DC 欄位 |
值 |
語言 |
DC.contributor | 化學學系 | zh_TW |
DC.creator | 余立中 | zh_TW |
DC.creator | Li-chung Yu | en_US |
dc.date.accessioned | 2010-7-23T07:39:07Z | |
dc.date.available | 2010-7-23T07:39:07Z | |
dc.date.issued | 2010 | |
dc.identifier.uri | http://ir.lib.ncu.edu.tw:444/thesis/view_etd.asp?URN=972203027 | |
dc.contributor.department | 化學學系 | zh_TW |
DC.description | 國立中央大學 | zh_TW |
DC.description | National Central University | en_US |
dc.description.abstract | 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。
| zh_TW |
dc.description.abstract | 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.
| en_US |
DC.subject | 金屬有機配位聚合物 | zh_TW |
DC.subject | 鑭系金屬 | zh_TW |
DC.subject | 自組裝 | zh_TW |
DC.subject | MOFs | en_US |
DC.subject | self-assembly | en_US |
DC.subject | lanthanides | en_US |
DC.title | 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 | zh_TW |
dc.language.iso | zh-TW | zh-TW |
DC.title | Self-assembly, Structure and Properties of Lanthanide Complexes with 1,2,4,5-Benzenetetracarboxylate | en_US |
DC.type | 博碩士論文 | zh_TW |
DC.type | thesis | en_US |
DC.publisher | National Central University | en_US |