- 學位論文
TEGylated 氮-雜環碳烯-金(I)和鈀(II)錯合物合成和其發展於雙金屬奈米材料
TEGylated N-heterocyclic Carbene Gold(I) and Palladium(II) Complexes: Syntheses and Their Applications in Bimetallic Nanomaterials
摘要
N-heterocyclic carbenes (NHCs) 是有機金屬化學中被廣泛使用的配體之一, 並運用在不同的應用上, 例如催化劑、金屬藥物和配位聚合物。最近, 已經發現NHCs可以代替金表面的硫, 在平坦的Au表面上形成超穩定的有機膜。從那以後, NHCs已在材料化學中得到廣泛利用。 本文利用有機化學中的酯化反應和醚連接合成了三種具有Triethylene glycol (TEG) 功能的NHC配體。另外, TEG部分可以增強配體的水溶性。有了這些配體, 我們進一步利用它們與金(I)和鈀(II)前驅物反應形成NHC-Au(I) 和NHC-Pd(II) 錯合物。這些金屬錯合物可以藉由核磁共振光譜 (NMR) 和質譜 (Mass) 去鑑定其結構與質量。 另一方面, 我們進行了NHC-Pd(II) 的還原反應以形成奈米粒子。然後, 我們利用賈凡尼置換反應成功合成了由NHC修飾表面的Pd-Au雙金屬奈米方塊的第一個實例。奈米粒子的光學性質可藉由紫外可見光譜(UV-vis) 測定。並通過具有能量色散X射線能譜 (EDX) 的穿透式電子顯微鏡 (TEM) 顯示出奈米顆粒的尺寸, 形態和組成。最後, 利用X射線光電子能譜 (XPS) 鑑定了NHC在表面的鍵結。
並列摘要
N-heterocyclic carbenes (NHCs) is one of the widely used ligands in organometallic chemistry, and have been applied in different applications, such as catalysts, metallodrugs, and coordination polymers. Recently, NHCs have been found that can replace sulfur on gold surface which is resulting in an ultra-stable organic films on flat Au surfaces. Since that, NHCs have been extensively utilized in material chemistry. In this thesis, we synthesized three different NHC ligands with TEG functionalities through esterification and ether connection. In addition, TEG moiety can enhance the ligand water solubility. With these ligands in hand, we further utilized them to react with gold(I) and Pd(II) precursors to form NHC-Au(I) and NHC-Pd(II) complexes The structures of these metal complexes can be determined by nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (Mass). On the other hand, we performed the reduction of NHC-Pd(II) to form the nanoparticles. Then, we successfully synthesized first example of NHC-functionalized Pd-Au bimetallic nanoparticles through the galvanic replacement reaction. The optical properties of nanoparticles were characterized by Ultraviolet–visible spectroscopy (UV-vis). And the size, morphology, and compositions of the nanoparticles were characterized by transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDX). Finally, the NHCs' bonding on the surfaces were identified by X-ray photoelectron spectroscopy (XPS).