Sheridan, Ursula
(2014)
Synthesis and Coordination Studies of Novel
Heteroaryl Tetrazoles.
PhD thesis, National University of Ireland Maynooth.
Abstract
This thesis describes the synthesis, characterisation and coordination studies of an array
of heteroaryl 5-substituted tetrazole ligands. A family of 5-substituted pyridyl tetrazole
ligands with various functionalities tethered to the tetrazole moiety were prepared and
fully characterised. These ligands were reacted with various MX2 salts (M = Cu, Ni, Co, Zn;
X = chloride, thiocyanate). A number of the resulting discrete metal complexes were
analysed by X-ray crystallography and their potential application as anti-cancer
therapeutics are discussed.
Carboxylate functionalised pyridyl tetrazole ligands were also synthesised and
characterised. These ligands were examined for their potential to form coordination
polymers. These investigations have been successful and have led to a series of
coordination polymers and discrete clusters, some of which were examined by X-ray
crystallography. Diamagnetic materials were subjected to solid state fluorescence studies
and exhibited (in all but one case) increased emission when compared to the free parent
ligands. EPR spectroscopic studies were also performed on Cu(II) materials.
We proceeded to develop these ligands into dicarboxylate systems in order to achieve
higher dimensional coordination polymers. This work yielded a plethora of novel 1-D
coordination polymers and dinuclear clusters with Cu(II), Ni(II), Co(II), Mn(II) and Zn(II)
as the metal ions. Interesting manifestations were observed in these investigations,
including the selective hydrolysis of an alkyl ester over an aromatic ester; selective
coordination of aromatic carboxylates to hard metal cations; and the presence of
coordinatively vacant carboxylate sites which open exciting avenues in the field of postsynthetic
modifications. X-ray crystallography was performed on ten products. EPR
spectroscopy was performed on Cu(II) materials and the solid state emission spectrum of
one Zn(II) complex displayed increased emission compared to its free ligand.
Continuing the theme of coordination polymers, we investigated the ability of carboxylate
functionalised bis-tetrazole ligands to form coordination polymers with Cu(II). Two
categories of bis-tetrazole systems were synthesised and examined: flexible linked and
rigidly linked tetrazoles. Investigations of pyrazine linked tetrazoles that were
functionalised with carboxylate groups led to two 2-D coordination polymers, one of
which contains water clusters and thus presents future opportunities for removal or
substitution of these molecules for guest uptake and future applications.
| Item Type: |
Thesis
(PhD)
|
| Keywords: |
Synthesis; Coordination Studies; Novel
Heteroaryl Tetrazoles; |
| Academic Unit: |
Faculty of Science and Engineering > Chemistry |
| Item ID: |
7760 |
| Depositing User: |
IR eTheses
|
| Date Deposited: |
16 Jan 2017 12:04 |
| URI: |
|
| Use Licence: |
This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available
here |
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