Syntheses, spectroscopic and microporosity analysis of novel phthalocyanines and porphyrin containing molecules and polymers were carried out. For this purpose, various bulky substituents were introduced on to the aromatic core in order to provide an awkward shape and hence avoid co-facial aggregation and efficient packing. Firstly, novel phthalocyanines containing dioxy-di-tert-butyl-dimethyltriptycene substituents were synthesised. UV-vis absorption spectra of these Pcs showed band broadening depending on concentration and solvent suggesting aggregation; although this aggregation was not found to be as significant as that of various phthalocyanines reported in the literature. Apparent BET surface areas of these materials were found to be in the range of 400 to 500 m2 g-1. For comparison, the spectroscopic behaviour of the related, literature based octa-tert-butyltetra-2,3-triptycenotetraazaporphyrins were examined which form discrete co-facial dimers in pentane solution. It was found that this high specific dimerisation can be prevented by introducing methyl substituents onto the bridgehead positions of the triptycene subunits. A third category of compounds, tetratriptycenoporphyrins were synthesised using the commercially available tetrakis(pentafluorophenyl)porphyrin precursor and dihydroxy-di-tert-butyl-dimethyltriptycene. UV-vis absorption and luminescence measurements showed these complexes to be non-aggregating and were found to be microporous with BET surface areas ranging from 450 to 600 m2 g-1. The synthesis and analysis of novel phthalocyanine and porphyrin based network polymers prepared via cyclotetramerisation of bis or tris phthalonitrile containing substituents of contortion (spirobisindane, ethanoanthracene and triptycene) or via nucleophilic aromatic substitution reaction starting from a preformed phthalocyanine or porphyrin precursor, was performed. UV-vis absorption measurements of these polymers proved difficult due to solubility issues, however nitrogen adsorption analysis revealed BET surface areas ranging from 300 to 1000 m2 g-1.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:646299 |
| Date | January 2014 |
| Creators | Mughal, Sabeeha |
| Publisher | Cardiff University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://orca.cf.ac.uk/72923/ |
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