Towards supramolecular multifunctional architectures

This thesis begins with the introduction of supramolecular chemistry and an explanation of why this synthetic strategy is aptly suited for the creation of increasingly larger and more complex structures, beyond the limits of traditional covalent synthesis. An extensive definition of self-assembly and the building blocks used by biological systems to create its functional supramolecular architectures is given. A review of novel synthetic finite and infinite supramolecular architectures is provided; despite these accomplishments there are few reports of biologically relevant synthetic architectures, as well as functional architectures. This thesis hypothesizes that new currently unattainable architectures can be achieved by using established metal-ligand interactions tethered to unique functional synthons.; The first supramolecular synthon is a functionalized cyclic peptide. Cyclic peptides can vertically self-assemble via H-bonds into well-defined organic nanotubes with useful inclusion and transport properties, which can be readily tuned to suit a potential application via a range of synthetic modifications. By adding a pyridyl ligand to the periphery the cycle is imbued with a horizontal metal-coordination self-assembly mode that may facilitate supramolecular membrane formation.; Our second supramolecular synthon has an "X-shaped" cruciform molecule terminated with two pyridyl ligand. Cruciform molecules have outstanding optical properties with potential electro-optical applications. A polymeric cruciform system may be well suited for device fabrications owing to the ease of solution processing. Therefore we investigated a supramolecular polymeric strategy, to rapidly create a set of functional and solution processable coordination polymers.; The metal recognition unit chosen was a bimetallic "pincer" complex. This rigid, linear ditopic complex has a fast and quantitative coordination to pyridyl units, which were exploited to rapidly grow our supramolecular architectures.; Synthesis of our cyclic peptide ligand is completed and preliminary coordination studies confirm quantitative formation of primitive membrane architectures. The next phases of this research along with long-term future directions are outlined. Finally, several synthetic solutions are given to overcome the current limitations of our first generation of cruciform coordination polymers.