Synthesis of novel metal organic framework (MOF) materials from s-block metals
File(s)
Author(s)
Ashworth, Emma
Type
Thesis
Abstract
Metal organic frameworks (MOFs) are a subset of coordination polymers comprising of metal nodes, often transition metals, and functionalised organic linkers, such as carboxylates, which are coordinatively bonded to form an extended structure. Main group metals are generally less toxic, and lighter than their transition metal analogues, and thus MOFs containing s-block metals may be advantageous in MOF synthesis and application, specifically those with alkoxide linkers, as they form strong, water stable bonds with ions like Na+ and Mg2+. However main group metal MOFs are not as widespread as transition metal MOFs, and s-block metal MOFs with alkoxide linkers are rare in the literature.
In this work, five new s-block metal MOF structures have been synthesised and structurally determined by Single Crystal X-Ray Diffraction, and two alkoxide compounds are reported. Bis-(3-methoxy,4-hydroxyphenyl)dimethylsilane and tris-(3-methoxy,4-hydroxyphenyl)methylsilane were both synthesised from guaiacol in a two-step synthesis. One alkoxide based MOF is reported, [Mg(C6H3(O)(OCH3)(CO2))(H2O)(DMF)], which is a 2D MOF with vanillate linkers containing both carboxylate and alkoxide functionality. Two s-block metal MOF structures have been synthesised from bis-(4-carboxyphenyl)dimethylsilane: A 3D Na-MOF, [Na2(Me2Si(C6H4CO2)2)(DMF)2·0.38DMF] and a 2D Mg MOF with formula [Mg(Me2Si(C6H4CO2)2)(DMF)0.5]. Additionally, a crystal structure of bis-(4-carboxyphenyl)dimethylsilane was obtained. Two 3D Na MOFs are reported with the linker tris-(4-carboxyphenyl)methylsilane; [Na3(MeSi(C6H4CO2)3)(DMF)0.75] and [Na3(MeSi(C6H4CO2)3)(H2O)0.21]·1.3DMF both display interesting nodal structures, the latter of which contains a rare 3D node.
In this work, five new s-block metal MOF structures have been synthesised and structurally determined by Single Crystal X-Ray Diffraction, and two alkoxide compounds are reported. Bis-(3-methoxy,4-hydroxyphenyl)dimethylsilane and tris-(3-methoxy,4-hydroxyphenyl)methylsilane were both synthesised from guaiacol in a two-step synthesis. One alkoxide based MOF is reported, [Mg(C6H3(O)(OCH3)(CO2))(H2O)(DMF)], which is a 2D MOF with vanillate linkers containing both carboxylate and alkoxide functionality. Two s-block metal MOF structures have been synthesised from bis-(4-carboxyphenyl)dimethylsilane: A 3D Na-MOF, [Na2(Me2Si(C6H4CO2)2)(DMF)2·0.38DMF] and a 2D Mg MOF with formula [Mg(Me2Si(C6H4CO2)2)(DMF)0.5]. Additionally, a crystal structure of bis-(4-carboxyphenyl)dimethylsilane was obtained. Two 3D Na MOFs are reported with the linker tris-(4-carboxyphenyl)methylsilane; [Na3(MeSi(C6H4CO2)3)(DMF)0.75] and [Na3(MeSi(C6H4CO2)3)(H2O)0.21]·1.3DMF both display interesting nodal structures, the latter of which contains a rare 3D node.
Version
Open Access
Date Issued
2018-09
Date Awarded
2019-03
Copyright Statement
Creative Commons Attribution NonCommercial NoDerivatives Licence
Advisor
Davies, Rob
Sponsor
Engineering and Physical Sciences Research Council
Grant Number
EP/M507878/1
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Master of Philosophy (MPhil)