Synthesis of thienyl-substituted BODIPY dyes towards metal ion sensing = 티에닐을 포함하는 BODIPY 물질의 합성과 금속이온 센싱에의 활용에 관한 연구

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In chapter 1, to explore the characteristics of potential fluorescent probes new 5-thienyl dipyrromethene derivatives have been prepared. 5-(2-thienyl)- ($\textbf{1a}$), 5-(3-thienyl)- ($\textbf{1b}$), and 5-(3-(2,5-dibromothienyl))-dipyrromethane ($\textbf{1c}$), were oxidized with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) separately to give the corresponding dipyrrins $\textbf{2a-2c}$. These were subsequently treated with $F_3B \cdot OEt_2$ to afford the respective N,N’-difluoroboryl-5-(thienyl)dipyrrin compounds, 3a-3c. Significant fluorescence signal enhancement is achieved with $\textbf{3a-3c}$ over $\textbf{2a-2c}$. An X-ray diffraction study of $\textbf{3a}$ was performed (orthorhombic, $P2_12_12_1$, a = 10.684(10) $\AA$, b = 15.208(13) $\AA$, c = 7.256(6) $\AA$, V = 1179.0(17) $\AA^3$, Z = 4, R1 = 0.0428, wR2 = 0.0686) and its geometry was studied by way of DFT (Gaussian 03; $B3LYP/6-31G^*$). Theoretical modeling of $\textbf{2a}$ demonstrated that the [N-H‥‥N] interaction is favored by ca. 10 kcal/mol, whereas [N-H‥‥S] bonding is sterically unattainable. In chapter 2, four novel tetra-thienyl-substituted boron-dipyrrin (BODIPY-type) complexes, 3-(R’)-4,4-di(R’)-8-R-4-bora-3a,4a-diaza-s-indacene ($\textbf{4a}$: R = 2-T, R’ = 2-T; $\textbf{4b}$: R = 2-T, R’ = 3-T; $\textbf{5a}$: R = 3-T, R’ = 2-T; $\textbf{5b}$: R = 3-T, R’ = 3-T. T = thienyl) have been prepared and fully characterized to explore patterns of stoichiometric $M^{n+}$ recognition in solution. Compounds $\textbf{4a}$ and $\textbf{4b}$ bear a neutral “scorpionate”_like [SSS] tridentate binding pocket. Extensive NMR, and UV-vis spectroscopic studies were performed on $\textbf{4a-5b; 5a, 4b,}$ and $\textbf{5b}$ were structurally characterized. The $\phi_F$ values for $\textbf{4a-5b}$ all decrease compared to the $BF_2$-containing parent molecules. Upon treatment with metal ion ($Ca^{2+}, Cs^+, Mn^{2+}, Co^{2+}, Cu^{2+}, Ag^+, Zn^{2+}, Cd^{2+}, Hg^{2+}, Pb^{2+}$) perchlorate salts, th...
Advisors
Churchill, David G.researcher처칠, 데이비드 죠지researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2009
Identifier
309363/325007  / 020025885
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2009.2, [ xiv, 359 p. ]

Keywords

BODIPY; thienyl substitution; sensing; metal ion; dye; BODIPY; 티에닐 치환; 센싱; 금속이온; 염료; BODIPY; thienyl substitution; sensing; metal ion; dye; BODIPY; 티에닐 치환; 센싱; 금속이온; 염료

URI
http://hdl.handle.net/10203/31712
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=309363&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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