Synthesis, Characterization, Photophysical Properties, and Small Molecule Sensing of Bis(salicyaldiminato)metal Copmlexes

[[abstract]]在本論文中我們合成了一系列雙亞胺酚基金屬錯合物 M(saldppy) (M = Zn, Mg, Pd)、M(saltBudppy) (M = Zn, Mg, Pd)、Zn(saltBuphpy) 及Zn(saltBudmpy)，其中，鋅金屬錯合物具有豐富的螢光性質。我們藉由改變雙亞胺酚基金屬錯合物之取代基和橋鍵後發現會有不同的螢光特性。利用螢光光譜儀，分別檢測四種鋅金屬錯合物Zn(saldppy)、Zn(saltBudppy)、Zn(saltBuphpy) 和Zn(saltBudmpy) 對硝基化合物的螢光感測能力。實驗結果顯示鋅金屬錯合物Zn(saldppy)、Zn(saltBudppy) 和Zn(saltBuphpy) 表現明顯地螢光焠熄現象。近一步檢測鋅金屬錯合物對銀鹽及陰離子的螢光感測性能。由螢光感測實驗可以發現，鋅金屬錯合物Zn(saldppy) 和Zn(saltBuphpy) 對含有醋酸根離子之化合物會產生螢光增強的現象；鋅金屬錯合物Zn(saltBudppy) 並沒有此現象，推測可能與醋酸根離子的配位有關。 此外，鋅金屬錯合物Zn(saldppy) 和Zn(saltBudppy) 也進行硝基化合物小當量滴定實驗。可以觀察到其對微量的硝基化合物具有不錯的偵測靈敏度及良好的螢光感測能力。[[abstract]]Four salen-type ligands, namely H2saldppy, H2saltBudppy, H2saltBuphpy, and H2saltBudmpy, and a series of bis(salicyaldiminato)metal complexes, M(saldppy) (M = Zn, Mg, Pd), M(saltBudppy) (M = Zn, Mg, Pd), Zn(saltBuphpy), and Zn(saltBudmpy), have been designed and synthesized. These compounds, especially Zn-complexes, have shown rich photophysical properties, making them being as candidates for small molecule sensing. In addition, by changing the functional group and diamine bridge of salen-type ligands would make impact influences on not only their fluorescent properties but also their sensing behaviors. Experimental results have shown that bis(salicyaldiminato)zinc complexes present the sensing ability towards nitro-compounds in the order of Zn(saltBudppy) > Zn(saldppy) > Zn(saltBuphpy) > Zn(saltBudmpy). This clear indicates that the functional group and diamine bridge of the salen-type ligand with strong electron-donating feature would increase the abilities of bis(salicyaldiminato)zinc complexes to sensing nitro-compounds. Further, bis(salicyaldiminato)zinc complexes Zn(saldppy), Zn(saltBudppy), and Zn(saltBuphpy) all exhibited significant fluorescence quenching upon the addition of silver salts, with exception of AgOAc in the case of Zn(saldppy) and Zn(saltBuphpy), which resulted fluorescent enhancement. Anion sensing examination showed that anion with strongly coordinating ability, such as OAc- and F- would cause fluorescence enhancement, while other anions cause no significant fluorescence quenching. As a result, fluorescence quenching observed in the silver salts can be reasonably attributed to the coordination of Ag-py. The change in, diamine bridge plays a role in influencing fluorescence of the Zn-complexes when recongnizing silver salts and/or anions.[[note]]碩