| 摘要: | 中文摘要 本論文乃根據實驗室之前所研究的化合物1-H與Zn2+離子錯合後會造成C-N鍵扭轉的特性而設計出一新的螢光離子感應分子，化合物1-DPhA，由其結果進而衍生出一系列化合物( 2-H、2-DPhA、3-DPhA和3-MPhA )的X-光晶體繞射結構及螢光感應機制的探討。 化合物1-DPhA與Zn2+離子錯合後螢光大幅減弱，而非預期的螢光增強現象，藉由化合物2-DPhA的比較，我們認為化合物 1-DPhA對Zn2+離子的螢光是因C-N鍵扭轉後導致PET的機制產生。我們也合成化合物2-H來探討化合物1-H的螢光感應機制是否也存在著PET現象。化合物2-H在乙腈中具有兩個放射峰，我們認為其中的一新放射峰來自於分子內的exciplex螢光。透過化合物3-DPhA和3-MPhA的比較，我們推測化合物2-H中的電子予體是dpa，而電子受體是二苯乙烯。當化合物2-H和Zn2+離子錯合之後，仍然有分子內exciplex的發生，但電子予體的角色由原本的dpa轉變為二苯乙烯，而電子受體的角色由二苯乙烯轉為dpa/Zn2+。此外，當化合物2-H和化合物3-DPhA 在乙腈中照光後，產生出另一新的具較強螢光的化合物。但化合物2-H與Zn2+離子錯合後，其光化學反應顯然有被抑制的現象產生。 Abstract In this thesis, we based on the laboratory that studied compound 1-H with Zn2+ ion complex caused the C-N band twisted, and we design a new fluorescent ion sensing molecular, compound 1-DPhA, and we through the result to design a series of compounds (2-H, 2-DPhA, 3-DPhA, 3-MPhA) to probe into the X-ray crystal structures and the mechanism of the fluorescent sensing. Compound 1-DPhA with Zn2+ complex to cause the largely decrease of the fluorescence, and not expect to increase, and we compare to compound 2-DPhA, and we consider that the fluorescence of the compound 1-DPhA with Zn2+ ion complex to make PET through C-N band twisted. We also synthesize compound 2-H to study the mechanism of the fluorescent sensing of the compound 1-H to have the mechanism of the PET. Compound 2-H have two emission bands in acetonitrile, and we consider a new emission band to come from the intramolecular exciplex. Compare to the compound 3-DPhA and compound 3-MPhA, we propose the electron donor is dpa, and the electron acceptor is stilbene of the compound 2-H. When compound 2-H with Zn2+ complex, still have the intramolecular exciplex. But the role of the electron donor and electron acceptor exchange, and the dpa/Zn2+ play the electron acceptor, and the stilbene play the electron donor. In addition to, compound 2-H and compound 3-DPhA to excitation, and to produce a new strong fluorescence compound. But compound 2-H with Zn2+ complex, and the photochemistry reaction restrained obviously. |
