林英智臺灣大學：化學研究所林鴻志Lin, Hung-ChihHung-ChihLin2007-11-262018-07-102007-11-262018-07-102005http://ntur.lib.ntu.edu.tw//handle/246246/51947一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。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.摘 要 5 Abstract 6 Schemes 7 Introduction 11 1. Metal–Salen Schiff base complexes in catalysis 11 2. NLO Properties of Metal–Salen Schiff base complexes 14 3. Photophysical Properties of Metal–Salen Schiff base complexes 16 4. Electroluminescent (EL) materials 18 5. Motivation 26 6. References 29 Results and Discussion 36 1. Synthesis of 5-Substituted Salicylaldehydes 36 2. Synthesis of Alkynyl-Substituted Zn(II) Schiff Base Complexes 41 3. Synthesis of Other Alkynyl-Substituted Zn(II) Schiff Base Complexes 54 4. Synthesis of Mg(II) Schiff Base Complexes 58 5. Synthesis of Unsymmetrical Zn(II) Schiff Base Complexes 64 6. Synthesis of Other Metal Schiff Base Complexes 67 7. Photophysical Properties The Zinc Series Complexes 68 a. Zn(II) Schiff Base Complexes with Alkynyl-Substitutent 68 b. Zn(II) Schiff Base Complexes with Other Alkynyl-Substitutents 72 c. Mg(II) Schiff Base Complexes 74 d. Unsymmetrical Zn(II) Schiff Base Complexes 75 8. TGA Properties of Schiff base Metal Complexes 78 9. Cyclic Voltammetric Study 79 10. Liquid Crystal Properties of Schiff base Metal Complexes 81 11. References 82 Experimental Section 83 Conclusion 1161686495 bytesapplication/pdfen-US席夫合成鑑定SchiffSynthesisCharacterizationthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51947/1/ntu-94-R92223060-1.pdf