Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16593
標題: 金屬乙基雙磷酸鹽超分子材料於可調控開關之應用
Switchable Supramolecular Materials Based on Metal-Ethylenediphosphonate
作者: 傅淑娟
Fu, Shu-Juan
關鍵字: supramolecule;超分子;ethylenediphosphonate;switchable;Co;Cu;乙基雙磷酸鹽;可切換;銅金屬;鈷金屬
出版社: 化學系所
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摘要: 
在超分子材料領域中,設計出具有特殊官能性的一維鏈狀、二維層狀及三維孔洞的金屬有機磷酸鹽分子,是一門非常重要的研究,可應用於離子交換、吸附、感測器、嵌入、磁性及仿生系統上。至今,只有少數的例子呈現金屬有機磷酸鹽的可調節開關特性,因此,研究及設計金屬有機磷酸鹽在外界的刺激下展現出可逆的雙穩定狀態(切換)的特性將會是一大挑戰。
在我們的實驗中,利用水熱和溶劑熱合成法,成功的合成出一系列以不同的過渡金屬為題材的一維、二維和三維超分子複合材料,分別是以銅金屬離子和鈷金屬離結合1,10-phenanthroline (phen) 及ethylenediphosphonic acid所建構的超分子金屬乙基雙磷酸鹽複合材料,並藉由單晶X-ray繞射儀鑑定出分別為{[Cu2(C12H8N2)2(HO3P-C2H4-PO3H)2(OH2)2]在我們的實驗中,利用水熱和溶劑熱合成法,成功的合成出一系列以不同的過渡金屬為題材的一維、二維和三維超分子複合材料,分別是以銅金屬離子和鈷金屬離結合1,10-phenanthroline (phen) 及ethylenediphosphonic acid所建構的超分子金屬乙基雙磷酸鹽複合材料,並藉由單晶X-ray繞射儀鑑定出分別為{[Cu2(C12H8N2)2(HO3P-C2H4-PO3H)2(OH2)2].2H2O (1DOP-Cu), [Co(C12H8N2)(HO3P -C2H4-PO3H)(OH2)2](1),[Co(C12H8N2)(HO3P-C2H4-PO3H)](2)和Cs[Co(C2H5P2O6)] (3)}。在此篇論文中分做兩大主題,第一主題,運用配位鍵超分子自組裝概念結合過渡金屬具氧化還原能力導入人造肌肉致動器的研究熱潮,而創造出不同風格的一維次超分子銅磷酸人造肌肉致動元件(1DOP-Cu),形成前所未見不同面貌的超分子模型來詮釋分子馬達運作的新機制探索。這其中主要的著眼點在於創造嶄新的超分子纖維(filament)並且在外加電壓的條件下進行離子嵌入及去嵌入可逆現象,使得1DOP-Cu呈現伸張和收縮的可逆過程,而這些材質將是人造肌肉致動器的研究新題材題;除此之外,1DOP-Cu在結構上具備穩定的骨架,當外加電壓時,電流呈現cyclability 之現象,這可說明此分子具有離子及電子導電特性,可當作另一項以一維次超分子為特色之鋰電池陰極材料電極。

另一主題,設計以共價鍵及非共價鍵型態之柔軟性超分子化合物為核心,並利用鈷金屬離子其具多重的配位環境而呈現出典型的變色及多重磁變化等特質在外界的刺激下,因而設計出化合物1 具有已鈷金屬的一個八面體中心, 為無限延伸的鏈狀結構,且其具柔軟性結構,固藉由配位水的調節可調整將化合物1轉變為五配為金屬鈷(雙三角椎型)為中心的化合物2, 並以晶體到晶體轉換的形式(crystal-to-crystal fansion)來進行在溶劑熱的方法下。所以此堆疊為3維的超分子化合物1呈現出可逆的配位水吸附和脫附的行為,並伴隨著顏色的改變。

因此我們相信這類的配位聚何物可以應用於感測器、致動器以及氣相分離器等。

Self-assembling coordination polymers based on metal-organodiphosphonate have been intensively studied, because of their potential applications in caltalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry, magnetism and material chemistry. More effects have been devoted into the designing and synthesis of 1-D, 2-D, and 3-D supramolecular architectures, which were constructed from metal ion as connectors, organodiphosphonate as bridge ligand, and introduction of pi-functional aromatic ligand. To date, only a few examples have been explored to switchable properties of metal-organodiphosphonate system. Studies on the reversible bistable state (switch) of metal-organodiphosphonate supramolecular materials in response on external stimuli have been a great challenge.
Herein, we had synthesized a series of 1-D, 2-D, and 3-D supramolecular architectures based on metal-ethylenediphosphonate {[Cu2(C12H8N2)2 (HO3P-C2H4-PO3H)2(OH2)2].2H2O (1DOP-Cu), and [Co(C12H8N2)(HO3P-C2H4-PO3H) (OH2)2] (1), [Co(C12H8N2)(HO3P-C2H4-PO3H)] (2) and Cs[Co(C2H5P2O6)] (3)} with pi-functional ligands by introducting 1-10-phenanthroline (phen) as aromatic units under hydrothermal/ solvothermal techniques. This thesis is divided into two parts. First, a mechanically robust corrugated sheet, 1DOP-Cu, is composed of mats of individual chain-bundles [-CuII-O3P-(CH2)2-PO3-CuII-], joined by pi - pi interactive forces from phen. By applying voltage, lithium ionic insertion/de-insertion of 1DOP-Cu can lead to layered contraction/extension during oxidation/reduction reaction of 1DOP-Cu. This work could not only approach the goal of new ionic-switched electrochemical artificial muscle but also lead to the development of all-solid-state rechargeable lithium batteries. Therefore, one dimension supramolecular copper containing organophosphonate system is the first example which has been developed the field of moving molecular machines. The electrochemical actuator process presented herein provides an approach for studying the actuating mechanism of natural molecular motor, this being one of the key goals for the progress of molecular motor technology.
Second, structure of 1 including of octahedral cobalt(II) center, [-Co-HO3P-(CH2)2-PO3H-Co-] , reveals infinite zigzag chains, in which the phen and water ligands are bound to the metal centers. A flexible corrugated sheet is composed of individual chain-bundles joined by pi - pi interactive forces. Aquo-ligands in 1 can be reversibly coordinated/de-inserted to the cobalt center accompanied by interchangeable coordination geometries from octahedra [coordination number (CN) = 6)] in 1 to trigonal-bipyramid (CN = 5) in 2 at the cobal(II) center, which was progressed in a crystal-to-crystal fashion under solvothermal method. The 3-D supramolecular network of 1 displayed a reversible dehydration/ rehydration behavior accompanying with chromatic property.
Therefore, we can believe that coordination polymers based on metal-ethylenediphosphonate will find applications for gas separations, sensor, and actuator.
URI: http://hdl.handle.net/11455/16593
其他識別: U0005-1101200815015700
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