새로운 전자 주게와 받게를 갖는 비이온성 전기광학 결정에 대한 연구
A dissertation submitted to the graduate faculty for the master’s degree of engineering
- 주제(키워드) 비선형광학결정 , 유기광학결정
- 발행기관 The Graduate School, Ajou University
- 지도교수 Kwon, O-Pil
- 발행년도 2011
- 학위수여년월 2011. 2
- 학위명 석사
- 학과 및 전공 일반대학원 분자과학기술학과
- 실제URI http://www.dcollection.net/handler/ajou/000000011693
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Organic nonlinear optical crystals have been attracted much interest due to their numerous design possibilities and larger and faster optical nonlinearities when compared to inorganic crystals. To investigate new nonlinear optic chromophores, we designed and synthesized (1) new cofigurationally locked polyene (CLP) choromophores, by changing the donor groups, (2) thiolte-based hydrazone chromophores, (3) cyanoacetate-based chromophore with new electron acceptor. Here, we mainly have investigated the new nonlinear molecules contaning sulfur, a series of thiolated-donor based configurationally locked polyene chromophores and thiolated-based hydrazone chromophores for second-order nonlinear optical applications. We synthesized a series of nonlinear optical chromophores based on thiolated electron donors(X : -H, -CH₃, -Ph,-PhSCH₃,-PhOSH₃). The first hyperpolarizability (β(_(max)) of thioladted polyene chromophores was investigated experimentally and theorically by quantum chemical calculations with, TD-DFTand finite-field (FF) method from the optimized (OPT)molecular structures with B3LYP/6-311+G(d). The thiolated polyene chromophores exhibit large molecular nonliearities than CLP chromophores with conventional donors such as OH1 (2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile) and DA (2-(3-(4-(dimethylamino)styryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile). But they have low molecular nonliearities at solution state. We approach the crystal analysis as solid state to know how it works lowing molecular nonliearities. We have investigated the hydrazone crystal, SM-NPH (4-(methylthio)benzealdehyde-(4-nitrophenylhydrazone) and SB-NPH (4-(4-phenylthio)benzealdehyde-4-nitrophenylhydrazone). Interestingly, the main supramolecular interaction is still maintaining lambda-shaped packing of nitrophenylhydrazone reported previously groups and is modified by herringbone-shaped packing of phenylthiobenzene groups. We also investigated the microscopic and macroscopic nonlinearities theoretically. As well as donor derivatives, we have developed the new DA derivative containong acetate acceptor, C2-COOMe (methyl 2-cyano-2-(3-(4-(dimethylamino)styryl)-5,5-dimethylcyclohex-2-enylidene)acetate). They are asymmetric molecular form unlike DA and were synthesized E and Z form. C2-COOMe has two isomers, E-form and Z-form and Z-form are consisted of two phase structure. E-form and Z-form(1) are consist of centrosymmetric structure with P 21/n and Z-form(2) dose acentric structure. Now we try to analysis the acentric crystals from Z-form(2).
more초록/요약
본 연구에서는 무기결정에 비해 높고 빠른 광학적 비선형성을 얻기위해 새로운 유기 결정을 개발하였다: 1) 싸이올(–S–) 기반의 새로운 전자 주게를 도입한 cofigurationally locked polyene (CLP) (X : –H, –CH₃, –Ph,– PhSCH₃,–PhOSH₃) 발색단 2) 싸이올 기반의 hydrazone 발색단 (X : –CH₃, –Ph). 3)새로운 전자 받게인 cyanoacetate 를 도입한 발색단을 설계,합성하고 결장을 성장시켰다. 본 연구를 통해 싸이올 기반의 전자 주게를 갖는 새로운 발색단은기존의 보편적인 전자 주게를 갖는 CLP 발색단에 비해 높은 hyperpolarizability (β_(max)) 이론적 계산 값을 갖지만 실험적으로 얻어진 발색단은 이론값보다 낮은 hyperpolarizability (β_(max)) 값을 보인다. 원인을 알기 위해 같은 결정구조를 갖는 두 형태이성질체 결정 구조 및 이론적 비선형 계산 값을 통해 이는 싸이올 결합의 용이한 회전에 의해 발생된 현상으로 전자 주게가 갖는 torsion 각에 따라 그 값이 달라지게 되는 사실을 발견하였다. 또한 싸이올 기반의 hydrazone 발색단인 SB-NPH(4-(4-phenylthio)benzealdehyde-4-nitrophenylhydrazone 을 합성하였다. 람다(lamda) 형태의 결정구조를 이루는 기존의 hydrazone 발색단의 성질은 유지하면서 싸이올 그룹의 성질인 헤링본 형태를 보이는)의 비대칭형 중심구조를 갖는 결정구조를 얻었다. 이는 또한 ㎔ 응용의 가능성을 확인하였다. 새로운 전자 주게 연구뿐만 아니라 CLP 에 새로운 전자 받게를 도입하여 비대칭형 중심구조를 갖는 결정을 얻었다. Cyanoacetate 기반의 C2-COOMe (methyl 2-cyano-2-(3-(4-(dimethylamino)styryl)-5,5-dimethylcyclohex-2-enylidene)acetate)라 불리는 발색단은 비대칭분자구조를 갖기 때문에 E 형과 Z 형이 존재한다. 결정구조내에 E 형은 대칭분자배열을 갖는 결정을 이루며 Z 형은 대칭형과 비대칭형 분자배열의 두가지의 결정형태를 이룬다.
more목차
I. Introduction 1
II. Brief Review 4
II .1 Nonlinear optical Effects and Materials 4
II.1.1 Nonlinear Optical Effects 4
II.1.2 Organic Nonlinear Optical Materials 5
II.1.3 Molecular Nonlinearities 7
II.2 Organic Nonlinear Single Crystals 8
II.2.1 Noncentrosymmetric Crystalline Packing: Approaches 8
II.2.2 Examples of Molecular Crystals 9
II.2.3 Crystal Growth of Organic Materials 11
II.2.4 Challenges of Organic Nonlinear Optical Crystals 12
III. Experiments 14
III.1 Chemical Structure 14
III.2 Synthesis 15
III.2.1 Materials 16
III.2.2 General Characterization 16
III.2.3 Synthesis of Thiolated Donor Molecules 16
III.2.4 Synthesis of the Chromophores 18
III.3 Macroscopic and Microscopic Nonlinearities 30
III.4 Crystal Structure Data for the MT, SB1, SB2 and C2-COOMe Crystal 30
IV. Results and Discussion 34
IV.1 New Configurationally Locked Polyene Chromophores with Tiolated Donor 34
IV.1.1 Design of New Configurationally Locked Polyene Chromophores 34
IV.1.2 Characterization and Nonlinear Optical Properties 34
IV.1.3 Single Crystal Structure of Isomorphic SM, SB1, and SB2 42
IV.2 New Thiolated-based hydrzone Chromophores 54
IV.2.1 Design of the Thiolated-based hydrzone Chromophores 54
IV.2.2 Single Crystal Structure of Thiolated-based hydrzone Chromophores 56
IV.2.3 Characterization and Nonlinear Optical Properties 58
IV.3 Assymetric isomerism with New Acceptor 63
IV.3.1 Design of C2-COOMe 63
IV.3.2 Characterization and Powder test 63
VI. Conclusions 65
VII. References 66
