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Structural control in metal-organic frameworks

Jones, Corey 2019. Structural control in metal-organic frameworks. PhD Thesis, Cardiff University.
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Abstract

This thesis explores the ways in which structural control can be exhibited in metalorganic frameworks. Chapter 1 describes the history of MOFs, particularly highlighting the importance of the structure-function relationship. The various ways in which the structural control can be exacted by synthesis, component design or external stimuli are outlined, forming the basis of the work in the subsequent chapters. Chapter 2 discusses the use of the CLASSIC NMR technique, carried out using the facilities at the UK 850 MHz Solid-State NMR Facility, to monitor the in-situ formation of five different frameworks containing NMR active nuclei. This approach enabled simultaneous monitoring of the liquid and solid phases during syntheses, highlighting its advantage as an alternative method to traditional diffraction studies to study the in-situ crystallisation processes. Chapter 3 summaries the syntheses of a novel series of coordination polymers with a benzimidazalone-based linker (H2L1). The linker has limited flexibility and the coordination geometry with various metal ions was explored. Crystal structures of the seven materials were obtained (MgL1, CaL1, SrL1, BaL1, MnL1, Cu3(L1)2, ZnL1) that showed the linker can bind to the metal nodes in two distinct conformations. Chapter 4 details the synthesis and photochemical characterisation of two spiropyranbased carboxylate linkers (H2L2 and H4L3) that can undergo a structural change upon exposure to multiple stimuli. The linkers were reacted with various metal salts in combinatorial reactions, with powder X-ray diffraction used to screen for promising crystalline frameworks. Seven materials (Zn-L2, Mg-L3, Ca-L3, Sr-L3, Ba-L3, Zn-L3 and Cu-L3) showed promise of spiropyran incorporation. Initial structural characterisation of Cu-L3 has been obtained crystallographically. UV-visible absorption spectroscopy was used to further understand the SP/MC equilibrium of H4L3 in solution under MOF reaction conditions, with the aim of predicting the conditions that can form crystalline materials in future syntheses.

Item Type: Thesis (PhD)
Date Type: Completion
Status: Unpublished
Schools: Chemistry
Date of First Compliant Deposit: 20 December 2019
Last Modified: 20 Dec 2019 11:29
URI: http://orca.cf.ac.uk/id/eprint/127676

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