| 研究生: |
黃雅玲 Ya-ling Huang |
|---|---|
| 論文名稱: |
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) |
| 指導教授: |
李光華
Kwang-hwa Lii |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 畢業學年度: | 95 |
| 語文別: | 中文 |
| 論文頁數: | 104 |
| 中文關鍵詞: | 鑭系草酸甲基磷酸 、水熱合成 |
| 外文關鍵詞: | hydrothermal, Lanthanide Oxalatophosphonates |
| 相關次數: | 點閱:10 下載:0 |
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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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