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산화환원 활성 다중자리 리간드 및 이를 이용한 다공성 배위 화합물의 설계

Design of Redox Active Multi-Interactive Ligand and Porous Coordination Networks

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  • 발행기관 포항공과대학교 일반대학원
  • 발행년도2016
  • 학위수여년월2016. 2
  • 학위명박사
  • 학과 및 전공일반대학원 첨단재료과학부
  • 본문언어영어
  • 저작권포항공과대학교 논문은 저작권에 의해 보호받습니다.
초록 moremore
In this doctoral thesis, I deal with the novel strategies to develop the functional porous coordination networks based on the redox-active multi-interactive ligand. Although many researchers highlighted radical inclusion into porous coordination networks, there was no detailed fundamental study. In...
In this doctoral thesis, I deal with the novel strategies to develop the functional porous coordination networks based on the redox-active multi-interactive ligand. Although many researchers highlighted radical inclusion into porous coordination networks, there was no detailed fundamental study. In that regard, theoretical and fundamental understanding of radical behavior will be a key issue in coordination chemistry. Through several experimental demonstrations, I studied how ligands cooperate for network formation and control network properties at a fundamental level. The experimental details are discussed in the following 5 chapters. In Chapter 1, I summarize the recent developments in porous coordination networks. Many kinds of research have been performed to find fascinating properties like gas sorption/desorption/separation, molecular recognition, drug delivery, magnetism, conductivity, catalyst and so on. This chapter describes the introductory aspects of rational ligand design for functional porous coordination networks and redox ligand cooperation system in coordination networks. In Chapter 2, I investigated the redox-active multi-interactive ligand, 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (TPDAP) which showed two-step redox activity. TPDAP was synthesized by four-step reactions and characterized by UV-vis-NIR, 1H NMR, cyclic voltammetry (CV), and single crystal X-ray structure analysis. Furthermore, TPDAP neutral radical was generated by oxidation and characterized clearly by continuous wave-electron spin resonance spectroscopic (cw-ESR). In Chapter 3, I demonstrate the selective formation of conductive/non conductive porous coordination networks using a redox active ligand. The unique self-oxidative reaction of the ligand produce the oxidized species. Depending on the oxidation state of TPDAP, I could selectively prepare electron-conducting (paramagnetic) or insulating (diamagnetic) porous networks. The porous coordination network properties were characterized by solid state cyclic voltammogram (CV), two-probe conductivity measurement and X-ray crystal structure analysis. The redox active networks showed different molecular arrangements and, based on the electronic state, exhibited both electron conductive and insulating natures. In Chapter 4, I demonstrate the potential applications taking advantage of the redox activity. Thanks to the three fold symmetrical nature of the ligand, TPDAP showed dichotomic network formation with TPHAP. This irregular system produce a more stable network than a TPDAP network. The dichotomic network system showed CT interactions between TPDAP and electron acceptor to confirm the donor property of TPDAP in a network structure.
목차 moremore
Contents

Chapter 1. General Introduction ..................... 1
...
Contents

Chapter 1. General Introduction ..................... 1
1.1. Insight into the Development of Porous Coordination Networks (PCNs) ..................................... 2
1.2. Rational Ligand Design for Functional Porous Coordination Networks ............................... 6
1.2.1. Non-conventional in situ Synthesis .......... 10
1.2.2. Conventional Synthesis ...................... 12
1.3. Redox Ligand Cooperation System in Coordination Networks ........................................... 14
1.3.1. Radical as a Ligand in Porous Coordination Networks ........................................... 14
1.3.2. Radical Cooperation into Porous Coordination Networks .......................................... 16
1.4. Survey of This Thesis ........................ 24
1.5. References ................................... 26
Chapter 2. Redox Active Diazaphenalenyl-Based Molecule and Neutral Radical Formation...................... 32
2.1. Introduction...................................33
2.2. Results and Discussion........................ 36
2.2.1. Synthesis of 2,5,8-tri(4′-pyridyl)-1,3-diazaphenalene (TPDAP, H+1?) ...................... 36
2.2.2. X-ray Crystallographic Analysis............. 37 2.2.3. The Preparation of Neutral Radical.......... 39
2.2.4. The Electronic Property of TPDAP ........... 41
2.3. Conclusion.................................... 43
2.4. Experimental Sections ........................ 44
2.4.1. General Experimental Information ........... 44
2.4.2. Syntheses .................................. 45
2.4.3. Single crystal X-ray structure determination 47
2.4.4. Electrochemistry ........................... 47
2.5. References and Notes ..........................58
Chapter 3. Formation of a Conductive Porous Network via
Autocatalytic Oxidation of a Redox Active Ligand... 60
3.1. Introduction ................................. 61
3.2. Results and Discussion ....................... 65
3.2.1. Oxidation of TPDAP Ligand .................. 65
3.2.2. The Formation of Paramagnetic Network Using TPDAP (H+1?)............................................. 65
3.2.3. The Formation of Diamagnetic Network Using TPDAP (H+1?). ........................................... 68
3.2.4. Redox Property of Both Network Crystals Cd-1ortho and Cd-1mono ...................................... 70
3.2.5. Electron Conductivity of Cd-1ortho and Cd-1mono Networks .......................................... 72
3.2.6. Autocatalytic Oxidation of H+1? : Mechanistic Study ............................................. 74
3.3. Conclusion ................................... 76
3.4. Experimental Sections ........................ 77
3.5. References and Notes ......................... 93
Chapter 4. Dichotomic Porous Network Formation Using Redox Active Ligand ..... ........................ 96
4.1. Introduction ................................ 97
4.2. Results and Discussion .......................100
4.2.1. Dichotomic Network Formation and X-ray Crystallographic Analysis .........................100
4.2.2. Exploration of Unique Reaction using Redox-Active Multi-Interactive Ligand ......................... 102
4.3.Conclustion .................................. 104
4.4.Experimental Section ..........................105
4.5. References and Notes .........................112
Summary ( in Korean )............................. 114
Acknowledgements ( in Korean ) ....................117
Curriculum Vitae ................................. 119