The Crystal Sponge (CS) method is a highly promising, proven technique where gold standard single crystal X-ray diffraction (SCXRD) can be applied to samples that can either only be produced in minute amounts (those too small to grow a crystal) or those that cannot be crystallised (gases, liquids, and oils) to obtain atomic resolution chemical structures. The analyte (guest) is soaked into a crystalline porous framework (host) and the aggregate crystal structure is subsequently solved, revealing new structural information on the guest. The structures of ~450 analytes have been published using the CS method to date, while many times more have been studied in commercially sensitive projects or remain to be published. However, there are ongoing problems with the CS-SCXRD method, including: 1.A lack of different sponges available, with most work carried out using a single generic sponge. 2. An associated limited analyte scope, due to inappropriate chemical compatibility and/or poor soaking, with a glaring lack of alternatives. 3. A lack of reliable synthetic methods to make suitable large, untwinned crystals of the known sponges. 4. Laborious solvent exchange and activation processes. 5. Long soaking times due to pore diffusion into large crystals and subsequent careful evaporation of loading solvent, with consequently poor reproducibility of analyte loading. 6. A relatively low hit-rate for successful data collections, meaning the process can be repetitious and time consuming. 7.Relatively poor data quality rendering structure refinements difficult and laborious. 8.Quality of results generally lower than the community accepted standard. These problems have resulted in poor uptake and accordingly there are few experts and limited adoption as an 'analytical' method for determining chemical structure. Electron Diffraction is a game changing technique that will improve this situation by offering structure determination on nanocrystals as small as 100nm in size, two orders of magnitude smaller than X-ray diffraction, as well as cryogenic loading and analysis of powders, fragile samples and solvates. We hypothesise that ED is, therefore, highly suited to CS analysis and our proposal focusses on developing the CS method for ED by demonstrating the following potential advantages: 1.Many more potential sponge materials will be explored (including highly inert sponges) as there is no longer a requirement for large single crystals. 2.Much more rapid and complete analyte soaking, due to ~6 orders of magnitude decrease in total sponge particle size, with concomitant decreases in required analyte amounts. 3.Quicker and simpler handling procedures, as there are minimal concerns about sponge nanocrystals drying out or cracking. 4.New soaking procedures and protocols become possible, e.g., soaking analytes into completely dry particles. 5.Novel sample preparation and presentation becomes possible, due to less technological constraints, e.g., multiple nanocrystals on sample grids (ED) versus individual crystals on a single pin-like mount (SCXRD). 6.Much faster data collection times, allowing analysis of multiple nanocrystals from one batch very quickly (potentially automated) on a single grid, therefore outrunning any sample/analyte instability. 7. Potential for screening multiple sponge materials on one grid with individual or multiple analytes, to rapidly determine which sponge is best for which material type. In doing so, we will demonstrate the CS method is applicable to a broad subset of new sponges and analytes, ultimately rejuvenating the technique in the eyes of academia and industry and finally unleashing its potential to become the go-to technique for structure determination of uncrystallisable molecules.

Recent environmental concern has raised our awareness of a low-carbon future, demanding immediate action towards sustainable energy solutions. Latest geopolitical events and rising energy prices have further stimulated a global sense of energy independence and security, calling for drastic expansion and deployment of homegrown renewable energy, such as wind, solar, tidal power etc, all of which require efficient grid storage systems for integration. It is in this context that batteries, particularly lithium-ion batteries (LIBs), come to the spotlight. Whilst LIBs have been dominating the market for mobility applications, such as portable electronics and electric vehicles, they also make up 90% of the current global grid storage market. However, Li's scarcity in Earth's crust with an uneven geographical distribution means that the Li-ion technology is not a sustainable net-zero solution in terms of affordability and ability to secure energy independence. In contrast, originating from the same alkali-metal family, K-ion chemistry shows several key advantages in its economic viability, strategic relevance, and cycling stability, placing K-ion batteries (KIBs) among the prioritised new battery technologies for future development, especially for stationary applications. This project aims to solve the bottleneck problem in the current KIB development on cathodes and will design a library of new metal fluoride open framework (MeFOF) materials that can meet the criteria for cathode application in both cost and durability. The design strategy of these materials stems from the structure diversity and chemical flexibility of the alkali-metal-fluoride chemistry and is corroborated by the recent progress in their mechanochemical synthesis. Their crystal structures are supported by corner-shared metal-fluoride-octahedra linkages and exhibit a variety of open-channel motifs with desirable cavity sizes to host large K ions. These unique motifs not only constitute a library of advantageous topologies for facile K ion transport, but also compose a robust and flexible scaffold for reversible K ion accommodation. In this work, an emphasis will be laid on elucidating the impact of the materials' cavity sizes, structural flexibility, and chemical substitution on their electrochemical performances. Through an investigation of MeFOFs' structure-property relationships, not only will their design principle and optimisation be established to facilitate KIB commercialisation, but a novel laboratory-based instrumentation for advanced atomic structure characterisation via pair distribution function technique will also be developed to expedite the development of novel functional materials that have complex structural properties, with a broader implication beyond energy storage.

Electron diffraction (ED) is about to become a quantitative technique that will be used routinely to solve and refine crystal structures from extremely small specimens. These materials are, at best, difficult to tackle with X-ray diffraction (XRD) and many are completely beyond the reach of current capabilities. The very different physics of electron scattering means that structures of crystals with grain sizes smaller than a micrometre, and materials containing light elements like hydrogen and lithium, can be solved. This step-change will be made possible by taking the methods and detectors currently used for XRD, which have been developed over decades to a high level, and combining them with a purpose-built electron diffractometer. The resulting equipment allows routine analysis of nanoscale materials. This new technology opens many doors, in some fields saving months of work in crystallisation and crystal growth. Unsurprisingly, there is intense interest both on a national and international level. Electron diffraction itself is not new, but the factors that allow it to reach beyond XRD, particularly multiple scattering, need to be considered when modelling the data produced in these measurements. This is still very much a work in progress, and it will be essential to bridge the gap between disciplines, bringing in knowledge and methods from electron microscopy, to develop the method to its full potential. These machines have become commercially available only in the last year. To remain competitive in structural science, the UK must invest in this area, and can take a global lead by doing so promptly. The widest benefit of this new capability for UK researchers will be provided by a national facility for ED that has both capacity and expertise to develop this nascent technology for routine and widespread use. The National Crystallography Service (NCS) at the University of Southampton (UoS) is well-placed to deliver such a facility, building on its success in routinely providing structure solution and refinement using high-value equipment that is unavailable to most researchers in their home institutions. The University of Warwick (UoW) has nationally leading electron microscopy and XRD facilities with a proven success in offering multiuser access. UoW also has a leading position in modelling and developing ED techniques and brings a suite of methods (cryogenic holders, heating holders, MEMS-based in-situ holders, graphene oxide support films) that will extend ED capabilities into new areas. Together, UoS and UoW will provide a dual site, single national facility that will build on existing world class lab infrastructure, deliver the technique immediately at both national and local scale, and develop the method going forward to take advantage of this opportunity for the UK. Four areas are identified as having the most to gain immediately from new ED techniques: pharmaceuticals; metal-organic frameworks; inorganic materials and molecular solids. Industry, in particular Pharma, realises the impact of ED and is keenly expressing a need for access to the technique. There is therefore strong support for the proposed facility from both academia and industry, and leading representatives from these communities in the UK have agreed to form an independent ED working group and act as champions to promote the method and facility. To understand how ED should develop, matching capacity and capabilities to the needs of the UK science community, the working group and the UoS/UoW team will undertake a landscaping exercise that will align with NCS national access cycles. This will allow new communities to be identified and aid strategically informed investment to grow UK capacity and research in the fundamental and essential area of atomic structure determination. The timing for this facility is ideal as ED technology now becoming available aligns with swathes of research communities demanding it.

The Periodic Table is mainly composed of metals. Thus, metal-metal bonding is a vast burgeoning field that is fundamental to driving step-changes in our understanding of structure, bonding, reactivity, and magnetism. Over 177 years the s-, p-, and d-blocks have produced numerous routinely isolable examples of varied metal-metal bonding motifs. In contrast, isolable actinide-actinide (An-An) bonding, one of the top goals of synthetic An-chemistry, has remained elusive in all that time, precluding assessment of reactivity patterns that are a central tenet of understanding metal-metal bonding. This adventurous project aims to exploit our recent discovery of molecular isolable thorium-thorium bonding (Nature 2021, 598, 72-75), which describes surprising sigma-aromatic bonding to record principal quantum number 6 and 7th row of the Periodic Table and multi-electron small molecule activation reactivity. Building on our preliminary result, this project seeks to expand the range of An-An complexes, determine their reactivity trends, and probe their electronic structure and physicochemical properties using a comprehensive range of experimental and theoretical characterisation techniques. This will involve a wide range of project partners and national and international research facilities brought together into a cohesive and interleaved approach. This research is strategically important with respect to the nuclear sector, as it will retain a skilled ECR and train two new ones in a known UK skills-shortage area, and together with stakeholders we will develop 'best practice' methods for handling radioactive elements, thus promoting knowledge transfer at the academia:industry interface. By studying the compounds outlined in the project, new applications of analytical techniques will be developed, and the resulting methodological advances will develop the capability and health of those disciplines in-house, and also more broadly because those techniques involve facilities and researchers that work across many other areas that could benefit from the transfer of new working ways. This project is timely to develop and our preliminary results show the work is achievable and impactful. Thus, we request funds commensurate with the scope and ambition of the proposed work to develop this promising area in order to capitalise on our breakthrough, stay at the international forefront of this newly created and exciting field, and generate results of international significance to An-chemistry.

The proposed CDT will address the UK's need for a pipeline of highly skilled scientists and engineers who will be able to secure the country's position as the global leader in the science and technology of two-dimensional materials (2DMs). Having started with the discovery of graphene at the University of Manchester, this research field now encompasses a vast number of 2DMs, 2DM-based devices, composites, inks, and complex heterostructures with designer properties. Numerous proposals for applications have emerged from research groups worldwide, some of them already picked up and being developed by big established companies and a large number of start-ups (30+ spin-outs just from the two partner universities, Manchester and Cambridge). Many of the ideas put forward require further research and validation and many more are expected to emerge, thanks to the unique properties of this new class of advanced materials and the ability to use modelling to predict new useful combinations of 2DMs or design conditions that bring about new properties. The CDT will support and enable new avenues of research and the development of 2DM-based technologies and work with industry partners to accelerate lab-to-market development of products and processes that leverage the exceptional properties of 2DMs. 2DMoT CDT will be an important part of graphene and 2D Materials eco-system centred on the Manchester and Cambridge innovation networks. It will contribute to the plans by the local authorities, in particular, of the Greater Manchester Combined Authority, to pilot Manufacturing Innovation Networks focused on graphene & nanomaterials, coatings and technical textiles. Industrial co-supervision of research projects will accelerate realisation of new products and technologies enabled by 2DMs, which is key to competitiveness. The CDT will implement a new approach to PhD research training by incorporating individual research projects into several overarching, multidisciplinary research missions with 2-3 CDT students a year joining each research mission, either at Manchester or Cambridge, and gradually forming 8-10 researcher teams incorporating CDT students at different stages of their PhD and involving several research groups with complementary expertise, working collaboratively and sharing ideas and knowledge. All students will have opportunities to shape their own projects and overall research missions, creating an inclusive environment, ideal for peer-to-peer learning and innovation. A 6-months-long formal taught programme at the start of PhD will be complemented by further advanced skills training during the research phase, transferrable skills training and research schools and workshops organised jointly with leading international research centres and the CDT business partners. Environmental sustainability of the developed products and technologies will be a focal point of the CDT programme, with specialist training and considerations of sustainability embedded in all research missions. Training in innovation and commercialization of research, project management, responsible research and innovation, and dealing with the media will be mandatory for all CDT students. To ensure that the benefits of CDT training are available to a wider group of PhD researchers, a range of CDT events - residential conferences, seminars, research workshops, commercialisation training - as well as some of the courses, will be open to non-CDT students whose research interests are aligned with the CDT research missions. Outreach events will form an important part of CDT activities, in particular participation in Science festivals, British Science weeks, Bluedot, Science X, with exhibits showcasing the science of 2DMs and their developing applications.