Biologically derived and pyrene-based metal-organic frameworks for advanced applications

Metal-Organic Frameworks (MOFs) represent a new type of multi functional porous materials. These materials can be obtained from the connection of metal centres or clusters and organic ligands in such way that extended ID, 2D or 3D structures can be isolated. The unlimited possibilities of connecting the different building blocks within these materials make possible the formation of networks with a range of pore sizes and applications in gas storage and separation, catalysis, molecular sensing and drug delivery. In this thesis, the synthesis and characterisation of adenine based and pyrene derived MOFs is presented. Based on the physical properties of these MOFs, we are demonstrating that they can potentially used for advanced applications in CO2 capture, C}--4 storage, C02/C}--4 separation, xylene separation, sensing and base pairing recognition. The first part of this thesis deals with the synthesis of novel adenine based MO F s. Within the isolated MOFs, adenine provides a wide range of binding modes for metal coordination and different protonated forms acting as a bridging or terminal ligand. The diverse functionality of small biologically relevant building blocks such as adenine can tune the chemistry of MOF type structures to permit increased chemical interactions with guest molecules (C02 and C}--4) for applications such as gas storage and separation. The second part describes the design of a tetracarboxylate ligand based on an optically active pyrene core, H4 TBAPy. The choice of the ligand for the construction of extended networks is important for the construction of fluorescent MOFs for sensing applications. The isolated MOFs show interesting properties for CO2 capture and CH4 storage and due to the specific size and shape of the channels and nature of the polyaromatic ligand used for the isolation of the frameworks, aromatic molecules were introduced for separation applications. The [mal part demonstrates the synthesis of a network based on Zn, adenine and }--4TBAPy. The Watson-Crick face of the nucleobase within this framework is located within the channels, responsible for the hydrogen bonding with thymine, the pair base of adenine. Thymine solution isotherms revealed that the 3D structure can adsorb thymine molecules and this is further confirmed with Infrared Spectroscopy and Thermogravimetric and Elemental Analyses. In conclusion, this thesis represents a small contribution to the extraordinary field of Metal-Organic Framework chemistry. The formation of novel materials with unprecedented network topologies and possible applications in gas storage, gas and liquid separation and molecular sensing is important in order to create novel materials with improved and advanced properties.