有機模板金屬磷酸鹽和金屬膦酸鹽的水熱合成、晶體結構與性質研究

Hydrothermal Synthesis, Crystal Structures and Properties of Organically Templated Metal Phosphates and Metal Phosphonates

張文明(Wen-Ming Chang)

指導教授 ： 王素蘭

國立清華大學/理學院/化學系/博士(2008年)

摘要

本論文研究主要以中溫中壓水熱合成法合成具有微孔結構或特殊性質的金屬磷酸鹽和1, 2-亞乙基二磷酸鹽材料，共合成出二十四個新穎的化合物，其中有十四個金屬草酸磷酸鹽、六個金屬磷酸鹽與四個金屬1, 2-亞乙基二磷酸鹽。所有的化合物皆利用單晶X光繞射分析來定出結構，並可進一步探討其合成條件、結構間的相關性以及各種結構之物理與化學性質。產物的純度以粉末X光繞射分析來證實、金屬元素種類和比例以電子微碳儀來鑑定、結構中之有機模板、水分子與配位基以元素分析、熱重分析與13C固態核磁共振光譜儀來證實、化合物的磁性現象以超導量子干涉磁量儀、固態光致發光光譜與反射式紫外光-可見光光譜分別以螢光光譜儀與紫外光-可見光光譜儀來測量。然而，依照有機與無機複合的種類不同可將化合物區分成三個部分：
第一個部分包含了十四個金屬草酸磷酸鹽化合物，分為系列A與系列B。系列A包含了十個銦的化合物，在A4、A5、A7與A9中，會有類似的層之連接型態；在A2、A3與A8中，是由D6R來當作二級建構單元所建構而成，然而在A2與A3中會更進一步連接形成一維的無限鏈狀。系列B包含了四個化合物，個別以鐵、錳、鋅/鋁與鎵為金屬中心。
第二部分包含了六個三維的鋅磷酸鹽化合物來當作系列C。C1至C5以兩個種類之線形有機胺來當作模板所建構而成的16環隧道之結構，而C6是以有機分子TREN(tris(2-aminoethyl)amine)來當作模板所建構而成的14環隧道之結構。除了一維的隧道外，C3至C5是由二維的16環隧道所組成。此外，C5擁有大於24環隧道結構ND-1之空隙。
第三部分以1, 2-亞乙基二磷酸根為主，包含了三個鎵的化合物與一個釩/鎵的化合物來當作系列D。D2為層狀化合物，D1、D3與D4是透過1, 2-亞乙基二磷酸根上之碳與碳相連接而形成三維開放性骨架結構。
本研究中，共發現了二十種新穎的結構型式，其中系列A與系列B分別詳述於第二章與第三章、系列C詳述於第四章與系列D詳述於第五章，並針對每一個化合物的晶體結構特徵進行描述與討論。

關鍵字

金屬磷酸鹽 ； 金屬膦酸鹽

並列摘要

This research focused on microporous metal phosphates and 1, 2-ethylenediphosphonates with new properties synthesized via mild hydrothermal synthesis. 24 new compounds were prepared, among them were 14 metal oxalatophosphates, 6 metal phosphates and 4 metal 1, 2-ethylenediphosphonates. All structures have been characterized by single-crystal X-ray diffraction and to be further discussed on their synthesis condition and physical properties. Samples with individual purity were preliminarily checked by powder XRD patterns. The metal ratio and types were confirmed by electron probe microanalysis data. Organic template, water molecules and ligands in the structure were confirmed by EA data, thermogravimetric analyses, and 13C NMR. The magnetic data was measured on a Quantum Design SQUID magnetometer. Solid-state PL spectra and Reflectance UV–vis spectra were studied. Based on the different organic and inorganic hybrid types, the compounds can be categorized into three parts:
The first part contains 14 metal oxalatophosphates which can be divided into series A and B: series A contains 10 indium compounds in which A4, A5, A7 and A9 exhibit similar layer topology. A2, A3, and A8 contain D6Rs as a common secondary building units which further connect into infinite chains in A2 and A3. Series B consists of four compounds respectively with Fe, Mn, Al/Zn and Ga as the metal center.
The second part contains 6 three-dimensional zinc phosphates as series C : C1 to C5 are 16R channel structures templated by two linear amines and C6 is a 14R channel structure using TREN（tris(2-aminoethyl)amine） molecules as templates. Other than 1D channels, C3 to C5 consists of 2D 16-ring channels. Furthermore, C5 shows larger nonframework space than ND-1.
In the third part are 3 gallium and 1 vanadium/gallium compounds (series D) with 1, 2-ethylenediphosphonic acids as ligands. D2 is a layer compound while D1, D3 and D4 are 3D open framework structures by connecting the carbon on 1, 2-ethylenediphosphonate ligands.
Among the 24 new compounds in this thesis, there are 20 new structure types. Series A and B are respectively described in Chapter 2 and Chapter 3, series C is described in Chapter 4 and Series D is described in Chapter 5 in which every compound is detailed on its structure characteristic.

並列關鍵字

HASH(0x1b0bc040) ； HASH(0x1b0bc0e0)

參考文獻

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