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  • 學位論文

鋅、鎂系統中含多烷鏈之炔基席夫鹼金屬錯合物: 合成,鑑定及光物理性質

Alkynylated Schiff Base Metal Complexes Containing Multiple-Alkyl Chains in Zn and Mg System: Synthesis, Characterization, and Photophysical Properties

指導教授 : 林英智

摘要


一系列的新穎含炔基之柳酫化合物可以經由sonogashira coupling偶合反應合成。再將柳酫化合物與醋酸鋅、雙胺化合物作用,即可得到一系列的鋅席夫鹼金屬錯合物。上述錯合物皆經由1H-NMR、13C-NMR及Mass的鑑定,再利用UV/vis、fluorescence、TGA之測量,可以得到其光色和熱穩定性。它們所發螢光範圍為橘光,且可藉由改變柳酫化合物的取代與雙胺化合物得到不同光色之金屬錯合物,此錯合物均具有不錯的量子效率。此類化合物具有極高的熱穩定性Td > 400 oC。 單核二價鎂席夫鹼金屬錯合物也是利用類似合成鋅席夫鹼金屬錯合物系統的方法製備,鎂錯合物所發螢光範圍為黃光,且大大提升了量子效率。此外,不對稱的鋅席夫鹼金屬錯合物也可以被合成出來,光物理性質與對稱的錯合物有些許的不同。

關鍵字

席夫 合成 鑑定

並列摘要


A new series of substituted-arylethynyl ligands have been synthesized via Sonogashira coupling reaction. A series of Schiff base metal complexes were obtained by a method that the ligands are first treated with metal salt followed by addition of the different diamines. These compounds were characterized by 1H and 13C NMR and mass spectroscopies. The optical properties and the thermal properties of these complexes were measured by UV/vis, PL (photoluminescent) and TGA spectroscopic studies. All of these complexes emit orange fluorescence in THF with good quantum efficiencies. All of these complexes exhibited highly thermal stability in nitrogen (Td > 400℃). The Mg(II) Schiff base derivatives were synthesized by the same methodology used for the preparation of Zn(II) analogues. These Mg-complexes emit yellow fluorescence in THF and the quantum yield was dramatically enhanced relative to Zn-complexes. Additionally, the unsymmetrical Zn(II) Schiff base complexes also can be prepared. The optical properties of unsymmetrical complexes are some different from that of symmetrical complexes.

並列關鍵字

Schiff Synthesis Characterization

參考文獻


第一部分
1. Schiff, H. Ann. Suppl. 1864, 3, 343.
2. (a) Jacobsen, E. N. in Catalytic Asymmetric Synthesis, Ed. I. Ojima, VCH, New York, 1993, p. 159. (b) Canali, L.; Sherrington, D. C. Chem. Soc. Rev. 1999, 28, 85-93.
3. Shrivastava, H. Y.; Kanthimathi M.; Nair, B. U. Biochem. Biophys.Res. Commun. 1999, 265, 311
4. (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; Chapter 4.1. (b) Jacobsen, E. N. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; Chapter 4.2.

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