- 學位論文
含新型吡啶或吡嗪配子之金屬錯合物之自組裝、結構與性質研究
Self-assembly, Structures and Properties of Unusual Pyridine- or Pyrazine-Containing Metal Complexes
摘要
本論文探討配位聚合物及超分子之合成策略，使用多種吡啶或吡嗪衍生物配子N,N´-di(pyrazyl)piperazine (4N)、N,N´-di(2´-pyridyl)piperazine (2PyN)、N,N´-di(pyrazinyl) dimethylethylendiamine (4DN)、N,N´-di(2´-pyridinyl)benzene-1,4-diamine (2PN)自組裝合成，產物皆經由核磁共振光譜、紅外線光譜、元素分析、質譜儀等儀器分析鑑定。 本論文分為三個部分討論，第一個部分為吡嗪衍生物與過渡金屬離子反應的研究，第二個部分為吡啶衍生物與金屬離子反應的研究，第三個部分為化合物6對分子辨識的研究。 第一部分使用吡啶衍生物4N與4DN配子，分別與硫氰酸鈷、硫氰酸鎳與硫氰酸鎘等金屬鹽類反應，得到不同的二維配位聚合物，{[(4N)2Co(NCS)2]•(CH2Cl2)•(MeOH)2}n (1)、[(4N)2Ni(NCS)2]n (2)、[(4DN)2Cd(μ-NCS-N,S)2]n (3)。 第二部份改用吡嗪衍生物2PyN與2PN配子，2PyN與分別與硫氰酸鎘、硒氰酸鎘、硫氰酸汞等金屬鹽類反應，此部分2PyN配子皆以雙牙螯合的方式與金屬離子鍵結，得到二維配位聚合物，(2PyN)Cd2(μ-NCS-N,S)4]n (4)、[(2PyN)Cd2(μ-NCSe-N,Se)4]n (5)、[(2PyN)Hg2(μ-NCS)2(SCN)2]n (6)。此部分另外介紹了兩個不同的超分子結構[(2PN)ZnCl2]2 (7)與(PBM)2ZnCl2 (8)，依序在室溫及水熱的條件下使用2PN配子與氯化鋅進行反應，在水熱的條件下2PN配子產生了C-N偶合反應，因此形成了新的配子7-(amino2-pyridyl) pyrido[1,2-a]benzimidazole (PBM)。 化合物8具有放光特性，使用波長為385 nm的光源激發，在507 nm具有放光訊號，此外化合物8具有Hg2+、Cr3+、Fe3+金屬離子辨識的能力，可藉由紫外光-可見光與螢光光譜上的位移辨識得知。化合物8與Hg2+金屬離子之結合常數使用Benesi-Hildebrand方程式計算為2.48 × 104 M-1。
並列摘要
This study describes a synthetic strategy for the preparation of coordination polymers and metallo-supramolecules using pyrazine or pyridine derivatives, such an N,N´-di(pyrazyl)piperazine (4N), N,N´-di(2´-pyridyl)piperazine (2PyN), N,N´-di(pyrazinyl)dimethyl-ethylendiamine (4DN) and N,N´-di(2´-pyridinyl)benzene-1,4-diamine (2PN) using self-assemble technique. The products were characterized by 1HNMR, IR, elemental analysis, mass spectroscopy etc. Their structures were further confirmed by X-ray analysis. The photophysical properties of the products were also investigated. The first part of this thesis describes the preparation of different 2D coordination polymers, {[(4N)2Co(NCS)2]•(CH2Cl2)•(MeOH)2}n (1), [(4N)2Ni(NCS)2]n (2) and [(4DN)2Cd(μ-NCS-N,S)2]n (3), which were assembled from ligand 4N and cobalt thiocyanate, nickel thiocyanate and cadmium thiocyanate, respectively. The second part of the thesis describes the preparation of 2D coordination polymers, such as (2PyN)Cd2(μ-NCS-N,S)4]n (4), [(2PyN)Cd2(μ-NCSe-N,Se)4]n (5), and [(2PyN)Hg2(μ-NCS)2(SCN)2]n (6), employing 2PyN ligand and cadmium thiocyanate, cadmium selenocyanate and mercury thiocyanate, respectively. This part also describes the preparation of two different supramolecules, such an [(2PN)ZnCl2]2 (7) and (PBM)2ZnCl2 (8), assembled from ligand 2PN and zinc chloride at ambient temperature and under hydrothermal conditions respectirely. Under hydrothermal conditions ligand 2PN underwent C-N coupling to afford PBM ligand, where PBM = 7-(amino2-pyridyl) pyrido[1,2-a]benzimidazole. Compound 8 exhibited luminescent properties to afford structureless photoluminescence centered at 507 nm, when excited at 385 nm. In addition, compound 8 can recognize Hg2+、Cr3+、Fe3+ ion, which is discernable by the shift of both UV-vis and luminescent spectra. The binding constant with Hg2+ ion was determined by Benesi-Hildebrand equation and found to be 2.48 × 104 M-1.