Phenylethynypyrene Derivatives : Synthesis, Photophysical and Electrochemical Studies
- 주제(키워드) pyrene , electrogenerated chemiluminescence , ECL , radical stability , phenylethynyl , cyclic voltammetry
- 발행기관 고려대학교 대학원
- 지도교수 김종승
- 발행년도 2014
- 학위수여년월 2014. 2
- 학위구분 박사
- 학과 일반대학원 화학과
- 세부전공 유기화학
- 원문페이지 170 p
- 실제URI http://www.dcollection.net/handler/korea/000000049272
- 본문언어 영어
- 제출원본 000045793872
초록/요약
Despite the remarkable developments in the past decade, the design of new high-performance semiconductors and a better understanding of the relationship between molecular structure and device properties are still the major challenges in modern molecular electronics. With this purpose in mind, a great effort has been devoted to the development of pyrene based molecules for electronic applications during Ph. D course. A strategy for enhancement of electrogenerated chemiluminescence and radical stability by peripheral multi-donors on alkynylpyrenes is described (Chapter 1). The five D-pi-A compounds were chosen according to the number and substituent position of peripheral donor moieties. The electrochemical instability of pyrene is improved by increasing the number of substituents of pheripheral DMA ethynyl. A series of tetrakis(ethynyl)pyrenes functionalized with N,N-dimethylaniline and 1-(trifluoromethyl)benzene as a peripheral electron donor and electron acceptor was dealt with in chapter 2. The redox peak reversibility depends on the number of peripheral donor and acceptors appended to tetrakis(ethylnyl)pyrenes as well as on their substitution pattern as revealed by cyclicvoltametric studies. The photophysical and electrochemical properties have been supported by the density functional theory (DFT) based calculation. In Chapter 3, a weakly donating group (n-propyl) has been used as a substituent at the para-position of the phenyl group for a series of phenylethynylpyren derivatives where the number of phenylethynyl peripheral arms appended to the pyrene core is varied. This system markedly improved the concurrently greatly improved electrogenerated chemiluminescence (ECL). Density functional theory (DFT)-based theoretical calculations supported the associated photohysical and electrochemical properties of the series compounds. The 1,3,6,8-tetrasubstituted pyrene in different molecular organizations from chapter 2 was also investigated in chapter 4. In this section, I suggest that intramolecular charge transfer (ICT) could cause to lower the efficiency of the electrogenerated luminescence.
more초록/요약
In this part, I designed and synthesized fluorene-based fluorescence imaging probe for detecting amyloid beta plaques in brain. The fluorescent probes Flu-VA contain a nitrogen donor group that is connected to a fluorene containing water solubilizing groups. The probe showed remarkable promise for the optical imaging of A aggregates. In addition, the stained A plaques exhibit fluorescence change in vivo mice.
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TABLE OF CONTENTS
ABSTRACT…………………………………………………………i
INTRODUCTION.…………………………………………………iii
SUMMARY …………………………………………………………vi
TABLE OF CONTENTS.................................................vii
LIST OF SCHEMES......................................................x
LIST OF FIGURES………………………………………………xii
LIST OF TABLES………………………………………………xviii
PART I
CHAPTER 1. Enhancement of Electrogenerated Chemilumine scence and Radical Stability by Peripheral Multi-Donors on Alkynylpyrene
1.1. Introduction………………………………………………………3
1.2. Results and Discussion…………………………………5
1.3. Conclusions………………………………………………14
1.4. Experiment section ……………………………………15
1.5. References……………………………………………………24
CHAPTER 2. N, N-Dimethylaniline- and 1-(trifluoromethyl)benzene –functionalized Tetrakis(ethynyl)pyrenes: Synthesis, Photophysical, Electrochemical and Computational Studies
2.1. Introduction…………………………………………………27
2.2. Results and Discussion……………………………………30
2.3. Conclusions…………………………………………………46
2.4. Experiment section ………………………………………48
2.5. References……………………………………………………61
CHAPTER 3. Enhanced Electrogenerated Chemiluminescence of Phenylethynylpyrene Derivatives: Use of Weakly Electron Donating Groups as a Substitutent
3.1. Introduction…………………………………………………66
3.2. Results and Discussion…………………………………69
3.3. Conclusions…………………………………………………85
3.4. Experiment section ……………………………………….87
3.5. References……………………………………………………98
CHAPTER 4. N,N-Dimethylamino Functionalzed Tetrakis (phenylethynyl)pyrenes
4.1. Introduction…………………………………………………104
4.2. Results and Discussion…………………………………107
4.3. Conclusions…………………………………………….…113
4.4. Experiment section ………………………………………114
4.5. References…………………………………………………121
PART II
CHAPTER 1. A Fluorescent Probe that Bind and Stain Amyloid Plaques
1.1. Introduction………………………………………………………126
1.2. Results and Discussion………………………………….128
1.3. Conclusions…………………………………………….…134
1.4. Experiment section ………………………………………135
1.5. References…………………………………………………146
