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Title: Immobilisation of polyazamacrocycles into porous materials
Author: Richards, Emma
ISNI:       0000 0004 2729 4504
Awarding Body: University of Liverpool
Current Institution: University of Liverpool
Date of Award: 2012
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The synthesis and characterisation of functionalised polyazamacrocycles and their subsequent immobilisation into porous materials were investigated and reported in this thesis. The incorporation of polyazamacrocycles into porous materials offers the potential to enhance their biomimetic and environmental properties with tuneable microenvironments around the macrocycles. Nine polyazamacrocycles have been synthesised that are functionalised with vinyl, pyridyl, carboxylate and iodide pendant arms in order to immobilise them into porous materials. Of these macrocycles nine metal complexes were successfully synthesised and their crystal structures are discussed. The most interesting of these metal complexes are complex 2, a cyclam based metal complex and complex 7, a [12]aneN3 based metal complex which both have coordinated water molecules and therefore are activated for hydrolase activity. Polyazamacrocycles have successfully been immobilised into organic cross-linked polymers using polar and non-polar cross-linkers and a systematic investigation has taken place in order to determine the effects of the nature and amount of porogen and the concentration of macrocycle within the polymer on the porous properties of the polymer. These effects include BET surface area, shape and size distributions of pores, and CO2 uptake capacities. The effect of incorporation of metal complexes and metal ions is also discussed. It was found that with non-polar based polymers, BET surface areas were find to be higher when non-polar porogens were employed and decrease with increasing polarity of the porogen. However, the nature of the macrocycle also plays an important role in the porosity of the resulting polymers. Zinc and copper metal organic frameworks containing cyclam based macrocycles with pyridyl pendent arms have been synthesised with 2D layered structures. The crystal structures reveal that triflate and hexafluorophosphate counterions play an important role in stabilisation of the framework but with the disadvantage of blocking possible porosity.
Supervisor: Bradshaw, Darren Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Q Science (General) ; QD Chemistry