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首页> 外文学位 >Engendering structural and chemical diversity in metal-organic framework materials via ligand elaboration and post-synthesis modification.
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Engendering structural and chemical diversity in metal-organic framework materials via ligand elaboration and post-synthesis modification.

机译：通过配体精加工和合成后修饰增强金属有机骨架材料的结构和化学多样性。

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摘要

Families of metal-organic frameworks (MOFs), possessing high levels of structural and chemical diversity were synthesized via the covalent elaboration of the constituent organic ligands both pre- and post-MOF synthesis. To engender structural diversity, a series of 4,4'-ethynylenedibenzoic acids were synthesized and used in the construction of Zn-based, mixed-ligand metal-organic frameworks. Through variation of the organic functionalities in the 3- and 3'-positions of these linkers, a collection of MOFs with differing connectivities and varying levels of interpenetration was obtained. This strategy was then employed in attempts to obtain catenation isomers via post-synthesis modification. A series of 3-ethynyl-4-[2-(4-pyridinyl)ethenyl]pyridine ligands with different chemically labile acetylene protecting groups were synthesized. The sizes of the protecting groups were used to affect the levels of catenation in Zn-based, mixed-ligand MOFs constructed using these ligands and 4,4'-(1,2-ethynediyl)bisbenzoic acid. The protecting groups may eventually be deprotected to generate catenation isomers.Post-synthesis elaboration of MOFs was employed to introduce chemical diversity both at the external surfaces of MOF crystals and throughout the entire framework. In the first case, the external surface of a 2-fold catenated, Zn-cornered, mixed-ligand MOF bearing trimethylsilyl-protected acetylenes was selectively deprotected and its surface was subsequently covalently decorated with azide-containing organic molecules via "click" chemistry. In the second case, a non-catenated Zn-based MOF material bearing silyl-protected acetylenes was first constructed. Via a solvent-based selective deprotection strategy, two different organic azides were then "clicked" onto the MOF, resulting in a material whose internal and external surfaces are functionalized differently. Finally, to demonstrate the utility of covalent post-synthesis modification in the construction of otherwise inaccessible MOFs, a glycol-bearing, Zn-based, mixed-ligand MOF was reacted with succininc anhydride. This reaction proceeded quantitatively to yield a new MOF containing free carboxylic acids that can be further modified via complexation with Cu 2+ ions.
机译：通过在MOF合成前和合成后对组成的有机配体进行共价精制，合成了具有高水平的结构和化学多样性的金属有机骨架（MOF）家族。为了引起结构多样性，合成了一系列的4,4'-乙炔二苯甲酸，并用于构建基于锌的混合配体金属-有机骨架。通过改变这些接头的3'和3'-位的有机官能团，可以获得具有不同连接度和互穿水平的MOF集合。然后将该策略用于尝试通过合成后修饰获得串联异构体的尝试。合成了具有不同化学上不稳定的乙炔保护基的一系列3-乙炔基-4- [2-（4-吡啶基）乙烯基]吡啶吡啶配体。保护基的大小用于影响使用这些配体和4,4'-（1,2-乙炔二基）双苯甲酸构建的Zn基混合配体MOF中的串联水平。保护基团最终可以被脱保护以产生串联异构体。MOF的合成后修饰被用于在MOF晶体的外表面和整个框架上引入化学多样性。在第一种情况下，对带有三甲基甲硅烷基保护的乙炔的2倍链状，Zn角，混合配体MOF的外表面进行选择性脱保护，然后通过“点击”化学方法将其表面用含叠氮化物的有机分子共价修饰。在第二种情况下，首先构建了带有甲硅烷基保护的乙炔的未连接锌基MOF材料。通过基于溶剂的选择性脱保护策略，然后将两种不同的有机叠氮化物“点击”到MOF上，从而得到内表面和外表面功能不同的材料。最后，为证明共价合成后修饰在构建否则无法获得的MOF中的实用性，将带有乙二醇的，基于Zn的混合配体MOF与琥珀酸酐反应。该反应定量地进行以产生含有游离羧酸的新的MOF，其可以通过与Cu 2+离子络合而进一步改性。

著录项

  • 作者

    Gadzikwa, Tendai.;

  • 作者单位

    Northwestern University.;

  • 授予单位 Northwestern University.;
  • 学科 Chemistry Inorganic.Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 143 p.
  • 总页数 143
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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