鹼土金屬與膦酸酯類之配位聚合物的水熱合成、結構鑑定與性質研究

Alkaline-Earth Metal Phosphonocarboxylates: Synthesis, Structural Characterization, and Properties.

李育珊(Yu-Shan Lee)

指導教授 ： 林嘉和 ； 葉瑞銘

中原大學/理學院/奈米科技碩士學位學程/碩士(2010年)

https://doi.org/10.6840/cycu201000260

摘要

在此論文中，我們成功了使鹼土金屬(Mg2+、Ca2+、Sr2+、Ba2+)與兩種有機配位基，N-(羧甲基)-N-(膦醯甲基)甘氨酸(H4PMIDA)與2-羧乙基膦基醋酸(H3CEPA)藉由中溫水熱合成法合成出九個不同的新穎有機金屬骨架。本文中所合成出的結構如下：
[Mg(H2O)(H2PMIDA)] (1) [Ca(H2O)(H2PMIDA)] (2)
[Sr(H2O)(H2PMIDA] (3) [Sr2(H2O)(PMIDA)] (4)
[Sr2(HPO4)(H2PMIDA)] (5) [Ba2(HPO4)(H2PMIDA)] (6)
[Ba2(H2O)(H2PMIDA)2] (7) [Sr4(HCEPA)4] (8)
[Ba(HCEPA)] (9)
化合物1、2、3及5-9經由單晶鑑定結果顯示為三維立體結構，化合物2是利用氫鍵作用力形成三維立體結構。而化合物3、5、6結構中具有螺旋性的排列，化合物3包含左右兩種方向的螺旋排列，左螺旋形成菱形迴路，而右螺旋則是形成方形迴路；化合物5跟6也是呈現左、右兩種螺旋排列。以上化合物1-9除了使用單晶X光繞射儀來鑑定其結構外，也利用了粉末X光繞射儀、元素分析儀、熱重分析儀、固態核磁共振儀、紫外-可見光吸收光譜儀、螢光放光光譜儀和紅外光共振光譜儀來探討其特性。
另外也將化合物1、5、6摻入鑭系金屬(Eu, Tb)，我們除了利用單晶X光繞射儀鑑定其結構發現到鑭系金屬取代了部分鹼土金屬的位置之外，也使用了粉末X光繞射儀、紫外-可見光吸收光譜儀及螢光放光光譜儀檢測，進而討論鑭系金屬對原化合物所造成的影響。

關鍵字

鹼土金屬 ； 水熱法 ； 膦酸酯

並列摘要

Nine new coordination polymers have been synthesized by hydrothermal reactions and structurally characterized. Two different phosphonates (N-(Phosphonomethyl) iminodiacetic acid hydrate and 2-carboxyethanephosphonic acid) were used as starting materials with alkaline-earth metal (Mg2+, Ca2+, Sr2+ and Ba2+). Compounds 1 to 9 structures are as follows:
[Mg(H2O)(H2PMIDA)] (1) [Ca(H2O)(H2PMIDA)] (2)
[Sr(H2O)(H2PMIDA] (3) [Sr2(H2O)(PMIDA)] (4)
[Sr2(HPO4)(H2PMIDA)] (5) [Ba2(HPO4)(H2PMIDA)] (6)
[Ba2(H2O)(H2PMIDA)2] (7) [Sr4(HCEPA)4] (8)
[Ba(HCEPA)] (9)
Single X-ray diffraction showed that compounds 1, 2, 3 and 5-9 are 3-D metal-organic frameworks. Compound 2 is 2D layer with hydrogen bonds induce the complex to a mimic 3-D structure. Compound 3, 5 and 6 are containing helical structure. Compound 3 have both helical structures (right and left). The right helical structure becomes a rhombus circle and the left helical structure becomes a square circle.Compound 5 and 6also have both helical structures (right and left). The novel compounds were also characterized by powder X-ray, elemental analysis, thermogravimetric analysis, solid state NMR, UV-vis spectra, photoluminescence and IR spectroscopy.
Furthermore, the experimentation base on compound 1, 5 and 6 that we added the lanthanides (Eu, Tb). In order to realize the influence of lanthanides to compounds that we not only use single-crystal X-ray diffractometer to identify their constructions but powder X-ray, UV-vis spectra, photoluminescence.

並列關鍵字

phosphonate ； solvothermal ； alkaline-earth metal

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