3-Hydroxy Flavone Derivatives for Developing a H+/F- Dual Analyte Fluorescent Probe and Probing Intramolecular hydrogen Bonds
Date Issued
2016
Date
2016
Author(s)
Hsu, Yu-Kun
Abstract
The thesis is focused on 3-hydroxyflavone derivatives serving as a H+/F- dual analyte fluorescent probe and intramolecular hydrogen bond probe, via its special 3-hydroxyl properties, which serves as the proton donor in the ESIPT process and is more acidic than normal alcohols. In the first part of the thesis, two 3-sily ether derivatives, namely 3-TBSFE and 3-TBSFA, were designed and synthesized. Upon addition of H+/F- the silyl ether is removed, while only in the present of H+ is the second step lactone product formed. The characteristic photo physical properties of each compound realized the goal to tell apart the concentration of H+/F- using one probe. With the help of HPLC, ESI-MS, and NMR, the working mechanism of 3-TBSFA was confirmed. In the second part of the thesis a serial 2’ phenol derivatives were designed and synthesized. The 2’ phenol may form 6-membered intramolecular H-bond and decrease the e- donating ability of the O atom in the ring, thus cause blue-shift in absorption spectrum. While when the 7-membered intramolecular H-bond formed, the acidity of 3-hydroxy increase which attribute to the long wavelength anion signal in absorption spectrum. Thought careful slovatochromism and acidity discussion of 2’ phenol derivatives, we conclude that the long wavelength absorption was related to the 7-membered intramolecular H-bond, while the blue-shift of absorption spectrum was due to steric-caused coplanarity decreasing. Via X-ray diffraction structure the formation of 7-membered intramolecular H-bond was confirmed. The free energy difference between 7- and 8-membered intramolecular ionic H-bond was also deduced from correlation of solvent H acceptor ability and absorbance.
Subjects
3-hydroxy flavone
dual analyte probe
intramolecular hydrogen bond
Type
thesis
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