腈蒽類共軛推-拉電子基化合物結構與性質之研究

Abstract

本篇論文利用Suzuki coupling及Sonogashira coupling合成出兩系列含有π電子共軛系統的化合物，分別為9-phenyl-10-anthronitriles ( PAN ) series 及9-phenylethynyl-10-anthronitriles ( PEAN ) series。並研究其光物理性質、電化學特性及電致化學發光性質 ( Electrogenerated ChemiLuminescence; ECL )。並利用理論計算( Density Functional Theory; DFT-B3LYP/6-31G* ) 的結果與所觀察到的電子性質相互比較。 這次的研究，我們藉由UV-Vis光譜儀及螢光光譜儀，做了UV-Vis吸收及螢光強度的測試並計算其量子產率，來探討這兩個系列化合物的光物理性質。接下來，用循環伏安計確認化合物的氧化還原電位，再利用ECL裝置使其在短時間內切換作用的氧化還原電位，產生足量且在此極短的時間內穩定的陰、陽離子自由基，進行反應。並於同一裝置內，以螢光儀偵測其化學發光。 根據實驗結果，得到的產物中PAN、AnAN、DMA-PAN及DMA-PEAN經由S-route放光，其餘的DTP-PAN、An2N-PAN、PEAN、AnEAN及DTP-PEAN為E-route放光，而An2N-PEAN沒有ECL放光。

Two series of π-conjugated bipolar compounds namely 9-phenyl-10-anthronitriles (PANs) and 9-phenylethynyl-10-anthronitriles (PEANs) having inherent redox centers have been synthesized and their UV-Vis absorption, fluorescence emission and electrochemical behavior are studied. Electrochemiluminescence of these molecules bearing weak, strong and spin polarized donors is also studied. The observed electronic properties are explained by means of Density Functional Theory (DFT- B3LYP/6-31G*) calculations. The structure-property relationships of all the molecules are discussed. In this study, we checked absorption and emission spectra in various solvents by the UV-Vis and fluorescence spectrometer respectively. Quantum yield (Φ) and other photophysical properties were also studied by the data. We used Cyclic Voltammetry ( CV ) to determine the electrochemical activities of all compounds. And then we checked ECL properties by triple-potential step.(fluorescence spectrometer as detector.) In conclusion, PAN、AnAN、DMA-PAN and DMA-PEAN with energy sufficient to populate singlet state, thus they followed S-route emission. DTP-PAN、An2N-PAN、PEAN、AnEAN and DTP-PEAN show ECL emission red-shifted and energy deficient, thus they followed E-route emission. An2N-PEAN is no ECL emission.