| 研究生: |
余立中 Li-chung Yu |
|---|---|
| 論文名稱: |
鑭系金屬與1,2,4,5-苯四酸配子之自組裝合成、結構與性質探討 Self-assembly, Structure and Properties of Lanthanide Complexes with 1,2,4,5-Benzenetetracarboxylate |
| 指導教授: |
李光華
Kwang-Hwa Lii 呂光烈 Kuang-Lieh Lu |
| 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: | 98 |
| 語文別: | 中文 |
| 論文頁數: | 148 |
| 中文關鍵詞: | 金屬有機配位聚合物 、鑭系金屬 、自組裝 |
| 外文關鍵詞: | MOFs, self-assembly, lanthanides |
| 相關次數: | 點閱:21 下載:0 |
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本文使用鑭系金屬離子和bezene-1,2,4,5-tetracarboxylic acid經由自組裝的方式合成出{[Sm2(btec)1.5(H2O)5]‧10H2O}n (1)、{[Gd2(btec)1.5(H2O)5]‧9H2O}n (2)、{[La2(btec)1.5(H2O)4]‧3H2O}n (3) 、{[Ce2(btec)1(H2btec)1(H2O)4]‧4H2O}n (4)、{[Gd(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (5)、{[Dy(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (6)、{[Ho(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (7)、{[Dy4(btec)3(H2O)8]‧4H2O}n (8)、{[Ho4(btec)3(H2O)8]‧4H2O}n (9)等九個化合物。
化合物1、2具有相似的固態結構,是以九配位的金屬中心形成具有雙核金屬簇的三維結構,結構中有二維的通道。化合物3是以九配位及十配位的金屬中心形成具有四核金屬簇的三維結構,四核金屬簇是以四個金屬離子為頂點以氧橋連接形成四邊型的結構。化合物4是以九配位及十配位的金屬中心形成具有金屬鍊的二維結構,結構中苯四酸有兩種配位模式,其中最特別的是以使用1、5號位的羧酸基鍵結四個金屬離子, 但保留了2、4號位置的羧酸基未鍵結任何金屬離子且羧酸基上的氫未脫去,形成文獻中未見的µ4-橋接配位模式。化合物5、6、7具有相似的固態結構,以九配位的金屬中心形成金屬鍊的三維結構。化合物8、9具有相似的固態結構,以八配位及九配位的金屬中心形成具有四核金屬簇的三維結構,四核金屬簇以Z字型的方式,以金屬為四個節點再以氧橋連接。以上化合物經由TGA鑑定,皆具有高的熱穩定性,達400~500 ℃才開始崩塌瓦解。由直流磁化率χmT的數據及擬合中可知化合物5~9整體的行為表現是反鐵磁性,但是由交流磁化率數據的虛數部分發現有磁緩現象,這是鑭系金屬化合物少見的磁性特質,此磁緩現象應是來自於結構中單一金屬離子或單一金屬鍊(簇)激發態所展現的行為。
A series of lanthanide complexes, {[Sm2(btec)1.5(H2O)5]‧10H2O}n (1)、{[Gd2(btec)1.5(H2O)5]‧9H2O}n (2)、{[La2(btec)1.5(H2O)4]‧3H2O}n (3) 、{[Ce2(btec)1(H2btec)1(H2O)4]‧4H2O}n (4)、{[Gd(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (5)、{[Dy(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (6)、{[Ho(btec)0.5(H2btec)0.5(H2O)1]‧2H2O}n (7)、{[Dy4(btec)3(H2O)8]‧4H2O}n (8)、{[Ho4(btec)3(H2O)8]‧4H2O}n (9), were synthesized. The crystal structure diffraction analysis showed that complexes 1 and 2 are isostructure, and reveals a three-dimensional framework for the construction of two nine-coordinated metal centers. In the complexes 1 and 2, the two-dimensional channels are obtained. Complex 3 also shows a three-dimensional framework with the quadrilateral tetranuclear building units comprising of both ten- and nine-coordinated lanthanum centers. Complex 4 is a two-dimensional structure comprising of 1D cerium chain. The metal chains in the complex 4 are composed both of ten- and nine-coordinated cerium centers bridged by carboxylate groups of btec ligand. Complexes 5-7 show isostructural of three-dimensional frameworks constructing from lanthanide metal chains, which contains nine-coordinated metal centers bridged by carboxylate groups of btec ligand. The zigzag tetranuclear complexes 8-9 are also isostructure and display a three dimensional framework comprising of both nine- and eight-coordinated metal centers.
The results of TGA studies indicated that complexes 1-8 are high thermal stability and their frameworks remain stable under heat treatment to 400-500 ℃. The magnetic results of complexes 5-9 indicate antiferromagnetic and spin-orbital coupling dominated between the metal ions in complexes 5-9. Surprisiely, slow magnetic relaxation was observed for complexes 6-9. The slow magnetic relaxation may be arise from the single-ion behavior of the metal ions or the exciting state of single metal chain rather than from the spin-spin coupling interaction between the metal ions.
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