臺灣博碩士論文加值系統

本篇論文中的研究主要是以鑭系金屬離子與含有羧基或磺基的有機配體，藉由自組裝( Self-assembly)的方式合成一系列多維度以及具有特殊性質的金屬–有機材料( Metal-organic materials)。而我們成功的合成出下列幾種不同的固態結構，分別如下：
{[Sm(2STP)(H2O)3](H2O)}n (1)
{K[Ln(4SBA)2(H2O)]}n { Ln = Sm (2), Eu (3), Tb (4), Nd(5)}
[Ln(mTATAB)(DMA)3]n
{ Ln = La (6), Ce (7), Pr (8), Nd (9), Sm (10), Eu (11), Gd (12), Tb (13), Dy (14)}
( 2STP = 2-sulfoterephthalate; 4SBA = 4-sulfobenzoic acid; mTATAB = 3,3’,3’’-s-Triazine-1,3,5-triyltri-m-aminobenzoate)
本文中將對它們的合成條件、分子結構、及熱性質與放光性質做較深入的探討。
化合物1的二維結構為中心金屬與氧原子的一維鏈與配基2STP的橋接所構成，所構出的層和層之間可藉由配位、空間中的水分子與2STP上的磺基形成氫鍵作用力。
化合物2~5為三維結構：以金屬—氧與配基4SBA形成二維網狀平面，再以橋接的水作連接成為一個三維骨架。
 
化合物6~14為二重交錯三維結構，金屬中心分別配位三個配基mTATAB與三個溶劑分子DMA，兩重結構互為中心對稱，對稱中心位晶格正中央(a/2, a/2, a/2)。該系列化合物移除溶劑分子後的體積占有率約45%，具有潛在的孔洞性。本文也會對化合物10做更詳盡的熱性質探討。
化合物1 (Sm)、2 (Sm)、3 (Eu)、4 (Tb)、10 (Sm)、11 (Eu)、13 (Tb)、14 (Dy)在可見光區皆有放光行為，其放光為金屬的特徵放光。其中不論何種配基，對於Tb來說配基分子的能量轉移效率極佳，具有顯著的天線效應；而Eu雖然尚有配基分子的放光，但仍是以金屬特徵放光占大多數，因此在紫外光燈下依然可觀察到強烈的紅光。

Here we report that the self-assembly of lanthanide ions with functional organic ligands, such as carboxylate group and sulfonate group.We have synthesized fourteen novel metal-organic materials, as following:
{[Sm(2STP)(H2O)3](H2O)}n (1)
{K[Ln(4SBA)2(H2O)]}n { Ln = Sm (2), Eu (3), Tb (4), Nd(5)}
[Ln(mTATAB)(DMA)3]n
{ Ln = La (6), Ce (7), Pr (8), Nd (9), Sm (10), Eu (11), Gd (12), Tb (13), Dy (14)}
( 2STP = 2-sulfoterephthalate; 4SBA = 4-sulfobenzoic acid; mTATAB = 3,3’,3’’-s-Triazine-1,3,5-triyltri-m-aminobenzoate)
In this thesis, their syntheses, structural characterization, thermal properties, and luminescence properties, are discussed.
Compounds 1 is a 2-D framework: The metal-oxide 1-D chain and 2STP constructed a 2-D network, and the 2-D sheet packed to a 3-D structure by hydrogen bonding from coordinated water and sulfonate group.
Compounds 2 to 5 are 3-D structures. It constructed a 2-D plane by metal-oxide, then form a 3-D framework with bridging water.
Compounds 6 to 14 are 3-D isostructures with 2-fold interpenetration. The coordination number of lanthanum metal is nine, including three mTATABs and three DMAs. The inversion center of two centrosymmetric domains is located at (a/2, b/2, c/2) of unit cell. The solvent-accessible free volumes of Ln(mTATAB)(DMA)3 calculated by PLATON, are approximately 45% of the crystal volume, which are potentially porous materials.
 
Compounds 1(Sm), 2(Sm), 3(Eu), 4(Tb), 10(Sm), 11(Eu), 13(Tb), 14(Dy) have luminescence properties in UV-vis range, which can contribute to characteristic lanthanide emissions. For compounds containing terbium or europium, which exhibit intence emissions, in other words, they have better energy transfer efficiency in antenna effect.

目錄 I
圖目錄 IV
表目錄 XI
附圖目錄 XIII
附表目錄 XIV
中文摘要 1
English Abstract 3
第一章 緒論 5
第二章 有機-無機配位材料開發 21
2.1 實驗儀器 21
2.2 藥品來源 22
2.3 合成步驟 24
2.3.1 {[Sm(2STP)(H2O)3](H2O)}n (1)之合成 24
2.3.2 {K[Ln(4SBA)2(H2O)]}n {Ln = Sm (2), Eu (3), Tb(4), Nd(5)}之合成 25
2.3.3 [Ln(mTATAB)(DMA)3]n {Ln = La (6), Ce (7), Pr (8), Nd (9), Sm (10), Eu (11), Gd (12), Tb (13), Dy (14)}之合成 27
2.4 X光單晶繞射實驗及構造解析 32
2.4.1 {[Sm(2STP)(H2O)3](H2O)}n (1) 32
2.4.2 {K[Sm(4SBA)2(H2O)]}n (2) 34
2.4.3 {K[Eu(4SBA)2(H2O)]}n (3) 35
2.4.4 [La(mTATAB)(DMA)3]n (6) 38
2.4.5 [Ce(mTATAB)(DMA)3]n (7) 40
2.4.6 [Pr(mTATAB)(DMA)3]n (8) 42
2.4.7 [Nd(mTATAB)(DMA)3]n (9) 44
2.4.8 [Sm(mTATAB)(DMA)3]n (10) 46
2.4.9 [Eu(mTATAB)(DMA)3]n (11) 48
2.4.10 [Gd(mTATAB)(DMA)3]n (12) 50
2.4.11 [Tb(mTATAB)(DMA)3]n (13) 52
2.4.12 [Dy(mTATAB)(DMA)3]n (14) 54
第三章 結果與討論 57
3.1 {[Sm(2STP)(H2O)3](H2O)}n (1) 57
3.1.1 合成 57
3.1.2 分子結構 58
3.1.3 紅外線光譜38 62
3.1.4 熱重分析 63
3.1.5 固態放光光譜 64
3.2 {K[Ln(4SBA)2(H2O)]}n {Ln = Sm (2), Eu (3), Tb(4), Nd(5)} 66
3.2.1 合成 66
3.2.2 分子結構 68
3.2.3 紅外線光譜40 71
3.2.4 熱重分析 73
3.2.5 固態放光光譜 74
3.3 [Ln(mTATAB)(DMA)3]n {Ln = La (6), Ce (7), Pr (8), Nd (9), Sm (10), Eu (11), Gd (12), Tb (13), Dy (14)} 79
3.3.1 合成 79
3.3.2 分子結構 80
3.3.3 紅外線光譜28 88
3.3.4 熱重分析 90
3.3.5 溶劑交換 98
3.3.6 固態放光光譜 102
第四章 結論 109
參考文獻 111
附圖 115
附表 130

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