林英智臺灣大學：化學研究所廖永宏Liao, Yong-HongYong-HongLiao2007-11-262018-07-102007-11-262018-07-102007http://ntur.lib.ntu.edu.tw//handle/246246/51827一系列的新穎含炔基之柳酫化合物可以經由sonogashira, Ullmann 或者其他偶合反應合成。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之測量，可以得到其光色。它們所發螢光範圍為黃綠光，且具有高度的量子產率. 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。 在嘗試改變柳酫化合物的取代位置,與加入雙氰基取代之雙胺化合物,結果發現在四號位置有胺基取代的柳酫化合物與雙氰基取代之雙胺化合物做縮合反應會得到一席夫鹼化合物,而其具有光敏感性,在溶液態中受到一般燈泡的照射下,會使其結構由原來是順勢的結構,達到順反式皆有的混合物且其比例約為5:1,而且幸運地能夠得到這兩種異構物的單晶結構光譜而使得這項實驗能夠更確定其互換的異構物結構,且我們可以簡單的由“氫原子-核磁共振”的光譜技術去追蹤,且可以利用一系列的光譜技術去了解其有趣的光物理,光化學行為.Various substituted salicylaldehydes have been synthesized via Sonogashira, Ullmann, or other coupling reaction. Some Schiff base metal complexes are obtained by treating the mixture of ligands, metal salt with different diamines. These compounds are characterized by 1H and 13C NMR and mass spectroscopies. The optical properties of these complexes were measured by UV/Vis, and PL (photoluminescent). Some of these complexes (20X) emit orange fluorescence in THF with high quantum efficiencies. Lastly, treatment of diaminomaleonitrile with 2-hydroxy-4-(di-p-tolylamino)benzaldehyde with one drop concentrated sulfuric acid in ethanol afforded compound 301. There are several attractive phenomena in the compound 301. Single crystal data are obtained for the two geometric isomers of 301. The experiments to obtain optical property of 301 were also carried out. It is proposed that conversion of isomers is induced by photo isomerization. Because the luminescence of 301 is strong enough its photophysical properties was carefully investigated. Thus, those experiments on 301 provide details on the mechanism of photo-induced-isomerization.Contents 摘 要 3 Abstract 4 Schemes 5 Introduction 8 Metal-Salen Type Complexes using in Catalysis 8 NLO Properties of Metal–Salen Schiff base complexes 11 (Salen)zinc Complexes using in Supramolecular Assembly 14 Photophysical Properties of Metal-Salen Schiff base Complexes 19 Aggregates 33 Cis-trans isomerization of organic molecules 37 　　　　　　　　　　　　　　　　　　　　References 40 Results and Discussion 53 Synthesis of 5-Substituted Salicylaldehydes 53 Synthesis of 5-Substituted Salicylaldehydes 54 Synthesis of 5-Substituted Zn(II) Schiff Base Complexes 56 Synthesis of Mg(II) Schiff Base Complexes 61 Synthesis of Metal-Free Schiff Base Compounds 65 Photo Induced Isomerization and J-aggregate of 301 69 The Photophysical Properties of Schiff Base Complexes 95 Conclusion 102 Experimental Section 103 References 120 ORTRP drawing and crystal data for the trans form of 301 123 ORTRP drawing and crystal data for the cis form of 301 1283579747 bytesapplication/pdfen-US席夫鹼Schiff BasePhoto Induced isomerizationthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51827/1/ntu-96-R94223063-1.pdf