Massey Documents by Type
Permanent URI for this communityhttps://mro.massey.ac.nz/handle/10179/294
Browse
3 results
Search Results
Item Metal-organic frameworks for selective gas separation : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand(Massey University, 2019) Taheri Qazvini, OmidWith an ever increasing need for a more energy-efficient and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties are in high demand. Metal–organic frameworks (MOFs), constructed from metalcontaining nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. However, the bottleneck in this context is that MOFs are expensive to be fabricated and majority of them are not stable in harsh environments, which are often required by industrial processes. In this thesis, we introduce three families of metal-organic frameworks with exceptional gas separation performance for a variety of different gas mixtures separation. Their unique separation performances are well supported by isotherm measurement, X-ray crystallography, DFT calculations, and breakthrough test. These MOFs are all readily synthesizable by inexpensive precursor and highly stable at extreme conditions.Item Physicochemical and structural studies of ferrocene schiff base derivatives and some associated adducts : a thesis presented in partial fulfilment of the requirements for the degree of Master of Science at Massey University(Massey University, 1995) Lowe, Andrew DavidThe results reported in this thesis are an investigation into the synthesis, characterisation, and coordination ability of some new Schiff base ferrocenyl derivatives. Chapter One gives a brief overview of the practical applications that ferrocene based compounds have been put to, since ferrocenes first synthesis in 1951. Chapter Two outlines the preparation and characterisation of six new Schiff base ferrocenyl derivatives, along with a new synthesis and full characterisation of a ferrocenyl thiosemicarbazide derivative which was first synthesised in 1968. The X-ray structure of bis-N-(0-hydroxybenzylidene) ferrocenylimine,(L11), was established, showing relatively strong intramolecular hydrogen bonding between the Schiff base nitrogen and the hydrogen of the hydroxy group on the phenol. In Chapter three reduction attempts of the ferrocene derivatives in Chapter 2 are reported. The synthesis and characterisation of a borane adduct of the N-(o-hydrazonylpyridine) ferrocenimine ligand, (L2.BH3 ), is studied. Its single crystal X-ray structure is determined and the adduct is compared to the parent L2 ligand. Chapter Four contains the preparation and characterisation of the complex [Zn(L1)Cl]2 , which is based on the N-(o-hydroxybenzylidene) ferrocenylimine ligand, (L1). Five new metal complexes are reported, [Co(L2)Cl 2 ], [Ni(L2)Br2 ], [Cu(L2)Cl2 ], [Co(L2)Br2 ] and [Zn(L2)Cl2 ] based on the L2 ligand, and these are characterised by mass and infra-red spectroscopies. In Chapter Five the ligands are studied by cyclic voltammetry and Mossbauer spectroscopies, with further cyclic voltammetry studies undertaken on the complexes. The electrochemical oxidation trends observed in the cyclic voltammetry studies on the Schiff base derivatives are in parallel with the Mossbauer studies, which have the results rationalised in terms of electron population movements within the 57 Fe d-orbitals and the p-orbitals of the cyclopentadienyl rings.Item Computationally synthesised inorganic and organometallic complexes : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Albany, New Zealand(Massey University, 2017) Sajjad, Muhammad ArifCatalytic aromatic ring C–H bond functionalisations by transition metal cyclometallation reactions are important for organic transformation reactions. The cyclometallated product, which contains a new metal–carbon bond is formed as a consequence of different types of carbon–hydrogen····metal (C–H····M) interactions. These C–H···M interactions have been known as anagostic, preagostic and agostic interactions. By nature, the anagostic interaction has mainly electrostatic components, the preagostic interaction has electrostatic components with some back-bonding from metal to C–H antibonding orbital involved and the agostic interaction has mainly covalent components when the C–H bond donates electron density to the partially occupied metal centre. Prior to the current thesis work, an in-depth study that addresses the influence of steric and electronic factors on the anagostic, preagostic and agostic carbon–hydrogen····metal interaction was missing. In this thesis, the influence of both the steric and electronic factors on the anagostic, preagostic and agostic C–H···M interactions has been studied. It is seen that the electronic and steric influences play differently for different ligand systems as with the flexible tetralone ligand, a maximum of steric and electronic influence results into another type of anagostic interaction named as the 'C-anagostic' interaction. It is also seen that a stronger steric and electronic effect can trigger agostic covalency at the anagostic stage of the reaction. The inflexible ligand ensures the short anagostic approach, which has some back-bonding character and the nature of the interaction lies into the preagostic category. Finally, the aromatic ring agostic interactions have more complexity as new donations named as 'syndetic' from C–C pi bond to metal antibonding orbitals were recognised which shares the same antibonding acceptor orbitals as the agostic donation does. The recognition of new bonding situations in C–H····M interactions can have significant implications for C–H bond functionalisation reactions.