Syntheses, structures, and characterizations of novel low-dimensional birefringent materials
- 주제어 (키워드) birefringence , lone pair electrons , π-conjugate group , crystal structure , DFT calculation
- 발행기관 서강대학교 일반대학원
- 지도교수 옥강민
- 발행년도 2025
- 학위수여년월 2025. 2
- 학위명 박사
- 학과 및 전공 일반대학원 화학과
- 실제 URI http://www.dcollection.net/handler/sogang/000000079679
- UCI I804:11029-000000079679
- 본문언어 영어
- 저작권 서강대학교 논문은 저작권 보호를 받습니다.
초록 (요약문)
Birefringent materials are crucial in laser-driven fields, with birefringence being a key parameter closely linked to anisotropy. Birefringence-active-group (BAG) with anisotropic distributed electron density, such as cations with lone pair electrons (LPEs) and π-conjugate groups, are cornerstones in constructing birefringent materials. Low-dimensional structures with inherent structural anisotropy, such as the in-plane vs. out-plane in two-dimensional structures, intra-chain vs. inter-chain in one-dimensional structures, are ideal for exploring large birefringence. In this dissertation, the main objectives are to utilize the different BAGs to construct the birefringent crystals with low-dimensional secondary structures. Lone pair electrons (LPEs) endow the cations with large polarizability anisotropy. To deeply explore how the LPEs cations affect the birefringence, K2Pb2Si2O7 and Mg(H2O)6[(IO2(OH))2(IO3)]2 were synthesized and examined. The relationship between spatial density, polarizability anisotropy of LPEs cations and birefringence will be discussed. The π-conjugate groups, B(OH)3, [HCO3]- and [C(NH2)3]+ show the large HOMO-LUMO gaps, while [NO3]-, [HC2O4]-, [C2O4]2-, 4-Hydroxypyridine (4HP), 2-Aminopyrimidinium (2APM) exhibit larger polarizability anisotropy but smaller HOMO-LUMO gaps. Based on these BAGs, three deep-ultraviolet (DUV) birefringent crystals of KF·B(OH)3, K2FHCO3∙H2O, C(NH2)3CH3SO3 have been synthesized and grown. The β-C(NH2)3Cl and γ-C(NH2)3Cl were hypothetically designed and the NH2COF was screened out as potential DUV birefringent materials. Eleven ultraviolet (UV) birefringent compounds including KHC2O4·B(OH)3, Sr(NO3)(NH2SO3)·H2O, [Mg(NO3)2∙6H2O]·(4HP)2, LiNO3·H2O·4HP, [LiNO3·H2O·4HP]·4HP, [(4HP)2ZnCl2], [(4HP)+]2[(ZnCl4)2-], (4HP)+(NO3)-, (4HP)+(HC2O4)-, (2APM)+(NO3)- and (2APM)+(HC2O4)-·H2O, have been synthesized and characterized. Through crystal structure analysis and DFT calculations, the effects of the spatial density, distribution, polarizability anisotropy of BAGs and the dimension of final compounds will be discussed.
more목차
1. Introduction 27
1.1. The Interaction of Light with Crystals 27
1.2. The Propagation of Light in Crystals and The Birefringence of Crystals 28
1.3. Birefringence Measurements 32
1.4. Second-Order Nonlinear Optical Effect 35
1.5. Research Status of Birefringent Materials 36
1.6. Birefringence-Active Groups 37
1.7. Research Background and Thesis Structure 39
1.8. References 46
2. Lone Pair Electron Cations-Based Compounds 53
2.1. Mg(H2O)6[(IO2(OH))2(IO3)]2 53
2.1.1. Experimental Section 53
2.1.2. Results and Discussions 57
2.1.3. Conclusion 65
2.1.4. References 66
2.2. K2Pb2Si2O7 69
2.2.1. Experimental Section 69
2.2.2. Results and Discussion 73
2.2.3. Conclusion 79
2.2.4. References 80
3. Coplanar Group-Based DUV Compounds 81
3.1. KF⸱B(OH)3 81
3.1.1. Experimental Section 81
3.1.2. Results and Discussion 86
3.1.3. Conclusion 98
3.1.4. References 99
3.2. C(NH2)3X (A = CH3SO3 and Cl) and NH2COF 102
3.2.1. Experimental Section 102
3.2.2. Results and Discussion 107
3.2.3. Conclusion 124
3.2.4. References 125
3.3. K2HCO3F·H2O 130
3.3.1. Experimental Section 130
3.3.2. Results and Discussion 134
3.3.3. Conclusion 140
3.3.4. References 141
4. Coplanar Group-Based UV Compounds with Large Birefringence 144
4.1. KHC2O4·B(OH)3 144
4.1.1. Experimental Section 144
4.1.2. Results and Discussion 149
4.1.3. Conclusion 158
4.1.4. References 159
4.2. Sr(NO3)(NH2SO3)·H2O 163
4.2.1. Experimental Section 163
4.2.2. Results and Discussion 168
4.2.3. Conclusion 179
4.2.4. References 180
5. Six-Membered-Ring-Based UV Compounds with Giant Birefringence 183
5.1. 4-Hydroxpyridine-Nitrates Cocrystals 183
5.1.1. Experimental Section 183
5.1.2. Results and Discussion 190
5.1.3. Conclusion 211
5.1.4. References 212
5.2. Zero-Dimensional 4-Hydroxypyridine-Zn-Cl Compounds 215
5.2.1. Experimental Section 215
5.2.2. Results and Discussion 220
5.2.3. Conclusion 233
5.2.4. References 234
5.3. Metal-Free Quasi-Chains Compounds with Giant Birefringence 239
5.3.1. Experimental Section 239
5.3.2. Results and Discussion 246
5.3.3. Conclusion 272
5.3.4. References 273
6. Conclusion 277
7. Publications and Corresponding Chapters 282
