Polar organometallic chemistry provides an essential toolkit for transforming inert bonds into reactive bonds to make new compounds and materials. Very few aromatic molecules (e.g., pharmaceuticals, agrochemicals, perfumes) are made without polar organometallic chemistry being practiced at some stage in their manufacture. Though this chemistry has a long and successful history, it is currently at an exciting crossroads in its development with seemingly impossible challenges within it now on the verge of becoming possible. This project is designed towards fundamentally reforming the practice of polar organometallic chemistry making it more air and moisture compatible, greener, more atom-economical and sustainable. Research will focus on the synthesis, cultivation and exploitation of new s-block metal multicomponent reagents made by co-complexation protocols. Preliminary work has shown that mixing different components within the same environment (for example, two distinct metal complexes; or one metal but with an assortment of ligands) can lead to useful synergistic effects not possible with unmixed systems. The scope of the chemistry and the ability to construct new compounds and new materials to meet societal needs are thus greatly broadened. Based on earth-abundant metals, these co-complex reagents will be screened in key organic transformations, focusing on deprotonative metallation and metal-halogen exchange reactions as well as in tandem C-C bond forming methods (as an alternative to more expensive and less environmentally benign transition-metal-mediated approaches) targeting synthetically relevant organic substrates. Stoichiometric reactions will be upgraded to catalytic regimes to establish the ground rules for s-block synergistic catalysis focusing on intramolecular hydroamination reactions of a range of unsaturated molecules. A key objective of the project is to pioneer and extend the use of multicomponent polar organometallic reagents in Deep Eutectic Solvents (DESs). These DESs will provide more cost-effective, greener and biorenewable reaction media to those volatile organic solvents (VOC's) in which most polar organometallic chemistry is carried out today. Progress in this aim will go a long way to eventually realising the "impossible" challenge in polar organometallic chemistry of synthesising and utilising chemoselective organometallic reagents under air and/or in aqueous media. Dispensing with the need for a dry inert atmosphere would have genuine worldwide implications for the practice of polar organometallic chemistry both in academia and industry.

Complex multicellular life first appeared on Earth some 800 million years ago and subsequently diversified through a bewilderingly complex pattern of species originations/extinctions. However, this was not a steady and uninterrupted process. On at least five occasions the biota of the planet was devastated by a catastrophe that eliminated a considerable proportion of total biodiversity--including entire groups of organisms (higher taxa). These so-called 'mass extinctions' fundamentally changed the nature of life on Earth by steering evolution into a completely different trajectory. Of the 'Big Five' mass extinctions by far the least understood is the Devonian mass extinction that occurred ca.370 million years ago. There is widespread debate regarding both the timing and nature of this event, which has led to a complete lack of consensus regarding its causes. This proposal seeks to investigate the Devonian mass extinction from a fresh perspective focussing on changes in carbon-cycling. The Earth currently has two carbon-cycles of similar magnitude: a marine one based on photosynthetic plankton and a terrestrial one based on photosynthetic land plants. Fundamental changes in carbon-cycling took place during the Devonian due to dramatic changes in the nature of terrestrial vegetation. At the start of the Devonian land plants were centimetres tall, rooted in very shallow soils and covered a limited area of the continents. By the end of the Devonian vast swathes of the continents were shrouded in forests of trees tens of metres tall that deep-rooted into mature soils. These major vegetation changes caused profound changes in the terrestrial carbon-cycle (due to carbon sequestration from chemical weathering and biomass burial). We hypothesise that it was dramatic changes to the terrestrial carbon-cycle that disrupted the Earth system and caused the Devonian mass extinction. However, we believe that it was not a single catastrophic event (such as the bolide impact that caused the end Cretaceous mass extinction) but rather it occurred sequentially as discrete morphological/anatomical innovations led to changes in plant size and coverage causing step-changes in the terrestrial carbon-cycle. The research project will focus on the Devonian sequences of northern Spain. These are ideal because they: (i) are remarkably complete and incorporate known extinction events at the Frasnian-Famennian and Devonian-Carboniferous boundaries; (ii) accumulated in isolation on a large microcontinent and as such are not influence by species immigration/emigration and habitat tracking; (iii) contain an excellent fossil record of both marine plankton (acritarchs and chitinozoans) and terrestrial vegetation (plant spores/pollen). We will study the evolutionary dynamics of both the marine plankton and terrestrial vegetation through a study of species origination/extinction patterns. This biodiversity profile will be integrated with geochemical analyses that will identify perturbations in the Earth's carbon-cycle (in addition to nutrient cycling, redox conditions and volcanic activity). These data will be fed into an Earth Systems model for the Devonian carbon-cycle that we generate using inverse modelling techniques. The model will also incorporate data on the appearance of major plant groups and novelties (e.g. first forests). Together these data will shed light on the nature and timing of Devonian extinction events among primary producers and link them to changes in the carbon-cycle. Our research will clarify many aspects of the Devonian mass extinction (nature and timing) and link it to the monumental changes in carbon-cycling brought about by the dramatic evolution of terrestrial vegetation. This will also serve as a warning for the present day regarding consequences of human induced changes to the Earth's carbon-cycle bought about by deforestation, soil erosion and other detrimental activities.

QMol will realise a new generation of switchable organic/organometallic compounds, with the potential to fulfil societal needs for flexible energy harvesting materials, low-power neuromorphic computing, smart textiles and self-powered patches for healthcare. The possibility of creating these exciting materials derives from a series of world firsts by the investigators, demonstrating that advantageous room-temperature quantum interference effects can be scaled up from single molecules to self-assembled monolayers, new strategies for controlling molecular conformation and energy levels, and new methods of molecular assembly, which can be deployed in printed scalable architectures. The demand for wearable electronic devices has increased enormously in recent years and integration of these devices into textiles is highly desirable. A key problem is the need for a power supply, typically in the form of a battery or supercapacitor, which need to be recharged. To overcome this problem, QMol will develop flexible thermoelectric materials that can covert waste heat from the body and other sources into electricity. Progress in this direction has been made using disordered, doped polymer composites [eg ACS Appl. Mater. Interfaces 2020, 12, 41, 46348], but there is a need to develop higher-performance, inexpensive, easily processable, flexible thermoelectric materials. The best inorganic materials cannot fulfil these requirements and therefore QMol will focus on the development of high-performance, thin-film, organic/organometallic materials. In parallel with these developments, it is widely recognised that dendritic-synaptic interconnections among neurons in the brain embed intricate logic structures enabling decision-making that vastly outperforms any artificial electronic analogues, with extremely low power requirements. Moreover, the network in a brain is dynamically reconfigurable, which provides flexibility and adaptability to changing environments. To build artificial neural networks, which mimic this behaviour, QMol will develop thin-film, organic/organometallic materials, which embed complex logic possibilities in the material properties of a single circuit element and outperform recent realisations of such logic elements. The resultant current-voltage characteristic of these molecular memristors will exhibit history-dependent, non-volatile switching transitions between different conductance levels. As demonstrators of the wide potential of these new materials, by the end of the Programme, we shall deliver (i) smart textiles with in-built thermal management, (ii) cross-plane, memristive devices, which are a fundamental building block of a neuromorphic computer (iii) flexible organic thermoelectric energy generators (TEGs) and self-powered patches for healthcare. We have demonstrated that room-temperature quantum interference effects in monolayer molecular films can be used to enhance memristive switching, energy harvesting and thermal control. Since transport is perpendicular to the plane of such films, long-range order within the films is not required. QMol recognises that although monolayer films are of fundamental scientific interest, they are not technologically useful, because for example, in a device, it is not possible to create a significant thermal gradient across a monolayer in a perpendicular direction. Therefore the new materials envisaged by QMol will be finite-thickness multi-layers, which move the above functionalities into the third dimension. The team comprises nine academics, with track records at the forefront of their fields. They are supported by twenty world leaders from industry and academia, comprising the six-member QMol Advisory Board and fourteen external partners. Eight postdoctoral researchers (PDRAs) will be employed by QMol and will be joined by eight PhD students, an industry-funded CASE student and an industry-funded PDRA.