Understanding and Controlling the Self Assembly of Nanoscale Polyoxometalate Clusters

Lead Research Organisation: University of Glasgow
Department Name: School of Chemistry

Abstract

Nanoscale polyoxometalate clusters are molecules of metal oxide 10,000 times thinner than a human hair (a common metal oxide is rust) and they provide arguably an unrivalled class of molecules displaying a wide range of very interesting physical properties (they can be used as molecular machines to 'help' one molecule turn into another very quickly without waste, they can change colour in light and be used to store information like dyes on a DVD, be used like a battery to store electricity and even as very small magnets). This is because they can be thought of being based on a common set of building blocks, or lego bricks, that can be put together in many ways to build different types of molecular objects in 'one step'. Although these molecules are large and contain many thousands of building blocks, the way they build themselves is not understood and it is not possible to design the molecules using a blueprint or any other plan. Also these molecules are fragile and easily fall apart.In this research we will develop an approach to look at the 'one step' construction of these very large clusters with the aim of working out exactly how they are built. To do this we will need to adopt a number of different styles of detective work, from examining the structure of these molecules by making them more stable by wrapping them in a type of plastic, to trapping the individual lego bricks before they assemble into the nanoscale cluster. We will do this by weighing the clusters and building blocks present, and by measuring their molecular fingerprint when we make the clusters. We will also design different plans and test them by trying to predict the shape of the cluster before we make them. We will also look at the clusters using an extremely powerful microscope so we can accurately make this comparison.

Publications

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Boulay AG (2012) Morphogenesis of polyoxometalate cluster-based materials to microtubular network architectures. in Chemical communications (Cambridge, England)

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Boyd T (2011) Investigating cation binding in the polyoxometalate-super-crown [P8W48O184]40-. in Chemistry (Weinheim an der Bergstrasse, Germany)

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Fujibayashi M (2016) Exploring the solvent mediated assembly and redox activity of a POM-organic hybrid [Na(SO)(PhPO)MoMoO]. in New journal of chemistry = Nouveau journal de chimie

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Gao J (2012) Assembly of molecular "layered" heteropolyoxometalate architectures. in Angewandte Chemie (International ed. in English)

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MacDonald L (2018) Selective hydrogenation of nitroarenes using an electrogenerated polyoxometalate redox mediator. in Chemical communications (Cambridge, England)

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Miras H (2011) Direct Synthesis and Mass Spectroscopic Observation of the {M40} Polyoxothiometalate Wheel in European Journal of Inorganic Chemistry

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Miras HN (2012) Engineering polyoxometalates with emergent properties. in Chemical Society reviews

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Mitchell SG (2011) A mixed-valence manganese cubane trapped by inequivalent trilacunary polyoxometalate ligands. in Angewandte Chemie (International ed. in English)

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Musumeci C (2011) Programmable Surface Architectures Derived from Hybrid Polyoxometalate-Based Clusters in The Journal of Physical Chemistry C

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Points LJ (2016) An all-inorganic polyoxometalate-polyoxocation chemical garden. in Chemical communications (Cambridge, England)

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Quesada Cabrera R (2012) Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure in Journal of Solid State Chemistry

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Sartzi H (2015) Trapping the d Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand. in Angewandte Chemie (International ed. in English)

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Surman AJ (2016) Sizing and Discovery of Nanosized Polyoxometalate Clusters by Mass Spectrometry. in Journal of the American Chemical Society

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Tsunashima R (2011) Exploring the thermochromism of sulfite-embedded polyoxometalate capsules. in Physical chemistry chemical physics : PCCP

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Wilson EF (2011) Real-time observation of the self-assembly of hybrid polyoxometalates using mass spectrometry. in Angewandte Chemie (International ed. in English)

 
Description New inorganic clusters that can have potential applications in materials and electronics, an increased knowledge on how some techniques like MS and NMR can be used to predict / decipher their structures and formation processes.
Exploitation Route The development of MS and NMR techniques for this type of molecules is of high interest for people working in the field of inorganic chemistry, but also for industries and academics wishing to develop new analytical techniques for materials and nanoelectronics starting materials.
Sectors Aerospace, Defence and Marine,Chemicals,Electronics,Energy,Pharmaceuticals and Medical Biotechnology

URL http://www.croninlab.com
 
Description The clusters discovered and the understanding of their formation generated by this work have been used in a range of different research areas such as catalysis, nanofabrication and in biological-like environments
Sector Chemicals