Final Report Summary - MECOFUPO (Metal-containing functional polymers through subcomponent self-assembly) In the first part of the MECOFUPO project we developed a new kind of material using the techniques of subcomponent self-assembly. The condensation of linear diamines and dialdehydes around copper(I) templates in the presence of bulky trioctylphosphine ancillary ligands gave a linear, conjugated polymeric material in Dimethyl sulfoxide (DMSO) solution. This new, unprecedented material was then characterised by different types of nuclear magnetic resonance (1H, 13C, 19F and 31P NMR), mass spectrometry, viscometry, micro-rheology, imaging techniques such as Scanning electron microscopy (SEM), Atomic force microscopy (AFM), Energy-dispersive x-ray spectroscopy (EDX), Ultraviolet imaging (UV), photoluminescence and conductivity. The polymer solution was observed to undergo sol to gel transition as the temperature was raised to 140 degrees Celsius, in contrast with the behaviour of most gel forming polymers, which did so upon cooling. We attributed the sol to gel transition to the formation of CuIN4 cross-links as the equilibria 2[CuIN2P2], [CuIN4] + [CuPn]+ + 4-n P favourer the right-hand side at higher temperatures. The material was also observed to exhibit thermochromism and photoluminescence, with the colour and intensity of both absorption and emission exhibiting temperature dependence. This material thus responded predictably to combinations of stimuli such as heat, light and mechanical shear, in an interconnected way, as was required to generate complex function. In addition, the viscoelasticity of the gel showed an unexpected two-step process gelation. Motivated by the results that were obtained for the first polymer generation we pursued building a different kind of polymer, based on double helicate architecture. The synthesised molecules were thought to act as molecular copper wire as shown during previous work. The obtained material was characterised by all standard techniques. The results obtained in particles' characterisation showed aggregation into larger structures either once deposited on a silicon surface or in solution. This suggested the feasibility of growing larger molecules with this type of system. Preliminary results on conductivity and electrochemistry demonstrated that the molecule was electro-active, therefore suggesting its potential use in electrochemical devices. This type of material was anticipated to find applications in nano-electronics. Different collaborations were set between three departments at the University of Cambridge in order to study the properties of this new, unprecedented material. Related documents Final Report - MECOFUPO (Metal-containing functional polymers through subcomponent self-assembly)
