釹/鐠草酸甲基磷酸鹽之合成、結構鑑定與性質研究; Synthesis , Crystal Structures and Properties of Lanthanide Oxalatophosphonates : Na[Ln3(H2O)4(C2O4)4(CH3PO3)]·2H2O (Ln = Nd and Pr)

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题名:	釹/鐠草酸甲基磷酸鹽之合成、結構鑑定與性質研究;Synthesis , Crystal Structures and Properties of Lanthanide Oxalatophosphonates : Na[Ln3(H2O)4(C2O4)4(CH3PO3)]·2H2O (Ln = Nd and Pr)
作者:	黃雅玲;Ya-ling Huang
贡献者:	化學研究所
关键词:	鑭系草酸甲基磷酸;水熱合成;hydrothermal;Lanthanide Oxalatophosphonates
日期:	2007-06-28
上传时间:	2009-09-22 10:16:29 (UTC+8)
出版者:	國立中央大學圖書館
摘要:	本論文研究利用中溫水熱法合成新穎鑭系金屬草酸甲基磷酸鹽化合物：Na[Ln3(H2O)4(C2O4)4(CH3PO3)]·2H2O [Ln = Nd (A) and Pr (B)]。藉由一系列鑑定方法，包括以Ｘ光單晶繞射法決定出化合物的結構與化學式，再搭配元素分析、紅外線光譜、粉末繞射、熱重分析及超導量子干涉等方法進行結構組成分析、熱穩定性、熱分解反應及磁性等研究。並利用螢光光譜法深入探討放光譜線與單晶結構之間的相關性。化合物A和B 為等結構，所有的Ln 都是九配位。當中的Ln(1)O9 和Ln(2)O9 以邊共用及面共用的方式形成四聚體，此四聚體與草酸和甲基磷酸連接形成單元層。而Ln(3)O9 則是與草酸形成Z 字型無限延伸鏈，此單元鏈與單元層再經由草酸連結形成三維結構。在磁性方面，化合物A 和B 皆為反鐵磁性，A 的μeff = 3.663 μb； B 的μeff = 3.795 μb，皆與其理論值接近。在放光光譜中，化合物A 的放光波段在近紅外光區，螢光生命期為1.6 ± 0.1 μs；化合物B 的放光波段則涵蓋了綠光及紅光區，螢光生命期為1.7 ± 0.1 μs 和2.6 ± 0.1 μs。兩者之螢光生命期皆遠低於理論值，這是由於化合物當中含水分子所造成的消激效應(Quenching Effect)。 A neodymium oxalatophosphonate and the praseodymium analogue, Na[Ln3(H2O)4(C2O4)4(CH3PO3)]·2H2O [Ln = Nd (A) and Pr (B)], have been synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. We studied the photoluminescence spectra as well as the magnetic properties of the both compounds. The structure consists of layers built of tetramers of edge- and face-sharing LnO9 polyhedra connected by oxalate and methylphosphonate units, which are linked by zigzag infinite chains of oxalate-bridged LnO9 polyhedra to form a 3-D framework. They are the first examples of lanthanide oxalate-methylphosphonate. The μeff of Nd is 3.663 μb and the μeff of Pr is 3.795 μb; both are very close to the theoretical values. The Nd compound displays characteristic emission bands in the near IR region with lifetime 1.6 ± 0.1 μs. Luminescence of the Pr compound consists of many emission bands at 480-760 nm with lifetime 1.7 ± 0.1 μs and 2.6 ± 0.1 μs, respectively. The lifetimes of both compounds are much shorter than the expected values due to the quenching effects of water molecules in the structure. Crystal data for the Nd compound follow: triclinic, P`1 (No. 2), a = 9.0682(2) Å, b = 9.5114(3) Å, c = 14.0066(4) Å, a = 74.975(2)°, b = 86.534(2)º, g = 82.725(2)°, and Z = 2. Crystal data for the Pr compound are the same as those for the Nd compound except a = 9.125(1) Å, b = 9.549(1) Å, c = 14.073(2) Å, a = 75.086(2)°, b = 86.611(2)º, and g = 82.545(2)°.
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