New methods for the preparation of extended structures are rightly highlighted as being of great importance to the UK. The EPSRC Grand Challenge 'Directed Assembly of Extended Structures with Targeted Properties' (referred to as the DA Grand Challenge) is championed by some of the UK's leading academic scientists. Interest from pharmaceutical companies in this initiative has been excellent, particularly based on the nucleation and crystallisation targets outlined in the Grand Challenge Documentation. Impact of the Grand Challenge Network on other areas is much less evident, although it is clear that the basic premise of the Challenge fits many other sectors. In this Established Career Proposal my vision is to demonstrate, through both transformative science and personal leadership, how the central tenets of the DA Grand Challenge Idea can be translated across disciplines. In particular I will focus on two areas, increasing the impact of the network in the chemicals sector, with a special emphasis on transformative new routes to heterogeneous zeolite catalysts (which strongly fits another EPSRC priority area), and novel multifunctionality in medical delivery agents. The proposed programme is firmly rooted in the EPSRC remit but is designed to be outward looking to maximise transdisciplinary impact cutting across to other important areas of science. The specific science proposed here focuses on nanoporous materials. Zeolites are one of the most important class of industrially applied catalysts we have. Manipulation of zeolites into hierarchical porous structures and ultra-thin layers has also risen to great prominence as a method of introducing new and beneficial features into zeolite catalysts. The journal Science rated this type of research as one of the ten most important current areas of current science, and so its importance is recognised internationally. Metal organic frameworks (MOFs) are some of the most exciting and fast-developing materials that have been prepared in the last decade or so. The great versatility of the chemistry of these solids leads to ultra-high porosity, extreme flexibility, post synthetic modification potential and many other interesting and conceivably useful attributes. Because of this wide ranging chemistry and function, potential applications of these solids range from gas storage, separation and delivery, catalysis, and sensing all the way to biology and medicine.

Photovoltaic technology is critical to securing the future energy supply of UK and the exploration and development of new technologies that may significantly enhance efficiencies would be a major breakthrough for photovoltaics, for national energy strategy and provide a head-start for new UK industry. The deployment of next generation, low-cost and high-efficiency solar cells is a multifaceted challenge that requires a multidisciplinary effort and includes fundamental physics, material synthesis/processing, process development/optimization and full device fabrication and characterization. Boosting efficiency and lowering costs can only be achieved with a full-span vision of all device-related aspects. Considerations on materials costs, availability and environmental impact are also mandatory. Current solar cell technologies all rely on fundamental physical principles that are intrinsically limiting device efficiency. In order to overcome this theoretical limit new approaches are required that exploit different physical mechanisms. The proposed project aims to bring together advanced and novel materials with unique properties that can overcome theoretical limits. Specifically silicon-based quantum confinement and novel tuned-bandgap metal oxide semiconductors with high hole conductivity will be used to deliver the first all-inorganic bulk-heterojunction photovoltaic device capable of exploiting carrier multiplication and offering the potential of efficiencies beyond the theoretical limit of current technologies. Utilising low cost, non-degradable, non-toxic, abundant and environmentally-friendly materials as well as low cost and scalable fabrication strategies, the aim is to open up novel and transformative approaches based on nanotechnology. The proposed devices will represent at the end of the project a serious contender for future high efficiency low-cost photovoltaics with limited environmental footprint and they will open up a new era for low-cost solar energy harvesting. The proposal will bring novel elements from chemistry, nanotechnology, materials and plasmas together with device engineering, and will access expertise from world-leading groups in materials and photovoltaics.

Catalysis is an extremely important branch of science, which is vital in our modern society. It is estimated that about 90% of all processed chemical compounds have, at some stage of their production, involved the use of a catalyst. As a result catalysis is recognized as a key strategic priority area by EPSRC. In general, catalytic reactions are more energy efficient and, at least in the case of highly selective reactions, lead to reduced waste and undesirable compounds, which is an important consideration with dwindling global reserves of raw materials. New catalysts are being developed for use in alternative energy sources and new conversion technologies, for manufacturing of new materials, for synthesis of molecules such as pure drugs, and for the production of chemicals with minimal energy input. The importance of these developments cannot be overstated. In the past 10 years alone the Nobel Prize in Chemistry was awarded on three separate occasions for the outstanding achievement of scientists whose work has a strong bias in catalysis. Their combined work has revolutionized the field of fine chemical synthesis and chiral feedstock production using well defined and discrete homogeneous organometallic catalysts. Despite the phenomenal success of these homogeneous catalysts, further improvements and developments of new asymmetric catalysts, bio-catalysts and indeed heterogeneous catalysts will benefit from a greater understanding of the mechanistic pathways involved in the catalytic cycles. Undoubtedly a greater understanding of the mechanism can lead to enhanced performance, even with well established systems. Therefore this advancement in our mechanistic understanding of how catalysts function and operate will require the application and development of new techniques that can probe the catalytic reaction and reveal the inner workings of the mechanism in unsurpassed detail. One approach to address this is the development of a unique high pressure system enabling advanced Electron Paramagnetic Resonance (EPR) methods to be used for the first time to study catalytic reactions under extreme conditions. In many cases, paramagnetic metal centers or reaction intermediates are involved in catalytic cycles, so that EPR spectroscopy and the related hyperfine techniques, such as ENDOR and ESEEM, are ideal characterization tools to study reactions at high pressures as a means to gain further insights into reaction mechanism. Since pressure is a primary thermodynamic parameter of central importance in reaction kinetics, chemical equilibria, molecular conformations and molecular interactions, it is very important in catalysis, and becomes a crucial and available parameter to study the reaction mechanisms. Since the equilibria, selectivity, population of states, conformations of the catalyst - substrate intermediates, role of solvent interactions, can all be affected, HP-EPR will be able to examine these properties. The structure, redox states, electronic and spin states, dynamics, non-covalent interactions, conformation changes, relaxation behavior, can all be analysed by these advanced EPR techniques, using the high pressure facility as a means of controlling and enhancing mechanistic variables in order to facilitate their investigations. Pressure also influences the outcome of most chemical processes, and therefore the HP-EPR facility developed in this project can also be applied to a range of other problems in chemistry involving free radicals, from organic and inorganic reactions, to electron transfer and activation of small molecules. Specific collaborative projects in heterogeneous catalysis, spin crossover phenomena, and electron spin states in condensed media, will all be explored using this new HP-EPR assembly.

A sustainable society requires the efficient use of energy and renewable matter. It consequently demands selective new methodologies for the preparation of advanced materials. In this context and as resources based on fossil reserves are rapidly depleting, there are two requirements: first, a change from traditional stoichiometric, high energy methods that produce huge amounts of chemical waste to mild and clean catalytic processes; second, a major step change in chemicals production with fossil fuels being replaced by renewable resources as chemical starter units. The long term aim and vision of catalysis research at EaStCHEM and of this Critical Mass proposal in particular is to develop all-catalytic routes to useful chemicals from renewable resources. We will provide a research environment that both improves and expands the wide range of catalytic processes used in the chemical and pharmaceutical industries. To do this we will exploit renewable and alternative feedstocks including CO2, lignocellulose and other feedstocks formed on multimillion tonnes scale as waste products from agriculture and wood processing. This proposed change in how we access our essential chemicals requires a new generation of catalysts. The challenge is even larger because the renewable substrates are not only difficult to activate (CO2, lignin) but are often available not as pure substrates but as components of a very diverse crude mixtures (e.g. methyl oleate in tall oil). Therefore, novel robust catalysts are required which are capable of combining high activity with superb selectivity and substrate compatibility. The required selectivity resulting in high atom economy, efficiency and environmental factor will only be feasible through the development of new scientific and technological tools. To achieve this challenging objective, existing catalysts must undergo major improvements and new catalysts must be designed for as yet uncatalyzed reactions. As we believe homogenous catalysts offer the unique combination of unprecedented activities and high selectivity, it is timely to combine EaStCHEM's strengths in homogeneous catalysis in this critical mass program to develop sustainable production methods by changing to all-catalytic conversions of renewable feedstocks. The switch to a society which relies on chemical production from all-renewable resources is a challenge of GRAND proportions, and a roadmap for this change must be broken down into smaller components with suitable experts addressing achievable goals. In this proposal we have assessed the strengths in catalysis across EaStCHEM and have designed projects at a variety of risk levels that will significantly impact on the overall change necessary in the challenging move "from oil to biomass". We will: 1. use CO2 as an ever abundant C1 building block in chemical processes that exploit newly developed state-of-the-art catalytic transformations for C-H activation/carboxylation, polymer formation, as well as electro- and chemical reduction processes. 2. We will develop optimal catalysts for ether cleavage in 'real life samples' of lignin for maximising the potential of lignocellulose as a source of fuels and fine chemicals. By combining our expertise in ligand design and computational methods we will develop efficient catalyst based on N-heterocyclic carbenes, wide bite angle phosphines and oxidative enzymes and chemocatalysts. 3. We will develop novel catalytic methods to convert renewable and waste feedstocks to important products such as fuels, chemicals and polymers. As we anticipate that this combined effort will include the de-novo development of new catalyst we will also create a ligand and catalyst synthesis and discovery centre which will support the catalyst development process of all the workpackages for the full duration of the project and thereafter. By focusing our experience and skills in catalysis, we will contribute to a post-fossil fuels world.

Burning petrol and other hydrocarbons from fossil fuels is damaging to the environment and wasteful of resources that could otherwise be used to make substances that improve the quality of life. However, the strength of the carbon-hydrogen bond, coupled with the difficulties associated with selectively accessing a specific site on a particular molecule, means that highly reactive metal compounds are needed to catalyse such processes.A single C-H bond in methane, the simplest and most abundant hydrocarbon, is potentially the most financially important target for selective functionalisation, but the activation of C-H bonds in more complex hydrocarbons is also a highly desirable 'toolbox' component for scientists working in all areas of chemical synthesis. This selectivity will become increasingly more important as our palette of platform chemicals changes from fossil fuel-derived to biomass-derived in the coming years.Organometallic compounds of the lanthanides and actinides first gave a tantalising glimpse of their potential with the selective cleavage of one C-H bond in methane some 25 years ago, but the limitations of the supporting ligands precluded any further functionalisation step. Since then, a variety of C-H bond activation chemistry has been demonstrated at d- and f-block metal centres that has increased our fundamental understanding of this reaction, but not yet provided profitable applications. Recent advances in organometallic f-block chemistry (both in terms of academic breakthroughs, and characterisation methods), and the desire to find C-H activation catalysts not based on the rare and expensive platinum group metals, is now pushing f-block metals back to the forefront of C-H bond activation chemistry.We have made a variety of contributions to organometallic f-block chemistry that challenge traditional views of f-block structure and bonding, such as the isolation of f-block complexes with new polar metal-element bonds (J. Am. Chem. Soc. 2007), and the demonstration of unprecedented reactivity of the U=O oxo groups of the uranyl dication towards C-Si and N-Si bond cleavage (Nature, 2008).The proposed programme of work focuses on the selective activation and functionalisation of hydrocarbon C-H bonds, and builds on our recent successes and proof-of-concept results in functional organolanthanide and actinide chemistry. We have identified three mechanistically distinct types of C-H bond activation, and have combined them into one programme, to offer the highest chance of success. A fellowship offers the ideal opportunity for the PI to manage this intensive and internationally collaborative research programme and deliver new f-block catalysts for hydrocarbon activation.This work contributes to the Energy priority, by providing catalytic, atom-efficient, low-energy chemical routes to convert hydrocarbons from biomass or fossil fuels into high-value chemicals, so benefitting both industry and society.The fundamental understanding that comes from the reactivity and bonding studies of unusual f-block compounds improves our ability to handle nuclear materials and wastes, while the researchers on this project will gain actinide handling skills that are identified as a key shortage in the UK. Finally, the demonstration of important hydrocarbon chemistry by depleted uranium compounds would help to enhance the public image of uranium in our future nuclear age.