pH Switching of Radical Reactivity and Orbital Conversion. Radicals are reactive species that have an unpaired electron, which is usually located in the highest occupied orbital. This proposal uses a combination of theory and experiment to design a new class of radical anions whose unpaired electron is not the highest occupied orbital, and whose electronic configuration reverts to the normal aufbau configuration upon protonation. These special radical anions will display unprecedented radical st ....pH Switching of Radical Reactivity and Orbital Conversion. Radicals are reactive species that have an unpaired electron, which is usually located in the highest occupied orbital. This proposal uses a combination of theory and experiment to design a new class of radical anions whose unpaired electron is not the highest occupied orbital, and whose electronic configuration reverts to the normal aufbau configuration upon protonation. These special radical anions will display unprecedented radical stability that is pH switchable, as well as ferromagnetism and conductivity upon oxidation. This project will exploit these unusual properties in the design of pH-switchable protecting groups for radicals for synthesis and polymerisation, and determine their role in oxidative stress and enzyme kinetics.Read moreRead less
Understanding and controlling the stereochemistry of free-radical polymerisation. The stereochemistry of a molecule, which relates to the relative spatial arrangement of its atoms, can have a profound effect on its physical and chemical properties. This project will use a computer-guided experimental approach to design new methods for controlling the stereochemistry of the polymers formed in free-radical polymerisation.
Controlling polymer microstructure with structured Lewis acids. Radical polymerisation is the most commercially important polymer process, favoured by industry for its broad scope and relatively low cost and environmental impact. However, its use in the synthesis of 'smart materials' for biomedical applications, molecular electronics and high-performance engineering applications has been hampered by the lack of microstructural control. This project aims to use a complementary combination of theo ....Controlling polymer microstructure with structured Lewis acids. Radical polymerisation is the most commercially important polymer process, favoured by industry for its broad scope and relatively low cost and environmental impact. However, its use in the synthesis of 'smart materials' for biomedical applications, molecular electronics and high-performance engineering applications has been hampered by the lack of microstructural control. This project aims to use a complementary combination of theory and experiment to develop novel structured Lewis acids for controlling the stereochemistry in free-radical polymerisation, and to utilise the recently discovered propagation catalysis conferred by simple Lewis acids to minimise defect structures and thereby improve the thermal and photostability of polymers.Read moreRead less
Shifting the trend in radical battery research . The project aims to address a growing problem of increasing energy consumption by storing intermittent energy from the sun in affordable and efficient flow batteries. The project expects to generate new knowledge in the areas of materials science and battery research by using innovative theoretical chemistry approaches to studying electrochemical properties of nitroxide radicals in ionic media. The project aims to develop radical organic flow batt ....Shifting the trend in radical battery research . The project aims to address a growing problem of increasing energy consumption by storing intermittent energy from the sun in affordable and efficient flow batteries. The project expects to generate new knowledge in the areas of materials science and battery research by using innovative theoretical chemistry approaches to studying electrochemical properties of nitroxide radicals in ionic media. The project aims to develop radical organic flow batteries by utilising ionic liquids to stabilise radicals. Intended outcomes of the project include improved efficiency of flow batteries that can store energy from widely used solar panels. This should provide significant benefits to Australia’s effort to switch to renewable energy technologies. Read moreRead less
Radicals in unconventional media - improving the sustainability of radical reactions through next generation ionic liquid radical chemistry. Despite significant advances over the past few decades, many free radical reactions are still carried out in organic solvents that are often toxic, flammable, difficult to recycle and employ undesirable reagents. It is timely that new free radical chemistry be developed that moves away from this "conventional" landscape. This proposal will develop a fundame ....Radicals in unconventional media - improving the sustainability of radical reactions through next generation ionic liquid radical chemistry. Despite significant advances over the past few decades, many free radical reactions are still carried out in organic solvents that are often toxic, flammable, difficult to recycle and employ undesirable reagents. It is timely that new free radical chemistry be developed that moves away from this "conventional" landscape. This proposal will develop a fundamental understanding of how free radicals interact with, and react in, (unconventional) ionic liquid solvents. This understanding will lead, in turn, to the development of new, more efficient, free radicals methods for the preparation of important materials that include biomolecules. Reduced environmental impact of free radical chemistry is the ultimate aim of this work.Read moreRead less
Quantum-chemical design of stereoregular polyphosphines for nanowires. In this project we will be designing and producing stereoregular polyphosphines that can self-assemble gold and silver complexes that mimic the molecular architectures of DNA and certain proteins. The longer gold complexes will behave as insulated nanowires, and are an exciting prospect for the development of nanotechnological devices. The shorter silver and gold complexes are expected to have significant antitumour propertie ....Quantum-chemical design of stereoregular polyphosphines for nanowires. In this project we will be designing and producing stereoregular polyphosphines that can self-assemble gold and silver complexes that mimic the molecular architectures of DNA and certain proteins. The longer gold complexes will behave as insulated nanowires, and are an exciting prospect for the development of nanotechnological devices. The shorter silver and gold complexes are expected to have significant antitumour properties. This project, which will use a unique theoretical-experimental approach to design the stereoregular polyphosphines, will enhance Australia's international scientific reputation, and will contribute to technological advancement in the national priority areas of nanotechnology and biotechnology.Read moreRead less
Electronic and Optical Properties of Doped Titanium Dioxide. Titanium dioxide, is widely used as a white pigment, owing to its high refractive index, second, only after diamond. Yellowing of rutile pigment particles, observed on prolonged exposure to sunlight, is a serious problem that pigment manufacturers would like to overcome. It is proposed that aluminium-doping of rutile limits this discolouration by altering the electronic structure of the rutile particles. This project seeks to identify ....Electronic and Optical Properties of Doped Titanium Dioxide. Titanium dioxide, is widely used as a white pigment, owing to its high refractive index, second, only after diamond. Yellowing of rutile pigment particles, observed on prolonged exposure to sunlight, is a serious problem that pigment manufacturers would like to overcome. It is proposed that aluminium-doping of rutile limits this discolouration by altering the electronic structure of the rutile particles. This project seeks to identify the specific electronic cause of the yellowing process, the nature of the Al defect,it's effect on the electronic structure of rutile, and the electronic perturbations that may occur when other dopants are used.Read moreRead less
Supramolecular Rip-n-Sew - New Computational Tools for Modelling Supermolecules. This project will develop new computational tools for predicting the chemical behaviour of large molecular and supramolecular systems with an accuracy and efficiency that has not previously been possible. It will also increase our mechanistic understanding of the principles governing supramolecular assembly in chemical and biological systems. This will enable cost and time savings in the design of advanced material ....Supramolecular Rip-n-Sew - New Computational Tools for Modelling Supermolecules. This project will develop new computational tools for predicting the chemical behaviour of large molecular and supramolecular systems with an accuracy and efficiency that has not previously been possible. It will also increase our mechanistic understanding of the principles governing supramolecular assembly in chemical and biological systems. This will enable cost and time savings in the design of advanced materials in the medical and agricultural contexts.Read moreRead less
A reliable physical model of molecular motion in crystals. The scientific benefits would flow, in the first instance, to the large national and international communities of scientists whose research makes use of the results of X-ray diffraction experiments. Applications of the research to amino acids and peptides will benefit investigations into the structure and molecular dynamics of biological systems, including proteins and enzymes. Studies of charge densities in crystals will obtain a standa ....A reliable physical model of molecular motion in crystals. The scientific benefits would flow, in the first instance, to the large national and international communities of scientists whose research makes use of the results of X-ray diffraction experiments. Applications of the research to amino acids and peptides will benefit investigations into the structure and molecular dynamics of biological systems, including proteins and enzymes. Studies of charge densities in crystals will obtain a standard tool for improved modelling of molecular motion, resulting in physically more realistic charge density functions, and hence greater insight into the relationship between properties of crystals and their constituent molecules.Read moreRead less
Metal Complexes for Activation and Scission of Small, Multiply-Bonded Molecules. The immediate outcome of this work is a series of new metal complexes capable of selectively cleaving the strong bonds present in a number of small molecules of industrial and synthetic importance. These outcomes will have a significant impact on the development of both novel transition metal systems for synthetic chemistry and new industrial procedures for the activation and cleavage of multiply-bonded molecules su ....Metal Complexes for Activation and Scission of Small, Multiply-Bonded Molecules. The immediate outcome of this work is a series of new metal complexes capable of selectively cleaving the strong bonds present in a number of small molecules of industrial and synthetic importance. These outcomes will have a significant impact on the development of both novel transition metal systems for synthetic chemistry and new industrial procedures for the activation and cleavage of multiply-bonded molecules such as molecular nitrogen and carbon dioxide. They will lead to new consumer products, better methods of production, and potential downstream applications such as nitric oxide/nitrogen dioxide converters and carbon dioxide emission controls.Read moreRead less