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년 월 2011 2 석사학위 논문
Application of Explosive Based on Benzo-annulated Triptycene
Germafluorene
조 선 대 학 교 대 학 원
화 학 과
엄 성 용
[UCI]I804:24011-200000241001
Application of Explosive Based on Benzo-annulated Triptycene
Germafluorene
을 기초로 한 Benzo-annulated Triptycene Germafluorene
폭발물 센서로의 응용
년 월 일
2011 2 25
조 선 대 학 교 대 학 원
화 학 과
엄 성 용
Application of Explosive Based on Benzo-annulated Triptycene
Germafluorene
지도교수 손 홍 래
이 논문을 이학석사학위신청 논문으로 제출함.
년 월
2010 10
조 선 대 학 교 대 학 원
화 학 과
엄 성 용
엄성용의 석사학위논문을 인준함
위원장 조선대학교 교수 조 성 동 인 ( ) 위 원 조선대학교 교수 이 범 규 인 ( ) 위 원 조선대학교 교수 손 홍 래 인 ( )
년 월
2010 11
조 선 대 학 교 대 학 원
- I -
TABLE OF CONTENTS
TABLE OF CONTENTS i
LIST OF SYMBOLS AND ABBREVIATIONS iv
LIST OF TABLES vi
LIST OF SCHEMES vii
LIST OF FIGURES vii
Abstract... 2
1. Introduction... 4
2. Experimental Section... 5
2.1. Generals... 7
2.2. All analysis material preparation... 8
2.2.1. Fabrication of DNT Solution 10ppm... 8
2.2.2 Fabrication of Picric Acid Solution 10ppm... 8
2.2.3. Preparation of 2,2-dibromobitriptycene 3... 8
2.3 Synthesis... 8
2.3.1. Preparation of 1,2,4,5-tetrabromobenzene... 9
2.3.2. Preparation of 2,3-dibromotriptycene... 9
2.3.3. Preparation of 2,2-dibromobitriptycene... 10
2.3.4. Preparation of 1,1-dichloro-4,5,8,9-bis(triptycene)germafluorene... 10
2.3.5. Preparation of 1,1-dihydro-4,5,8,9-bis(triptycene)germafluorene... 11
2.3.6. Preparation of 1,1-diphenyl-4,5,8,9-bis(triptycene)germafluorene... 11
2.3.7. Preparation of 1,1-dichlorogermafluorene... 12
3. Results and Discussion... 13
3.1. Research of Sensor and Photoluminescence materials... 13
3.2. Synthesis and Characterization of Triptycene Metallafluorene... 13
3.3. Synthesis and Characterization of Metallafluorene... 19
3.4 The principle of O-LED... 25
3.5 Organic Light-emitting Diodes based on Metallafluorene and Triptycene Metallafluorene... 27
3.5.1 Structure of O-LED... 29
3.5.2 PL and EL spectra... 31
3.5.3 Analysis of I-V-L Characteristics... 33
3.6. Quenching mechanism of Photoluminescence materials... 35
3.7 Detection of Nitro compounds based on Triptycene metallafluorene... 36
3.7.1 Detection of PA based on 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluo -rene... 38
- III -
3.7.2 Detection of TNT based on 1,1-methylhydro-4,5,8,9-bis(triptycene)silafl
-uorene... 39
3.7.3 Detection of DNT based on 1,1-methylhydro-4,5,8,9-bis(triptycene)silafl -uorene... 40
3.7.4 Detection of PA based on 1,1-methylhydro-1-silafluorene... 41
3.7.5 Detection of TNT based on 1,1-methylhydro-1-silafluorene... 42
3.7.6 Detection of DNT based on 1,1-methylhydro-1-silafluorene... 43
4 Conclusion... 44
5 References... 47
LIST OF SYMBOLS AND ABBREVIATIONS
PSi Porous silicon TNT Trinitrotoluene
HF Hydrofluoric Acid
㎛ Micrometer
% Percent
m3 Cubic Meter
M Molarity
FE-SEM Field Emission-Scanning Electron Microscope
d Density
CCD Charge-Coupled Detector A.U. Arbitrary Units
PL Photoluminescence
LED Light Emitting Diode
Pt Platinum
n Refractive Index
Hz Hertz
FWHM Full-Width at Half-Maximum
nm Nanometer
THF Tetrahydrofuran
FT-IR Fourier Transform Infrared Spectroscopy
- V - UV-Vis Ultraviolet-Visible
mL Milliliter
Ω Ohm
λ lambda
mmol Millimole
Pt Platinum
V Volume
㎍ Microgram
π Pi
δ Delta
Mw Molecular Weight
σ Sigma
λem Emission Wavelength
mg Milligram
mA Milliampere
λmax Maximum Wavelength A.U. Arbitrary Units
LUMO Lowest Unoccupied Molecular Orbital HOMO Lowest Unoccupied Molecular Orbital
ppm Part per Million ppb Part per Billion R.T. Room Temperature DNT Dinitrotoluene
EL Electroluminescene
FWHM Full-Width at Half-Maximum LED Light Emitting Diode
LIST OF TABLES
Table 1 Total Comparison of stern-Volmer Constants K(M-1)
- VII -
LIST OF SCHEMES
Scheme 1 Synthesis of Compound 1.
Scheme 2 Synthesis of Compound 2.
Scheme 3 Synthesis of Compound 3.
Scheme 4 Synthesis of Compound 4, 5, 6.
Scheme 5 Synthesis of Compound 7.
Scheme 6 Synthesis of Compound 8, 9, 10, 11
LIST OF FIGURES
Figure 1 Thermal Ellipsoid Drawing of Chain Structure of Compound 9 Figure 2 UV-Vis absorption spectra of Compound 8
Figure 3 UV-Vis absorption spectra of Compound 9
Figure 4 UV-Vis absorption and Fluorescence spectra Compound 10 Figure 5 UV-Vis absorption and Fluorescence spectra Compound 11 Figure 6 X-ray crystal structure of Compound 10
Figure 7 O-LED 셀의 구조 단면도 및 단분자 O-LED 구조
Figure 8 Molecular orbital amplitude plots of the HOMO(a) and LUMO(b) of the 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene molecule and, HOMO(c) and LUMO(d) of the 1,1-dimethyl-4,5,8,9-bis(triptycene)sila -fluorene molecule
Figure 9 Molecular orbital amplitude plots of the HOMO(a) and LUMO(b) of the 1,1-methylhydro-1-silafluorene molecule and, HOMO(c) and LUMO(d) of the 1,1-dimethyl-1-silafluorene molecule
Figure 10 Structure of O-LED Shell Figure 11 PL and EL spectra of
1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (A) and 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (B) materials.
- IX -
Figure 12 PL and EL spectra of 1,1-methylhydro-1-silafluorene (A) and 1,1-methylhydro-1-silafluorene (B) materials.
Figure 13 Applied voltage versus luminance and current density plot of
1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (A) and 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (B) materials.
Figure 14 PL and EL spectra of 1,1-methylhydro-1-silafluorene (A) and 1,1-methylhydro-1-silafluorene (B) materials.
Figure 15 Detection MEchanism for Explosives Figure 16 Properties of Iptycene
Figure 17 Detection of Nitro compounds based on Triptycene metallafluorene
Figure 18 Quenching PL Spectra Stern-Volmer plot of
1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene for PA
Figure 19 Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-4,5,8,9-bi -s(triptycene)silafluorene for TNT
Figure 20 Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-4,5,8,9-bi -s(triptycene)silafluorene for DNT
Figure 21 Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-1-silafluo -rene for PA
Figure 22 Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-1-silafluo -rene for TNT
Figure 23 Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-1-silafluo -rene for DNT
Application of
Explosive Based on Benzo-annulated
Triptycene
Germafluorene
- 2 -
π
- 4 - 1. Introduction
π
π σ π
σ σ π
π
σ
- 6 -
σ π
σ π
σ σ
π
2.1. Generals
δ
- 8 - 2.2. All analysis material preparation
2.2.1. Fabrication of DNT Solution 10 ppm
2.2.2. Fabrication of Picric Acid Solution 10 ppm
2.2.3. Fabrication of TNT Solution 10 ppm
2.3.1. Preparation of 1,2,4,5-tetrabromobenzene
δ δ
2.3.2. Preparation of 2,3-dibromotriptycene
- 10 -
δ
δ
2.3.3. Preparation of 2,2-dibromobitriptycene
δ
δ
2.3.4. Preparation of 1,1-dichloro-4,5,8,9-bis(triptycene)germafluorene
δ
2.3.5. Preparation of 1,1-dihydro-4,5,8,9-bis(triptycene)germafluorene
δ
δ
2.3.6. Preparation of 1,1-diphenyl-4,5,8,9-bis(triptycene)germafluorene
- 12 -
δ
δ
2.3.7. Preparation of 1,1-dichlorogermafluorene
δ δ
3.1. Research of Sensor and Photoluminescence materials π π
σ
σ π
σ π
3.2. Synthesis of Characterization of Triptycene Metallafluorene
- 14 - : 1,2,4,5-tetrabromobenzene
Br
Br
+ FeBr 3
CCl 4
Br 2 Br Br
Br Br
Scheme 1. Synthesis of Compound 1.
Br Br
Br Br
+ Toluene
n-BuLi
Br Br Scheme 2. Synthesis of Compound 2.
Br Br
Toluene 1/2 n-BuLi
Br Br Scheme 3. Synthesis of Compound 3.
- 16 -
Ge Cl Cl
Ge
H H Ge
Ph Ph
c d
Br Br Li Li
a
b
4
5 6
Scheme 4. Synthesis of Compound 4,5,6.
- 18 -
- 20 - Br Br
a
Li Li
Si Si Si Ge
Me H Me Me Cl Cl Cl Cl
8 9 10 11
b c d e
Scheme 6. Synthesis of Compound 8, 9, 10, 11.
200 250 300 350 400 450 500 550 600 650 700 0.0
0.2 0.4 0.6 0.8 1.0
Normalized Intensity (arb. unit)
Wavelength (nm)
: UV-vis abs.
: PL spectrum
λ
λ
- 22 -
200 250 300 350 400 450 500 550 600 650 700 750 800 0.0
0.2 0.4 0.6 0.8 1.0
Normalized Intensity (arb. unit)
Wavelength (nm)
: UV-vis abs.
: PL spectrum
λ
- 24 -
셀의 구조 단면도 및 단분자 구조
Figure 7. O-LED O-LED
- 26 - π
Metallafluorene
Figure 8. Molecular orbital amplitude plots of the HOMO (a) and LUMO(b) of the 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene molecule and, HOMO
(c) and LUMO(d) of the 1,1-dimethyl-4,5,8,9-bis(triptycene)silafluorene molecule
- 28 - π
Figure 9. Molecular orbital amplitude plots of the HOMO (a) and LUMO(b) of the 1,1-methylhydro-1-silafluorene molecule and, HOMO (c) and LUMO(d) of
the 1,1-dimethyl-1-silafluorene molecule
3.5.1. Structure of O-LED
Figure 10. Structure of O-LED Shell
- 30 -
Figure 11. PL and EL spectra of
1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (A) and 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (B) materials.
- 32 -
Figure 12. PL and EL spectra of 1,1-methylhydro-1-silafluorene (A) and 1,1-methylhydro-1-silafluorene (B) materials.
Figure 13. Applied voltage versus luminance and current density plot of 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (A) and
1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene (B) materials.
- 34 -
Figure 14. Applied voltage versus luminance and current density plot of 1,1-methylhydro-1-silafluorene (A)
and 1,1-methylhydro-1-silafluorene (B) materials.
Figure 15. Detection Mechanism for Explosives
- 36 -
3.7. Detection of Nitro compounds based on Triptycene metallafluorene
Figure 16. Properties of Iptycene
π π
- 38 -
3.7.1. Detection of PA based on 1,1-methylhydro-4,5,8,9-bis(triptycene)silaf -luorene
Fig 18. Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene for PA
-fluorene
Fig 19. Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene for TNT
- 40 -
3.7.3. Detection of DNT based on1,1-methylhydro-4,5,8,9-bis(triptycene)sila -fluorene
Fig 20. Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-4,5,8,9-bis(triptycene)silafluorene for DNT
3.7.4. Detection of PA based on1,1-methylhydro-1-silafluorene
1,1-methylhydro-1-silafluorene for PA
- 42 -
3.7.5. Detection of TNT based on1,1-methylhydro-1-silafluorene
Fig 22. Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-1-silafluorene for TNT
Fig 23. Quenching PL Spectra Stern-Volmer plot of 1,1-methylhydro-1-silafluorene for DNT
- 44 -
- 46 -
Table 1. Total Comparison of Stern-Volmer Constants K(M-1)
5. References
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저작물 이용 허락서
학과 화학과 학
번 20097029 과
정 석사 박사ㆍ 성명 한글 엄 성 용 한문 嚴 誠 鎔 영문 Um Sung Yong 주소 광주 광역시 서구 화정동 대주피오레 201동 1405호
연락처 e-mail : [email protected]
논문제목
한글 Benzo-annulated Tripycene Germafluorene을 기초로한 폭발물 센서로의 응용
영문 Application of Explosive Based on Benzo-annulated Triptycene Germafluorene
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1. DB ,
기억장치에의 저장 전송 등을 허락함,
위의 목적을 위하여 필요한 범위 내에서의 편집과 형식상의 변경을 허락함 다만 저
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배포 전송된 저작물의 영리적 목적을 위한 복제 저장 전송 등은 금지함
3. ㆍ , ,
4. 저작물에 대한 이용기간은 년으로 하고 기간종료 개월 이내에 별도의 의사 표시가5 , 3 없을 경우에는 저작물의 이용기간을 계속 연장함
해당 저작물의 저작권을 타인에게 양도하거나 출판을 허락을 하였을 경우에는 개월
5. 1
이내에 대학에 이를 통보함
조선대학교는 저작물 이용의 허락 이후 해당 저작물로 인하여 발생하는 타인에 의한 6.
권리 침해에 대하여 일체의 법적 책임을 지지 않음
소속 대학의 협정기관에 저작물의 제공 및 인터넷 등 정보통신망을 이용한 저작물의 7.
전송 출력을 허락함ㆍ
동의여부 : 동의( v ) 반대( ) 년 월 2011 2
저작자 : 엄 성 용 (인)
