Studies on Synthesis and Characterization of Supramolecular Assemblies Consisting of Chiral Amphiphiles and One-Dimensional Mixed Valence Platinum Complexes

다국어 초록 (Multilingual Abstract)

I sincerely thanks to Professor Nobuo Kimizuka for his very kind suggestions, discussions and advices for last 3 years. I am also grateful to Professor Masahiro Goto and Professor Hiroyuki Furuta for reading, evaluating and valuable comments on the entire contents of this thesis to the final page. In addition, I would like to express gratitude to Associate Professor Kazunori Matsuura, Assistant Keita Kuroiwa, Secretary Reiko Ando and my all companions in Kimizuka Lab for valuable discussion and support.
I express great gratitude to Associate Professor Kenji Kaneko, Laboratory of High-Voltage Electron Microscopy at Kyushu University, for measurements of HRTEM, and also acknowledge Assistant Keita Kuroiwa and Mr. Imada, graduate student of Kajiyama Laboratory for measurements of Powder XRD.
I wish also to acknowledge the significant help from Professor Jae-Sup Shin (Chungbuk University at Korea) and lecturer Seung-Woo Lee (Kitakyushu University) for my living in Japan
Finally, I express my thankfulness to my parents, brother and sister, and especially my beloved wife (Su-Eun) and son (Joo-Ha) for their being patient and understanding throughout my courses of study.

목차 (Table of Contents)

• Contents
• Chapter 1 General Introduction = 1
• 1-1. Supramolecular chemistry of discrete transition metal complexes = 1
• 1-1-1. Supramolecular self-assembled complexes = 1
• 1-1-2. Fabrication of organic / inorganic nanostructures = 2
• 1-2. Quasi-one-dimensional halogen-bridged mixed valence complexes = 4
• 1-2-1. Structure of one-dimensional halogen-bridged mixed valence complexes 5
• 1-2-2.Charge transfer exiton in halogen mixed-valence Pt complexes = 6
• 1-3. Construction of supramolecular self-assemblies consisting of anionic amphiphile and chloro-bridged mixed valence Complex = 7
• 1-4. Outline of this thesis = 11
• 1-5. References = 12
• Chapter 2 Synthesis of halogen-bridged mixed valence Pt complexes and anionic amphiphiles = 14
• 2-1. Introduction = 14
• 2-2. Synthesis of halogen-bridged mixed valence Pt complexes = 16
• 2-2-1. Synthesis of chloro-bridged mixed valence Pt(Ⅱ)/Pt(Ⅳ) complex = 16
• 2-2-1-1. Synthesis of bis（diethylamine）Pt（Ⅱ）chloride = 16 2-2-1-2. Synthesis of bis（diethylamine）Pt（Ⅳ）chloride = 17
• 2-2-1-3. Synthesis of chloro-bridged mixed valence Pt(Ⅱ)/Pt(Ⅳ) complex = 18
• 2-2-2. Synthesis of iodide-bridged mixed valence Pt(Ⅱ)/Pt(Ⅳ) complex = 18
• 2-2-3. Synthesis of bromide-bridged mixed valence Pt(Ⅱ)/Pt(Ⅳ) complex = 19
• 2-2-3-1. Synthesis of bis（diethylamine）Pt（Ⅳ）bromide = 19
• 2-2-3-2. Synthesis of bromide-bridged mixed valence Pt(Ⅱ)/Pt(Ⅳ) complex = 19
• 2-3. Synthesis of chiral anionic amphiphiles = 20
• 2-3-1. Synthesis of dialkyl-L-glutamate hydrochloride (n = 12, 14, 16) = 20
• 2-3-2. Synthesis of dialkyl-L-glutamate sodium sulfoethanoyl acid (n=12,14,16) = 21
• 2-3-3. Synthesis of didodecyloxyethyl-L-glutamate hydrochloride = 24
• 2-3-4. Synthesis of didodecyloxyethyl-L-glutamate sodium sulfoethanoyl acid = 25
• 2-3-5. Synthesis of didodecyl-L-glutamate sodium sulfophenyl acid = 26
• 2-3-6. Synthesis of didodecyl-L-asparnate sodium hydrochloride = 28
• 2-3-7. Synthesis of didodecyl-L-asparnate sodium sulfoethanoyl acid = 29
• 2-3-8. Synthesis of dodecyl-L-alaninate hydrochloride = 30
• 2-3-9. Synthesis of dodecyl-L-alaninate sodium sulfoethanoyl acid = 31
• 2-3-10. Synthesis of dodecyl glycinate hydrochloride = 32
• 2-3-11. Synthesis of dodecyl glycinate sodium sulfoethanoyl acid = 33
• 2-3-12. Synthesis of oleyl-L-glutamate hydrochloride = 34
• 2-3-13. Synthesis of oleyl-L-glutamate sodium sulfoethanoyl acid = 35
• 2-4. Conclusion = 38
• 2-5. References = 39
• Chapter 3 Effect of chain structure and spacer groups in supramolecular assemblies consisting of one-dimensional mixed valence Pt complexes and anionic lipids = 40
• 3-1. Introduction = 40
• 3-2. Effect of alkyl chain length and incorporation of ether linkages in the anionic amphiphiles = 43
• 3-2-1. Preparation of lipid/chloro-bridged mixed valence Pt complexes = 43
• 3-2-2. UV-visible spectra = 47
• 3-2-2-1. Dependence of CT absorption characteristics on the alkyl chain structures = 47
• 3-2-2-2. Thermal properties by alkyl chain structure = 49
• 　3-2-3. Transmission Electron Microscopy (TEM) = 52
• 3-3. Solvatochromic nanowires self-assembled from, cationic chloro-bridged linear platinum complexes and anionic amphiphiles = 55
• 3-3-1. Preparation of lipid / chloro-bridged mixed valence Pt complex = 55
• 3-3-2. Transmission Electron Microscopy (TEM) = 57
• 3-3-3. UV-visible and CD spectra = 59
• 3-3-3-1. Solvatochromism by charge transfer = 59
• 3-3-3-2. Thermal stability by UV-visible and CD spectra = 61
• 3-4. Conclusion = 65
• 3-5. References = 66
• Chapter 4 The Effect of amphiphilic chemical structure on the structural and spectroscopic properties of lipid/one-dimensional mixed valence Pt complexes = 69
• 4-1. Introduction = 69
• 4-2. Preparation of lipid / halogen-bridged mixed valence Pt complexes = 73
• 4-3. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) = 77
• 4-3-1. Change of morphology depending on amphiphilic structure and temperature = 77
• 4-3-2. High Resolution Transmission Electron Microscopy (HRTEM) = 79
• 4-4. Electronic properties and crystalline structures of the lipid-packaged one-dimensional complexes = 82
• 4-4-1. Electronic states of the one-dimensional lipid complexes = 82
• 4-4-2. Crystalline structures by Powder X-ray Diffraction = 86
• 4-4-3. ICD-exciton coupling = 92
• 4-4-4. Temperature dependence of UV-visible and CD spectra = 94
• 4-5. Conclusion = 98
• 4-6. References = 99
• Chapter 5 Effect of halogen ions on the charge transfer characteristics of lipid-packaged, one-dimensional mixed valence Pt complexes = 102
• 5-1. Introduction = 102
• 5-2. Preparation of lipid / halogen-bridged mixed valence Pt complexes = 105
• 5-3. Transmission Electron Microscopy (TEM) = 109
• 5-4. Effect of halogen ions on the charge transfer characteristics of one-dimensional mixed valence Pt complexes = 111
• 5-5. Conclusion = 117
• 5-6. References = 118
• Chapter 6 Pillared honeycomb nano-architectures formed on solid surfaces by the self-assembly of lipid-packaged one-dimensional Pt complexes = 119
• 6-1. Introduction = 119
• 6-2. Preparation of lipid / chloro-bridged mixed valence Pt complex = 123
• 6-3. UV-visible and CD spectra of the lipid-packaged complexes = 125
• 6-4. Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Dark-Field Optical Microscopy = 130
• 6-5. Dependence of the humidity and the concentration of solution for the formation of honeycomb structure for the formation of honeycomb structure = 138
• 6-5-1. Effect of relative humidity = 138
• 6-5-2. Effect of concentration = 139
• 6-6. Vapochromism observed for the cast films = 141
• 6-7. Conclusion = 147
• 6-8. References = 148
• Chapter 7 Summary and Conclusion = 151
• Acknowledgements = 156