林英智臺灣大學：化學研究所郭凱倫Kuo, Kai-LunKai-LunKuo2007-11-262018-07-102007-11-262018-07-102006http://ntur.lib.ntu.edu.tw//handle/246246/51961一系列新穎多核不對稱含炔基之席夫鹼金屬化合物成功的被合成。在這篇論文裡，利用了新穎的合成方法，藉由簡易的合成與純化歨驟並利用一歨合成法都能成功的得到產物，產率也相當不錯。經由實驗証明，合成新穎多核不對稱含炔基之席夫鹼金屬化合物必須先製備三芽基含胺之席夫鹼，再藉由滴定三芽基含胺之席夫鹼於不同的雙柳醛化合物及金屬鹽類中。經由此合成歨驟，多核及不對稱含炔基之席夫鹼金屬化合物中每個金屬中心都具有不對稱的化學環境。上述的錯合物皆經由1H -NMR、13C -NMR及Ｍass的鑑定，再利用UV/Vis、PL、TGA之測量，可以得到其光色和熱穩定性。所有的化合物在溶液中皆能放出螢光且具有不錯的量子產率。另外，在柳醛基上加入炔基與推電子基亦可提升其螢光強度及量子產率。所有的多核與不對稱含炔基之席夫鹼金屬化合物都具有極高的熱穩定性，裂解溫度都在400˚C以上。A series of novel multinuclear and unsymmetrical alkynylated Schiff base metal complexes have been successfully synthesized. In our study, the new synthetic strategy is utilized due to facile handling of the reactants, simple purification of the products, and use of one-pot reaction process in the preparation. It is demonstrated that multinuclear alkynylated Schiff base metal complexes could be prepared via firstly synthesizing the terdentate amino-Schiff base. These bases then were added slowly into a mixture of metal salts and different bis-salicylaldehyde compounds. By this way, these multinuclear and unsymmetrical Schiff base complexes with each metal center at asymmetric coordinating environment can be obtained. These compounds are characterized by 1H and 13C NMR and mass spectroscopies. The optical properties and the thermal properties of these complexes were investigated by UV/Vis, PL (photoluminescence) and TGA studies. All of these complexes emit fluorescence in solution with good quantum efficiencies. Additionally, incorporation of the ethynyl group connected with electron-donating groups into the salicylidene moiety also enhances the fluorescence intensity and quantum yield. Furthermore, all these complexes exhibited highly thermal stability under nitrogen with decomposition temperature above 400˚C.Contents Abstract VII Overall Shemes VIII Introduction 1 1. Metal-Salen Type Complexes using in Catalysis 1 2. (Salen)zinc Complexes using in Supramolecular Assembly 4 3. NLO Properties of Transition Metal Complexes 6 4. Photophysical Properties of Metal-Salen Schiff base Complexes 10 5. Electroluminescent (EL) Devices and Phosphorescent Materials 13 6. Motivation 19 References of Introduction 20 Results and Discussion 28 1. Synthesis of Terdentate Amino-Schiff Base Ligands 28 2. Synthesis of Bis-salicylaldehyde 32 3. Synthesis of Novel Dimeric Alkynylated Schiff Base Metal Complexes 37 4. Synthesis of Other Dimeric Alkynylated Schiff Base Metal Complexes 46 5. Synthesis of 5-Substituted Salicylaldehydes 51 6. Synthesis of No Alkynyl-Substituted Zn(II) Schiff Base Complexes 54 7. Synthesis of Bidentate Alkynyl-Substituted Zn(II) Schiff Base Complexes 60 8. Synthesis of Asymmetric Zn(II) Schiff Base Complexes 62 9. Synthesis of Novel Trinuclear Alkynylated Schiff Base Metal Complexes 75 10. Photophysical Properties of the Schiff Base Metal Series Complexes 81 a. Dimeric Alkynylated Schiff Base Metal Complexes 81 b. Other Dimeric Alkynylated Schiff Base Metal Complexes 93 c. No Alkynyl-Substituted Schiff Base Metal Complexes 98 d. Bidentate Alkynyl-Substituted Zn(II) Schiff Base Complexes 103 e. Asymmetric Schiff Base Metal Complexes 104 f. Trinuclear Alkynylated Schiff Base Metal Complexes 113 11. TGA Properties of Schiff Base Metal Series Complexes 115 References of Results and Discussion 116 Conclusion 119 Experimental Section 1223332403 bytesapplication/pdfen-US席夫鹼金屬多核不對稱光物理性質Schiff BaseMultinuclearUnsymmetricalPhotophysical PropertiesElectroluminescencePhotoluminescencethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51961/1/ntu-95-R93223040-1.pdf