含鋰、鈣之配位聚合物的水熱合成、結構解析 與性質研究

Hydrothermal Synthesis, Crystal Structures and Properties of Lithium, Calcium Coordination Polymers.

梁珀菁(Po-Ching Liang)

指導教授 ： 林嘉和

中原大學/理學院/化學研究所/碩士(2009年)

https://doi.org/10.6840/cycu200900757

摘要

在此論文中，我們成功了利用中溫水熱合成法成出十三個不同的新穎有機金屬骨架。本論文中依照不同的中心金屬(鋰、鈣)來區分，則將分成兩部分進行探討，本文中所合成出的結構如下：
(H2N(CH3)2)2[Li2(BTEC)] (1)
(H2N(CH3)2)2[Li3(BTEC)(HCO2)]•H2O (2)
[Li8(BTEC)(HCO2)4] (3)
[Li4(BTEC)(H2O)6] (4)
[Li3(BTC)(H2O)] (5)
[Li3(BTC)(H2O)6] (6)
[Li(H2BTC)(H2O)] (7)
{[Ca3(BTC)2(DMF)2(H2O)2]•3H2O} (8)
[Ca(BDC)(DMF)(H2O)] (9)
[Ca(IDC)(H2O)] (10)
[Ca2(DOBDC)2(DMF)2] (11)
[Ca(DOBDC)2(H2O)2] (12)
[Ca(DOBDC)2(H2O)2] (13)
第一部分主要是利用金屬鋰與有機配位基H4BTEC合成出化合物1-3其利用溶劑含量比例的不同；化合物4則是將化合物1做陽離子交換的反應所得到的結構，經由單晶鍵定結果顯示皆為三維的立體結構。另一個則是利用金屬鋰與H3BTC所合成出的化合物5-7分別三維骨架、二維層狀和一維鏈狀等不同有機金屬骨架的結構，化合物6是將化合物5加熱後經由吸水後所產生的新結構；化合物7雖為一維無限延伸的的鏈狀結構，但經由氫鍵的作用力而轉變成三維骨架的結構。
第二部分是利用金屬鈣與不同的有機配位基形成六種不同的結構為化合物8-13，鑑定結果顯示此六個骨架皆屬於三維的結構，其中化合物8利用有機模板、配位基和溶劑橋接形成一個有條理左螺旋方式無限延伸。
以上化合物1-13除了利用單晶X光繞射儀鑑定其結構外，也利用其他的儀器，例如：粉末X光繞射儀、元素分析、熱重分析、紫外-可見光吸收光譜、螢光放光光譜、紅外光共振光譜和氮氣的吸脫附來探討其它的特性。

關鍵字

有機金屬骨架 ； 水熱合成法

並列摘要

Thirteen new coordination polymers have been synthesized by hydrothermal reactions and structurally characterized. Two different lithium and calcium were used as starting materials and will discussed in two section. Compounds 1 to 13 structure are as follows :
(H2N(CH3)2)2[Li2(BTEC)] (1)
(H2N(CH3)2)2[Li3(BTEC)(HCO2)]•H2O (2)
[Li8(BTEC)(HCO2)4] (3)
[Li4(BTEC)(H2O)6] (4)
[Li3(BTC)(H2O)] (5)
[Li3(BTC)(H2O)6] (6)
[Li(H2BTC)(H2O)] (7)
{[Ca3(BTC)2(DMF)2(H2O)2]•3H2O} (8)
[Ca(BDC)(DMF)(H2O)] (9)
[Ca(IDC)(H2O)] (10)
[Ca2(DOBDC)2(DMF)2] (11)
[Ca(DOBDC)2(H2O)2] (12)
[Ca(DOBDC)2(H2O)2] (13)
In section one, lithium and ligand H4BTEC were used as starting materials to synthesize three new coordination compounds 1 to 3, with different proportions of solvents. By using cation exchange reaction, compound 4 can be prepared from compound 1. Compounds 1 to 4 are all 3-D metal-organic frameworks, and compound 5 to 7 are 3-D, 2-D, and 1-D metal-organic framework, respectively. Compound 5 heated and absorbed water molecule which form a new structure compound 6. Compound 7 is a 1-D chain structure linked by hydrogen-bonds to form a 3-D metal-organic framework.
In section two, calcium and different ligands were used as starting material to synthesize six new coordination polymers, which are 3-D metal-organic framework. Compound 8 shows helical or straight 1-D inorganic chain connected by organic linker and formation of solvent template neutral and anionic frameworks.
The novel compounds were also characterized by powder X-ray, elemental analysis, thermogravimetric analysis, UV-vis spectra, photoluminescence, IR spectroscopy and gas absorption.

並列關鍵字

hydrothermal reactions ； coordination polymers

參考文獻

[2] Uemura, K.; Matsuda, R.; Kitagawa, S. J. Solid State Chem. 2005, 178, 2420.

[3] Robin, A.Y.; Fromm, K.M. Coord. Chem. Rev. 2006, 250, 2127.

[4] Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem. Int. Ed. 2004, 43, 2334.

[5] Beatty, A., M. Coordin. Chem. Rev. 2003, 246, 131.

[6] Vishweshwar, P.; Nangia,A.; Lynch, V., M. Gryst. Growth. Des.2003, 3, 783.