Metal-Organic Frameworks and Supramolecular Assemblies for Dyes and other Inclusions

This thesis concerns the synthesis and characterisation of novel CTV-based
coordination polymers and supramolecular assemblies, and analysis of the dye uptake
and degradation abilities of these subsequent materials.
An in-depth review of CTV-based coordination polymers was first undertaken to discern
any trends that could be used to inform the rational design of these materials. From this
study, it was found that there were too few examples to take any meaningful lessons,
and as of yet there were no systematic approaches to design materials with desirable
qualities.
A range of CTV-based ligands were synthesised and used in the synthesis of a range
of novel materials. A series of Cu(II)-based catenane structures, C1 and C2, were
shown to contain a novel trans-octahedral [Cu4(μ-Cl)6Cl2(OH2)2] bridges. C2 is believed
to be the only example of a polymeric catenated material featuring CTV-based ligands.
These material were also shown to undergo single-crystal-to-single-crystal
transformations upon solvent exchange. Additionally, a series of 2D silver-based
materials, Ag1, were constructed which exhibited the relatively rare Kagome Dual
(kgd) network. A further silver-containing coordination polymer was constructed, Ag2,
which formed a 2D network of kgd layers, bridged together forming metallo-capsules.
These materials, along with a previously-made Re-based coordination polymer, Re1,
were then tested for their dye uptake and degradation efficacies. None of the
coordination polymers were shown to uptake dye, however some of these materials
were able to degrade dyes under UV light, with Re1 performing the best, degrading
methylene blue by 44% after one hour of irradiation. This represents the first such
example of a rhenium-based coordination polymer being used for this purpose, as well
as the first study of CTV-based coordination polymers.
Lastly, initial investigations into the self-assembly of CTV-based metal-organic
polyhedra took place. A synthetic protocol was determined using a simpler analogous
reaction, yielding four novel metal helicate structures, HEL1-4. This protocol was then
adapted to the CTV-based ligands and analysed using DOSY NMR. This showed that a
large species was being formed with a hydrodynamic radius of approximately 18.6 Å,
though the structure could not be confirmed.