This thesis details the synthesis of fluorescent and redox active compounds for their incorporation into metal-organic coordination polymers. In particular, we report the synthesis of ligands bearing flexible imidazolate and/or carboxylate donors, their reaction with first row transition metal ions and the structural properties of the resulting materials. Chapter 1 introduces the properties, synthesis and applications of metal-organic coordination polymers, in particular crystalline three -dimensional (3~) frameworks, with reference to notable successes within the field. Chapter 2 details the synthesis of five metal-organic coordination polymers based on a novel 2,5-bis(3-(1-imidazolyl)propylcarbamoyl)terephthalate ligand and Zn2+, C02+, Mn2+ and Cu 2+ cations. The coordination environments and structural connectivities within each are compared, with particular attention paid to a rare example of Mn2+ -based supramolecular tological isomers. In Chapter 3 we investigate the use of a N,N'-bis(3-(1 -imidazolyl)propyl)-l,4,5,8- naphthalene-tetracarboxylicdiimide ligand for the formation of nano-scale metalorganic coordination polymers (NCPs). In particular, we examine the effect of both nature of metal ion and starting material concentration on particle size and morphology. Synthesis of comparable crystalline macro-scale materials and subsequent spectroscopic studies allow us to draw conclusions on the effect of metal ion on polymer dimensionality and NCP morphology: whilst two-dimensional (20) Mn(II) -based coordination sheets adopt a nano-rod morphology, onedimensional (10) Cu(II)-based chains form nano-spheres. Chapter 4 details the synthesis of porphyrin ligands bearing flexible imidazolate or carboxylate donors. We report both 10 and 20 coordination polymers based on a 5,15-dimesityl- 10,20-bis(4-phenylacetate)porphyrin ligand and Mn2+ ions, and iii both networks are unusual in that they comprise free base porphyrins and hydrogen bond with encapsulated uncoordinated ligand to afford 2D and 3D frameworks respectively. In Chapter 5 we report a series of borondipyrrin (BODIPY) compounds and investigate the effect of functional and positional substitutions on the electrochemical and optical properties of these chromophores. We further characterise the optical properties of electrochemically generated BODIPY anions and cations and examine the locations of the unpaired electrons of these species via density functional theory calculations and electron paramagnetic resonance spectroscopy. The series of compounds extends into the first examples of BODIPY dimers connected via their boron centres and we detail efforts to incorporate these species into metal-organic coordination polymers. iv
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:602423 |
| Date | January 2013 |
| Creators | Richards, Victoria Jane |
| Publisher | University of Nottingham |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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