Metal-organic frameworks: The design, synthesis and investigation of new materials

Abstract

The research in this thesis describes the synthesis and characterisation of new metal organic framework (MOF) materials, in addition to assessment of systematically selected known materials for their gas storage potential. The majority of these compounds were characterised using single crystal X-ray diffraction techniques.

In Chapter 1 the background to MOFs is introduced, with a brief description of their applications and in particular their use as gas storage materials.

Thirteen new compounds were synthesised and characterised in Chapter 2 in an attempt to obtain a series of compounds with larger pores than [Cu2(bza)4(pyz)]. Of these, ten were shown to contain the paddle wheel SBU, with the majority containing larger pores.

The use of the Environmental Gas Cell (EGC) was investigated in Chapter 3. The compound [Zn2(ox)(atz)2]·2MeOH was tested and shown via single crystal X-ray diffraction to contain 0.42 molecules of SO2 per asymmetric unit.

In Chapter 4 the synthesis and characterisation of eleven new frameworks, using the bisox ligand and a range of silver(I) salts are described. In particular, one structure exhibited a solid state interconversion on removal of the solvent, monitored using powder X-ray diffraction and TGA.

Seven new compounds based on functionalised β-diketonate ligands, Group 13 and lanthanide metals were synthesised and characterised in Chapter 5. This series of compounds demonstrated that the construction of mixed-metal organic frameworks can be achieved through a two-step reaction forming a metalloligand as an intermediate, and also how hydrogen bonding networks can also be formed from the same ligands.

The final chapter in this thesis concerns the use of the Cambridge Structural Database (CSD) as a means of examining MOF structures that contain guest solvent and gas molecules. The aim of this investigation was to gain an understanding of how these guests interact with the frameworks, with a view to informing the design of new framework materials.

Date of Award	1 Jun 2011
Original language	English
Awarding Institution	University of Bath
Supervisor	Paul Raithby (Supervisor), Andy Burrows (Supervisor) & Mary Mahon (Supervisor)