤젠 (5/5) 100 mL에 넣고 환류 시킨 후, 피페리딘 3 mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스(파라메톡시스티릴)벤젠 1.4 g을 얻었다. 수득율 46 %; mp 165-167。C; IR (KBr, cm-1) 1606 (C=C); NMR (300 MHz, CDCl3) δ7.38 (d, 6H, J = 8.7 Hz), 6.90 (d, 3H, J = 16 Hz), 6.89 (d, 6H, J = 8.7 Hz), 6.63 (d, 3H, J = 16 Hz), 3.84 (s, 9H). 원소분석 결과; C33H27N309에 대한 계산치 (%) C, 65.02; H, 4.46; N, 6.89. 실험치: C, 65.03; H, 4.55; N, 6.98.1,3,5-trinitro-2,4,6-trimethylbenzene (1.2 g, 4.7 mmol) and 4-methoxyaldehyde (2.1 g, 16 mmol) were added to 100 mL of ethanol / benzene (5/5) and refluxed. After the addition, 3 mL of piperidine was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 1.4 g of trinitro-2,4,6-tris (paramethoxystyryl) benzene was obtained. Yield 46%; mp 165-167 ° C; IR (KBr, cm −1 ) 1606 (C = C); NMR (300 MHz, CDCl 3 ) δ7.38 (d, 6H, J = 8.7 Hz), 6.90 (d, 3H, J = 16 Hz), 6.89 (d, 6H, J = 8.7 Hz), 6.63 (d, 3H, J = 16 Hz), 3.84 (s, 9H). Elemental analysis results; Calcd for C 33 H 27 N 3 0 9 (%) C, 65.02; H, 4. 46; N, 6.89. Found: C, 65.03; H, 4.55; N, 6.98.
실시예 2 : 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠의 합성Example 2 Synthesis of 1,3,5-trinitro-2,4,6-tris [p- (N-diethylamino) styryl] benzene
1,3,5-트리니트로-2,4,6-트리메틸벤젠 (1.51 g, 5.90 mmol)과 4-디에틸아미노벤즈알데히드 (3.45 g, 19.5 mmol)을 에탄올/벤젠 (5/5) 100 mL에 넣고 환류 시킨 후 피페리딘 3mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠 1.8 g을 얻었다. 수득율 42 %; mp 240。C; IR (KBr, cm-1) 1593 (C=C); NMR (300 MHz, CDCl3) δ 7.28 (d, 6H, J = 8.7 Hz), 6.83(d, 3H, J = 16 Hz), 6.60 (d, 6H, J = 8.7 Hz), 6.48 (d, 3H, J = 16 Hz), 3.38 (q, 12H, J = 7.2 Hz), 1.17 (t, 18H, J = 7.2 Hz). 원소분석 결과; C45H48N6O6에 대한 계산치 (%) C, 68.83; H, 6.60; N, 11.47. 실험치: C, 68.86; H, 6.59; N, 11.48.1,3,5-trinitro-2,4,6-trimethylbenzene (1.51 g, 5.90 mmol) and 4-diethylaminobenzaldehyde (3.45 g, 19.5 mmol) were added to 100 mL of ethanol / benzene (5/5). After refluxing, piperidine 3mL was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 1.8 g of trinitro-2,4,6-tris [p- (N-diethylamino) styryl] benzene were obtained. Yield 42%; mp 240 ° C .; IR (KBr, cm −1 ) 1593 (C = C); NMR (300 MHz, CDCl 3 ) δ 7.28 (d, 6H, J = 8.7 Hz), 6.83 (d, 3H, J = 16 Hz), 6.60 (d, 6H, J = 8.7 Hz), 6.48 (d, 3H , J = 16 Hz), 3.38 (q, 12H, J = 7.2 Hz), 1.17 (t, 18H, J = 7.2 Hz). Elemental analysis results; Calcd for C 45 H 48 N 6 O 6 (%) C, 68.83; H, 6. 60; N, 11.47. Found: C, 68.86; H, 6.59; N, 11.48.
실시예 3 : 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노스티릴)벤젠의 합성Example 3: Synthesis of 1,3,5-trinitro-2,4,6-tris (parapiperidinostyryl) benzene
1,3,5-트리니트로-2,4,6-트리메틸벤젠 (1.4 g, 5.5 mmol)과 4-피페리디노벤즈알데히드 (3.1 g, 17 mmol)을 에탄올/벤젠 (5/5) 100 mL에 넣고 환류 시킨 후 피페리딘 3 mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노스티릴)벤젠 2.3 g을 얻었다. 수득율 54 %; mp 211-212。C; IR (KBr, cm-1) 1586 (C=C); NMR (300 MHz, CDCl3) δ 7.31 (d, 6H, J = 8.7 Hz), 6.85 (d, 6H, J = 8.7 Hz), 6.85 (d, 3H, J = 16.5 Hz), 6.55 (d, 3H, J = 16.5 Hz), 3.30(t, 12H, J = 4.5 Hz), 1.67(m, 18H). 원소분석 결과; C45H48N6O6에 대한 계산치 (%) C, 70.3, H, 6.29, N, 10.9. 실험치: C, 70.3; H, 6.34; N, 10.9.1,3,5-trinitro-2,4,6-trimethylbenzene (1.4 g, 5.5 mmol) and 4-piperidinobenzaldehyde (3.1 g, 17 mmol) were added to 100 mL of ethanol / benzene (5/5). After refluxing, piperidine 3 mL was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 2.3 g of trinitro-2,4,6-tris (parapiperidinostyryl) benzene was obtained. Yield 54%; mp 211-212。 C; IR (KBr, cm- 1 ) 1586 (C = C); NMR (300 MHz, CDCl 3 ) δ 7.31 (d, 6H, J = 8.7 Hz), 6.85 (d, 6H, J = 8.7 Hz), 6.85 (d, 3H, J = 16.5 Hz), 6.55 (d, 3H , J = 16.5 Hz), 3.30 (t, 12H, J = 4.5 Hz), 1.67 (m, 18H). Elemental analysis results; Calcd for C 45 H 48 N 6 O 6 (%) C, 70.3, H, 6.29, N, 10.9. Found: C, 70.3; H, 6. 34; N, 10.9.
실시예 4 : 1,3,5-트리시아노-2,4,6-트리스(파라메톡시스티릴)벤젠의합성Example 4 Synthesis of 1,3,5-Tricyano-2,4,6-tris (paramethoxystyryl) benzene
1,3,5-트리시아노-2,4,6-트리메틸벤젠 (1.5 g, 7.7 mmol)과 4-메톡시벤즈알데히드 (3.5 g, 25 mmol)을 에탄올/벤젠 (5/5) 100 mL에 넣고 환류 시킨 후 피페리딘 4 mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리시아노-2,4,6-트리스(파라메톡시스티릴)벤젠 2.5 g을 얻었다. 수득율 59 %; mp 144-145。C; IR (KBr, cm-1) 2220 (CN), 1565 (C=C); NMR (300 MHz, CDCl3) δ 7.74 (d, 3H, J = 16.5 Hz), 7.61 (d, 6H, J = 8.6 Hz), 7.31 (d, 3H, J = 16.5 Hz), 6.96 (d, 6H, J = 8.6 Hz), 3.87 (s, 9H). 원소분석 결과; C36H27N3O3에 대한 계산치 (%) C, 78.7; H, 4.95; N, 7.65. 실험치: C, 78.3; H, 5.10; N, 7.55.1,3,5-tricyano-2,4,6-trimethylbenzene (1.5 g, 7.7 mmol) and 4-methoxybenzaldehyde (3.5 g, 25 mmol) were added to 100 mL of ethanol / benzene (5/5). After refluxing, piperidine 4 mL was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 2.5 g of tricyano-2,4,6-tris (paramethoxystyryl) benzene was obtained. Yield 59%; mp 144-145 ° C; IR (KBr, cm −1 ) 2220 (CN), 1565 (C = C); NMR (300 MHz, CDCl 3 ) δ 7.74 (d, 3H, J = 16.5 Hz), 7.61 (d, 6H, J = 8.6 Hz), 7.31 (d, 3H, J = 16.5 Hz), 6.96 (d, 6H , J = 8.6 Hz), 3.87 (s, 9H). Elemental analysis results; Calcd for C 36 H 27 N 3 0 3 (%) C, 78.7; H, 4.95; N, 7.65. Found: C, 78.3; H, 5. 10; N, 7.55.
실시예 5 : 1,3,5-트리시아노-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠의 합성Example 5 Synthesis of 1,3,5-Tricyano-2,4,6-tris [p- (N-diethylamino) styryl] benzene
1,3,5-트리시아노-2,4,6-트리메틸벤젠 (0.4 g, 2.0 mmol)과 4-디에틸아미노벤즈알데히드 (1.2 g, 6.7 mmol)을 에탄올/벤젠 (5/5) 50 mL에 넣고 환류 시킨 후 피페리딘 2 mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리시아노-2,4,6-트리스[p-(N-디에틸아미노)스티릴]벤젠 0.9 g을 얻었다. 수득율 67 %; mp 270-272。C; IR (KBr, cm-1) 2214 (CN), 1595 (C=C); NMR (300 MHz, CDCl3) δ 7.75 (d, 3H, J = 16.2 Hz), 7.52 (d, 6H, J = 8.8 Hz), 7.20 (d, 3H, J = 16.2 Hz), 6.67 (d, 6H, J = 8.8 Hz), 3.42 (q, 12H, J = 7.2 Hz), 1.21 (t, 18H, J = 7.2 Hz). 원소분석 결과; C45H48N6에 대한 계산치 (%) C, 80.3; H, 7.19; N, 12.5. 실험치: C, 80.3; H, 7.22; N, 12.4.1,3,5-tricyano-2,4,6-trimethylbenzene (0.4 g, 2.0 mmol) and 4-diethylaminobenzaldehyde (1.2 g, 6.7 mmol) were added to 50 mL of ethanol / benzene (5/5). After refluxing, piperidine 2 mL was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 0.9 g of tricyano-2,4,6-tris [p- (N-diethylamino) styryl] benzene was obtained. Yield 67%; mp 270-272 ° C .; IR (KBr, cm- 1 ) 2214 (CN), 1595 (C = C); NMR (300 MHz, CDCl 3 ) δ 7.75 (d, 3H, J = 16.2 Hz), 7.52 (d, 6H, J = 8.8 Hz), 7.20 (d, 3H, J = 16.2 Hz), 6.67 (d, 6H , J = 8.8 Hz), 3.42 (q, 12H, J = 7.2 Hz), 1.21 (t, 18H, J = 7.2 Hz). Elemental analysis results; Calcd for C 45 H 48 N 6 (%) C, 80.3; H, 7. 19; N, 12.5. Found: C, 80.3; H, 7.22; N, 12.4.
실시예 6 : 1,3,5-트리시아노-2,4,6-트리스(파라피페리디노스티릴)벤젠의 합성Example 6 Synthesis of 1,3,5-Tricyano-2,4,6-tris (parapiperidinostyryl) benzene
1,3,5-트리시아노-2,4,6-트리메틸벤젠 (1.2 g, 6.1 mmol)과 4-피페리디노벤즈알데히드 (3.6 g, 20 mmol)을 에탄올/벤젠 (5/5) 50 mL에 넣고 환류 시킨 후 피페리딘 4 mL를 서서히 첨가 시켰다. 이 용액을 3-5일 동안 환류시킨 후 용매를 감압 제거하고, 생성물은 실리카젤에 흡착시켜 헥산/에틸 아세테이트 (4/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리시아노-2,4,6-트리스(파라피페리디노스티릴)벤젠 0.9 g을 얻었다. 수득율 65 %; mp 204-205。C; IR (KBr, cm-1) 2208 (CN), 1596 (C=C); NMR (300 MHz, CDCl3) δ 7.74 (d, 3H, J = 16.2 Hz), 7.54 (d, 6H, J = 8.6 Hz), 7.25 (d, 3H, J = 16.2 Hz), 6.91 (d, 3H, J = 8.6 Hz), 3.31 (m, 12H), 1.67 (m, 18H). 원소분석 결과; C48H48N6에 대한 계산치 (%) C, 81.3; H, 6.82; N, 11.9. 실험치: C, 81.4; H, 6.82; N, 11.8.1,3,5-tricyano-2,4,6-trimethylbenzene (1.2 g, 6.1 mmol) and 4-piperidinobenzaldehyde (3.6 g, 20 mmol) were added to 50 mL of ethanol / benzene (5/5). After refluxing, 4 mL of piperidine was slowly added. The solution was refluxed for 3-5 days, then the solvent was removed under reduced pressure, and the product was adsorbed onto silica gel and purified by column chromatography using hexane / ethyl acetate (4/1) as the eluent to obtain 1,3,5- 0.9 g of tricyano-2,4,6-tris (parapiperidinostyryl) benzene was obtained. Yield 65%; mp 204-205 ° C .; IR (KBr, cm −1 ) 2208 (CN), 1596 (C = C); NMR (300 MHz, CDCl 3 ) δ 7.74 (d, 3H, J = 16.2 Hz), 7.54 (d, 6H, J = 8.6 Hz), 7.25 (d, 3H, J = 16.2 Hz), 6.91 (d, 3H , J = 8.6 Hz), 3.31 (m, 12H), 1.67 (m, 18H). Elemental analysis results; Calcd for C 48 H 48 N 6 (%) C, 81.3; H, 6. 82; N, 11.9. Found: C, 81.4; H, 6. 82; N, 11.8.
실시예 7 : 1,3,5-트리니트로-2,4,6-트리스(파라메톡시페닐에티닐)벤젠의 합성Example 7: Synthesis of 1,3,5-trinitro-2,4,6-tris (paramethoxyphenylethynyl) benzene
4-메톡시페닐아세틸렌 (0.75 g, 5.7 mmol)을 THF 15 mL에 녹인 용액에 -78。C에서 n-BuLi (3.5 mL, 5.6 mmol)을 서서히 첨가한다. 이 용액을 -78。C에서 2시간동안 저어주고, 온도를 실온까지 올려서 20분 동안 더 저어 주었다. 이 용액을 -78。C로 냉각시키고, 소량의 THF에 녹인 1,3,5-트리클로로-2,4,6-트리니트로벤젠 (0.5 g, 1.6 mmol)을 서서히 첨가한 다음, 0。C에서 1시간 동안 저어주었다. 이 용액에 과량의 물을 붓고 생성물은 CH2Cl2로 추출하였다. 이것을 실리카젤에 흡착시켜 헥산/아세톤 (6/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스(파라메톡시페닐에티닐)벤젠 0.23 g을 얻었다. 수득율 24 %; mp 156-158。C; IR (KBr, cm-1) 2210 (C≡C); NMR (300 MHz, CDCl3) δ 7.55 (d, 6H, J = 8.4 Hz), 6.92 (d, 6H, J = 8.4 Hz), 3.85 (s, 9H). 원소분석 결과; C33H21N3O9에 대한 계산치 (%) C, 65.70; H, 3.51; N, 6.96. 실험치: C, 65.90; H, 3.60; N, 6.95.To the solution of 4-methoxyphenylacetylene (0.75 g, 5.7 mmol) in 15 mL of THF is added slowly n-BuLi (3.5 mL, 5.6 mmol) at -78 ° C. The solution was stirred at -78 ° C for 2 hours, and the temperature was raised to room temperature and stirred for another 20 minutes. The solution was cooled to -78 ° C, slowly added 1,3,5-trichloro-2,4,6-trinitrobenzene (0.5 g, 1.6 mmol) dissolved in a small amount of THF and then at 0 ° C. Stir for 1 hour. Excess water was poured into this solution and the product was extracted with CH 2 Cl 2 . It was adsorbed onto silica gel and purified by column chromatography using hexane / acetone (6/1) as eluent to purify 1,3,5-trinitro-2,4,6-tris (paramethoxyphenylethynyl) benzene 0.23 g was obtained. Yield 24%; mp 156-158. C; IR (KBr, cm −1 ) 2210 (C≡C); NMR (300 MHz, CDCl 3 ) δ 7.55 (d, 6H, J = 8.4 Hz), 6.92 (d, 6H, J = 8.4 Hz), 3.85 (s, 9H). Elemental analysis results; Calcd for C 33 H 21 N 3 0 9 (%) C, 65.70; H, 3.51; N, 6.96. Found: C, 65.90; H, 3. 60; N, 6.95.
실시예 8: 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)페닐에티닐]벤젠의 합성Example 8: Synthesis of 1,3,5-trinitro-2,4,6-tris [p- (N-diethylamino) phenylethynyl] benzene
4-디에틸아미노페닐아세틸렌 (3.4 g, 20 mmol)을 THF 100 mL에 녹인 용액에 -78。C에서 n-BuLi (12 mL, 19 mmol)을 서서히 첨가한다. 이 용액을 -78。C에서 2시간동안 저어주고, 온도를 실온까지 올려서 20분 동안 더 저어 주었다. 이 용액을 -78。C로 냉각시키고, 소량의 THF에 녹인 1,3,5-트리클로로-2,4,6-트리니트로벤젠 (1.7 g, 5.3 mmol)을 서서히 첨가한 다음, 0。C에서 1시간 동안 저어주었다. 이 용액에 과량의 물을 붓고 생성물은 CH2Cl2로 추출하였다. 이것을 실리카젤에 흡착시켜 헥산/아세톤 (6/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스[p-(N-디에틸아미노)페닐에티닐]벤젠 0.6 g을 얻었다. 수득율 16 %; mp 150。C; IR (KBr, cm-1) 2204 (C≡C); NMR (300 MHz, CDCl3) δ 7.45 (d, 6H, J = 8.9 Hz), 6.63 (d, 6H, J = 8.9 Hz), 3.40 (q, 12H, J = 6.9 Hz), 1.19 (t, 18H, J = 6.9 Hz). 원소분석 결과; C42H42N6O6에 대한 계산치 (%) C, 69.40; H, 5.82; N, 11.60. 실험치: C, 69.12; H, 6.60; N, 11.50.To a solution of 4-diethylaminophenylacetylene (3.4 g, 20 mmol) in 100 mL of THF is added slowly n-BuLi (12 mL, 19 mmol) at -78 ° C. The solution was stirred at -78 ° C for 2 hours, and the temperature was raised to room temperature and stirred for another 20 minutes. The solution was cooled to -78 ° C, slowly added 1,3,5-trichloro-2,4,6-trinitrobenzene (1.7 g, 5.3 mmol) dissolved in a small amount of THF and then at 0 ° C. Stir for 1 hour. Excess water was poured into this solution and the product was extracted with CH 2 Cl 2 . It was adsorbed onto silica gel and purified by column chromatography using hexane / acetone (6/1) as eluent to give 1,3,5-trinitro-2,4,6-tris [p- (N-diethylamino) 0.6 g of phenylethynyl] benzene was obtained. Yield 16%; mp 150 ° C .; IR (KBr, cm −1 ) 2204 (C≡C); NMR (300 MHz, CDCl 3 ) δ 7.45 (d, 6H, J = 8.9 Hz), 6.63 (d, 6H, J = 8.9 Hz), 3.40 (q, 12H, J = 6.9 Hz), 1.19 (t, 18H , J = 6.9 Hz). Elemental analysis results; Calcd for C 42 H 42 N 6 O 6 (%) C, 69.40; H, 5. 82; N, 11.60. Found: C, 69.12; H, 6. 60; N, 11.50.
실시예 9 : 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노페닐에티닐)벤젠의 합성Example 9 Synthesis of 1,3,5-trinitro-2,4,6-tris (parapiperidinophenylethynyl) benzene
4-피페리디노페닐아세틸렌 (1.5 g, 8.0 mmol)을 THF 30 mL에 녹인 용액에 -78。C에서 n-BuLi (4.9 mL, 7.8 mmol)을 서서히 첨가한다. 이 용액을 -78。C에서 2시간동안 저어주고, 온도를 실온까지 올려서 20분 동안 더 저어 주었다. 이 용액을 -78。C로 냉각시키고, 소량의 THF에 녹인 1,3,5-트리클로로-2,4,6-트리니트로벤젠 (0.75 g, 2.4 mmol)을 서서히 첨가한 다음, 0。C에서 1시간 동안 저어주었다. 이 용액에 과량의 물을 붓고 생성물은 CH2Cl2로 추출하였다. 이것을 실리카젤에 흡착시켜 헥산/아세톤 (6/1)를 용리제로 사용하여 관 크로마토 그래피로 정제하여 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노페닐에티닐)벤젠 0.35 g을 얻었다. 수득율 25 %; mp 221-223。C; IR (KBr, cm-1) 2210 (C≡C); NMR (300 MHz, CDCl3) δ 7.47 (d, 6H, J = 8.7 Hz), 6.87 (d, 6H, J = 8.7 Hz), 3.29 (m, 12H), 1.67 (m, 18H). 원소분석 결과; C45H42N6O6에 대한 계산치 (%) C, 70.80; H, 5.55; N, 11.00. 실험치: C, 70.90; H, 5.60; N, 11.50.To a solution of 4-piperidinophenylacetylene (1.5 g, 8.0 mmol) in 30 mL of THF, slowly add n-BuLi (4.9 mL, 7.8 mmol) at -78 ° C. The solution was stirred at -78 ° C for 2 hours, and the temperature was raised to room temperature and stirred for another 20 minutes. The solution was cooled to -78 ° C, slowly added 1,3,5-trichloro-2,4,6-trinitrobenzene (0.75 g, 2.4 mmol) dissolved in a small amount of THF and then at 0 ° C. Stir for 1 hour. Excess water was poured into this solution and the product was extracted with CH 2 Cl 2 . This was adsorbed onto silica gel and purified by column chromatography using hexane / acetone (6/1) as eluent to give 1,3,5-trinitro-2,4,6-tris (parapiperidinophenylethynyl) benzene. 0.35 g was obtained. Yield 25%; mp 221-223。 C; IR (KBr, cm −1 ) 2210 (C≡C); NMR (300 MHz, CDCl 3 ) δ 7.47 (d, 6H, J = 8.7 Hz), 6.87 (d, 6H, J = 8.7 Hz), 3.29 (m, 12H), 1.67 (m, 18H). Elemental analysis results; Calcd for C 45 H 42 N 6 O 6 (%) C, 70.80; H, 5.55; N, 11.00. Found: C, 70.90; H, 5. 60; N, 11.50.
실시예 10 : HRS방법에 의한 팔중극자 분자의 비선형 광학 성질(β)의 측정Example 10 Measurement of Nonlinear Optical Properties (β) of Octodex Molecules by HRS Method
위의 일반식 (I), (II)로 나타낼 수 있는 팔중극자 분자의 비선형 광학 성질(β)은 hyper-Rayleigh scattering(HRS) 방법으로 측정하였다[Clays, K.; Persoon, A. Phys. Rev. Lett., 1991, 66, 2980-2983, Clays, K.; Persoon, A. Rev. Sci. Instrum., 1992, 63, 3285-3289]. 이 목적으로 Q-switched Nd:YAG 레이저를 광원으로 하고 이차조화파에 해당하는 간섭필터와 광전증배관(PMT) 및 boxcar 신호 평균기(signal averager)를 이용하여 HRS 신호를 관찰했다.The nonlinear optical properties (β) of the octapole molecules represented by the general formulas (I) and (II) above were measured by the hyper-Rayleigh scattering (HRS) method [Clays, K .; Persoon, A. Phys. Rev. Lett., 1991, 66, 2980-2983, Clays, K .; Persoon, A. Rev. Sci. Instrum., 1992, 63, 3285-3289. For this purpose, the HRS signal was observed using a Q-switched Nd: YAG laser as a light source, an interference filter corresponding to a second harmonic wave, a photomultiplier tube (PMT), and a boxcar signal averager.
비선형 광학분자를 CHCl3에 녹인 용액에 쪼여준 빛의 세기 I0와 방출되는 HRS신호의 세기 I2ω의 관계는 식(1)과 같이 나타낼 수 있다. 따라서 비선형 광학분자의 농도변화에 따른 I2ω를 측정하여 전자에 대해 후자를 도시하면 직선관계가 나타난다. 위의 실시예 9의 방법에 따라 합성한 1,3,5-트리니트로-2,4,6-트리스(파라피페리디노페닐에티닐)벤젠(VI-3)을 CHCl3에 녹인 용액의 농도변화에 따른 비선형 광학성질의 관계는 제 10도에 예시하였다. 제 10도는 이와 같은 직선관계가 잘 얻어짐을 보여주는 결과이다. 위의 실시예 1-9에서 합성한 모든 팔중극자 화합물의 농도와 HRS신호사이의 관계도 모두 이와 같은 직선을 나타내었다. 이 직선의 기울기(Slope)와 절편(Intercept)은 각각 식(2) 및 (3)과 같으며, 여기서 g는 상수이다. 위의 실시예 1-9에서 합성한 모든 팔중극자 화합물의 β값은 기울기를 절편으로 나눈 값 R과 용매의 number density (Nsolvent) 및 용매의 β값 (βsolvent)를 식 (4)에 대입하여 구하였다.The relationship between the intensity I 0 of the light and the intensity I 2ω of the emitted HRS signal in a solution in which nonlinear optical molecules are dissolved in CHCl 3 can be expressed by Equation (1). Therefore, when I 2ω is measured according to the concentration change of nonlinear optical molecules and the latter is shown for the former, a linear relationship appears. Change in the concentration of a solution of 1,3,5-trinitro-2,4,6-tris (parapiperidinophenylethynyl) benzene (VI-3) dissolved in CHCl 3 synthesized according to the method of Example 9 above The relationship between the nonlinear optical properties is illustrated in FIG. 10. 10 is a result showing that such a linear relationship is well obtained. The relationship between the concentrations of all the octapole compounds synthesized in Example 1-9 and the HRS signal was also shown as such a straight line. The slope and intercept of the straight line are shown in equations (2) and (3), respectively, where g is a constant. Β values of all the octapole compounds synthesized in Example 1-9 above were substituted into Equation (4) with the value R of the slope divided by the intercept, the number density (N solvent ) of the solvent , and the β value (β solvent ) of the solvent . It was obtained.
이 화합물들의 β(0)값은 위에서 구한 β값과 식 (5)를 이용하여 계산하였다.Β (0) values of these compounds were calculated using the above β values and equation (5).
여기서 μ01(μ11'), E01및 ω는 각각 전이 쌍극자 모멘트, 바닥상태와 축퇴된 들뜬 상태의 에너지 차이 및 레이저의 진동수를 나타내며, ħ는 플랑크상수를 나타낸다 [Dhenaut, C.; Ledoux, I.; Samuel, Ifor D. W.; Zyss, J.; Bourgault, M.; Bozec, H. S. Nature, 1995, Vol, 374, 339-342].Where μ 01 (μ 11 ′ ), E 01 and ω represent the transition dipole moments, the energy difference between the ground state and the degenerate excited state, and the frequency of the laser, and ħ represents Planck's constant [Dhenaut, C .; Ledoux, I .; Samuel, Ifor DW; Zyss, J .; Bourgault, M .; Bozec, HS Nature, 1995, Vol, 374, 339-342.
이와 같은 방법으로 구한 팔중극자 화합물들의 선형 및 비선형 광학적 성질은 표1-3에 정리하였다. 이 표에서 보듯이 팔중극자 비선형 광학물질 III, V, VII은 그것에 상응하는 이중극자 물질 IV, VI, VIII에 비해 이차 비선형 광학성질[β(0)]이 1-22배 정도 크게 나타났다. 따라서 같은 양의 물질을 사용할 경우 훨씬 더 큰 비선형 광학 성질을 나타낼 것이며, 고체상태에서 같은 방향으로 배열시키기가 용이하므로 비선형 광학 성질이 매우 큰 유기 비선형광학물질을 제조하는 데 사용할 수 있다.The linear and nonlinear optical properties of the octapole compounds obtained in this way are summarized in Table 1-3. As shown in the table, the bipolar nonlinear optical materials III, V, and VII exhibited a second nonlinear optical property [β (0)] by 1-22 times larger than the corresponding dipole materials IV, VI, and VIII. Therefore, when the same amount of material is used, it will show much larger nonlinear optical properties, and since it is easy to arrange in the same direction in the solid state, it can be used to prepare an organic nonlinear optical material having very high nonlinear optical properties.
표 1. 1,3,5-트리니트로-2,4,6-트리스(스티릴)벤젠 유도체의 선형 및 비선형 광학 특성Table 1. Linear and nonlinear optical properties of 1,3,5-trinitro-2,4,6-tris (styryl) benzene derivatives
표 2. 1,3,5-트리시아노-2,4,6-트리스(스티릴)벤젠 유도체의 선형 및 비선형 광학 특성Table 2. Linear and Nonlinear Optical Properties of 1,3,5-Tricyano-2,4,6-tris (styryl) benzene Derivatives
표 3. 1,3,5-트리니트로-2,4,6-트리스(페닐에티닐)벤젠 유도체의 선형 및 비선형 광학특성Table 3. Linear and nonlinear optical properties of 1,3,5-trinitro-2,4,6-tris (phenylethynyl) benzene derivatives
상기 시험예에서 나타나듯이 본 발명의 비선형 광학물질은 기존의 이중극자유기 비선형 광학물질에 비해 크게 향상된 비선형 광학성질을 가지고 있으며, 열적 안정성이 우수하고, 고체상태에서 같은 방향으로 배열시키기가 용이하므로 분자집합체로서의 비선형 광학성질을 향상시키기가 용이한 유기 비선형 광학물질을 제조하는데 제공될 수 있게 되었다.As shown in the above test example, the nonlinear optical material of the present invention has a greatly improved nonlinear optical property compared to the existing bipolar organic nonlinear optical material, has excellent thermal stability, and is easy to arrange in the same direction in a solid state. It has become possible to provide an organic nonlinear optical material that is easy to improve nonlinear optical properties as an aggregate.
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