MECOFUPO · Metal-containing Functional Polymers through Subcomponent Self-Assembly
FP7 — People (Marie Curie Actions)
- Duration
- 2009-05-01 → 2011-04-30
- EU contribution
- €171,301
- Participants
- 1
- Scheme
- MC-IEF
Lines connect the coordinator with its partners.
Results in brief
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.
Data: CORDIS, © European Union
Project objective
This research proposal comprises two projects grouped around the idea of generating new polymeric materials using the technique of subcomponent self-assembly, which allows the preparation of complex structures from simple building blocks that come together around metal-ion templates via coordinative and covalent bond formation. The success of Part A will result in the preparation of double-helical polymers consisting of two self-assembled organic polymer strands that wind around a linear array of copper(I) ions. Initial studies have validated the concepts behind our synthetic strategy, and electrochemical measurements together with DFT calculations indicate a high level of electronic delocalization between the copper ions indicating that these polymers could serve as electrically conductive “molecular wires”. Part B will generate a different series of modular metal-organic polymers, consisting of a poly(imine)chain built up using a high-yielding imine exchange reaction. This chain will be bound to and stabilised by copper(I) ions that are also linked to ancillary ligands that fit snugly around the polymer chain using the idea of “steric complimentarity”. Once we have worked out the scope of the chemical reactions underpinning the formation of these polymers, a wide variety of different polymeric materials are predicted to be accessible. Key properties of these materials, such as strength, flexibility, and conductivity, will be tuneable through the incorporation of different monomer units. The self-assembly reactions used to generate these polymers will be carried out in aqueous solution. Water will be the only by-product of many of the condensation reactions that generate polymers. Our objectives in undertaking this project are twofold: to generate new polymeric materials that might possess useful properties (such as electrical conductivity and the ability to self-repair through dynamic reassembly), and to advance the knowledge of molecular self-assembly.
Original text from CORDIS.
Participants
- THE CHANCELLOR MASTERS AND SCHOLARS OF THE UNIVERSITY OF CAMBRIDGE · CAMBRIDGECoordinatorUnited Kingdom
Links
Data: CORDIS, © European Union