Final Report Summary - SPIM (Metallopolymers with Metal-Metal Bonds: The Synthesis, Characterization and Applications of Novel Molecular Wires)
Various paddlewheel dimetallic precursors (Ru2, Re2) with halides at axial position were synthesised. Organic heterocyclic spacers based on thiophene and benzothiadiazole systems containing alkynyl groups were synthesised and characterised.
After synthesis of functional organic ligands containing alkynyl groups, coupling reactions (Pd or Cu-catalysed) were explored to afford functional metallopolymers with M-M bonds. For example, reaction of the [Ru2(O2CR)4Cl2] species with alkynyl functional groups (e.g. [HC2ArC2H]) afforded conjugated hybrid materials with M-M and C-C bonds in the main chain (including with thiophene-based spacers). The synthesised materials would be of considerable interest as emissive and conductive nanowires. Due to the rigid-rod like structure, the synthesised polymers were not fully soluble in common organic solvents. However solubility was improved by incorporating longer alkyl groups (R) on the dimetallic precursors.
In an unexpected development, we also found that some of the polythiophene materials alone undergo interesting self-assembly behaviour in their own right.
In addition to the metal-containing polymer work we also observed that the polythiophene based materials undergo interesting self-assembly in solution, to give nanowires. In this regard, amphiphilic polythiophene based materials are of particular interest. Self-assembly of these materials was explored to generate conductive and emissive nanowires which is of intense interest for its nanoscale electronic and optoelectronic applications.
I have been working on other projects in collaboration with other researchers in Prof. Ian Manners' group involving synthesis, characterisation and self-assembly of functional metallopolymers containing various transition metals. Together with Dr Joe Gilroy we synthesised well-defined main-chain hetero-bimetallic (Fe and Co) block copolymers via photocontrolled ring-opening polymerisation (ROP). The self-assembly in solution was of our interest to access to new redox-active hetero-bimetallic block co-micelle architectures. With Dr Laurent Chabanne, we developed the route to synthesise well-defined organic-organometallic block copolymers (such as polystyrene-b-polyferrocenylsilane) via photocontrolled ROP. Together with the Ph.D. student Rumman Ahmed, we explored organic-organometallic hierarchical organised nanostructures. With the Ph.D. student David Lunn, we started to investigate the scope of cylindrical metal-containing 1D micelles for using as effective tandem catalyst platforms. Collaborations have been set up with other research groups (such as Prof. Rob Richardson in Physics) that are involved in characterising the materials that have been prepared.
3. Some of the work have been published in international journals, and also presented in conferences as oral presentation (94th Canadian Chemistry Conference and Exhibition, Montreal, Canada, 2011; 242nd ACS National Meeting, Denver, United States, 2011).
The results on p-conjugated and metal-containing polymers advance the important area of functional polymer based nanostructures. The work on the conjugated systems with M-M, C-C, and thiophene moieties in the main chain certainly opens up an area of new functional hybrid materials although these materials suffer from solubility problems and also the synthetic routes towards these materials are not straightforward. The self-assembly of thiophene based polymers yielding conductive nanowires is of great interest as these materials represent one of the most well-studied crystalline p-conjugated polymers and has been investigated as an active component of organic-field effect transistors, solar cells, and light emitting diodes. Some of the results have been published in some of the best scientific journals and a number of future papers are being written up for similar reputed journals (Macromolecules, Angew. Chem., Int. Ed., J. Am. Chem. Soc.).
The fellowship has provided Dr Sanjib K. Patra with a tremendous boost with regard to career development. As a result, the fellowship has helped him to obtain academic position (Assistant Professor) in one of the highly reputed institutes in India (Indian Institute of Technology). The training and experience gained while working with one of the world leaders in polymer science and nanoscience (Prof. Ian Manners) during the Marie Curie fellowship, will be very crucial to help him to start his independent academic career in India. On his return to India there are high possibilities for long term collaborative research to develop the new area emerged through this Marie Curie program, thus providing an excellent means of engagement between the Indian and European scientific communities.
After synthesis of functional organic ligands containing alkynyl groups, coupling reactions (Pd or Cu-catalysed) were explored to afford functional metallopolymers with M-M bonds. For example, reaction of the [Ru2(O2CR)4Cl2] species with alkynyl functional groups (e.g. [HC2ArC2H]) afforded conjugated hybrid materials with M-M and C-C bonds in the main chain (including with thiophene-based spacers). The synthesised materials would be of considerable interest as emissive and conductive nanowires. Due to the rigid-rod like structure, the synthesised polymers were not fully soluble in common organic solvents. However solubility was improved by incorporating longer alkyl groups (R) on the dimetallic precursors.
In an unexpected development, we also found that some of the polythiophene materials alone undergo interesting self-assembly behaviour in their own right.
In addition to the metal-containing polymer work we also observed that the polythiophene based materials undergo interesting self-assembly in solution, to give nanowires. In this regard, amphiphilic polythiophene based materials are of particular interest. Self-assembly of these materials was explored to generate conductive and emissive nanowires which is of intense interest for its nanoscale electronic and optoelectronic applications.
I have been working on other projects in collaboration with other researchers in Prof. Ian Manners' group involving synthesis, characterisation and self-assembly of functional metallopolymers containing various transition metals. Together with Dr Joe Gilroy we synthesised well-defined main-chain hetero-bimetallic (Fe and Co) block copolymers via photocontrolled ring-opening polymerisation (ROP). The self-assembly in solution was of our interest to access to new redox-active hetero-bimetallic block co-micelle architectures. With Dr Laurent Chabanne, we developed the route to synthesise well-defined organic-organometallic block copolymers (such as polystyrene-b-polyferrocenylsilane) via photocontrolled ROP. Together with the Ph.D. student Rumman Ahmed, we explored organic-organometallic hierarchical organised nanostructures. With the Ph.D. student David Lunn, we started to investigate the scope of cylindrical metal-containing 1D micelles for using as effective tandem catalyst platforms. Collaborations have been set up with other research groups (such as Prof. Rob Richardson in Physics) that are involved in characterising the materials that have been prepared.
3. Some of the work have been published in international journals, and also presented in conferences as oral presentation (94th Canadian Chemistry Conference and Exhibition, Montreal, Canada, 2011; 242nd ACS National Meeting, Denver, United States, 2011).
The results on p-conjugated and metal-containing polymers advance the important area of functional polymer based nanostructures. The work on the conjugated systems with M-M, C-C, and thiophene moieties in the main chain certainly opens up an area of new functional hybrid materials although these materials suffer from solubility problems and also the synthetic routes towards these materials are not straightforward. The self-assembly of thiophene based polymers yielding conductive nanowires is of great interest as these materials represent one of the most well-studied crystalline p-conjugated polymers and has been investigated as an active component of organic-field effect transistors, solar cells, and light emitting diodes. Some of the results have been published in some of the best scientific journals and a number of future papers are being written up for similar reputed journals (Macromolecules, Angew. Chem., Int. Ed., J. Am. Chem. Soc.).
The fellowship has provided Dr Sanjib K. Patra with a tremendous boost with regard to career development. As a result, the fellowship has helped him to obtain academic position (Assistant Professor) in one of the highly reputed institutes in India (Indian Institute of Technology). The training and experience gained while working with one of the world leaders in polymer science and nanoscience (Prof. Ian Manners) during the Marie Curie fellowship, will be very crucial to help him to start his independent academic career in India. On his return to India there are high possibilities for long term collaborative research to develop the new area emerged through this Marie Curie program, thus providing an excellent means of engagement between the Indian and European scientific communities.