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.
Organisations
People |
ORCID iD |
| Leroy Cronin (Principal Investigator) |
Publications
Pradeep CP
(2008)
"Bottom-up" meets "top-down" assembly in nanoscale polyoxometalate clusters: self-assembly of [P4W52O178](24-) and disassembly to [P3W39O134](19-).
in Journal of the American Chemical Society
Ritchie C
(2009)
Spontaneous assembly and real-time growth of micrometre-scale tubular structures from polyoxometalate-based inorganic solids.
in Nature chemistry
Miras HN
(2010)
Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}.
in Chemical communications (Cambridge, England)
Rosnes MH
(2010)
Assembly of modular asymmetric organic-inorganic polyoxometalate hybrids into anisotropic nanostructures.
in Journal of the American Chemical Society
Pradeep CP
(2011)
Design and synthesis of "dumb-bell" and "triangular" inorganic-organic hybrid nanopolyoxometalate clusters and their characterisation through ESI-MS analyses.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Vilà-Nadal L
(2011)
Combined theoretical and mass spectrometry study of the formation-fragmentation of small polyoxomolybdates.
in Inorganic chemistry
Tsunashima R
(2011)
Exploring the thermochromism of sulfite-embedded polyoxometalate capsules.
in Physical chemistry chemical physics : PCCP
Mitchell SG
(2011)
A mixed-valence manganese cubane trapped by inequivalent trilacunary polyoxometalate ligands.
in Angewandte Chemie (International ed. in English)
Akutagawa T
(2011)
Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines.
in Inorganic chemistry
Miras H
(2011)
Direct Synthesis and Mass Spectroscopic Observation of the {M 40 } Polyoxothiometalate Wheel
in European Journal of Inorganic Chemistry
Cooper GJ
(2011)
Osmotically driven crystal morphogenesis: a general approach to the fabrication of micrometer-scale tubular architectures based on polyoxometalates.
in Journal of the American Chemical Society
Wilson EF
(2011)
Real-time observation of the self-assembly of hybrid polyoxometalates using mass spectrometry.
in Angewandte Chemie (International ed. in English)
Mitchell SG
(2011)
Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays.
in Inorganic chemistry
Vilà-Nadal L
(2011)
Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters.
in Physical chemistry chemical physics : PCCP
Gao J
(2011)
Self-assembly of a family of macrocyclic polyoxotungstates with emergent material properties
in Chemical Science
Hutin M
(2011)
Controlling the Molecular Assembly of Polyoxometalates from the Nano to the Micron Scale: Molecules to Materials
in Israel Journal of Chemistry
Musumeci C
(2011)
Programmable Surface Architectures Derived from Hybrid Polyoxometalate-Based Clusters
in The Journal of Physical Chemistry C
Boyd T
(2011)
Investigating cation binding in the polyoxometalate-super-crown [P8W48O184]40-.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Miras H
(2012)
Sulfite Anions as Structure-Directing Templates for the Engineering of Modular Polyoxometalates
in European Journal of Inorganic Chemistry
Endo D
(2012)
Molecular Motions and Hydrogen-Bonding Networks in ( o -Aminoanilinium)-(Crown Ethers)-[PMo12O40]4- Crystals
in Bulletin of the Chemical Society of Japan
Gao J
(2012)
Assembly of molecular "layered" heteropolyoxometalate architectures.
in Angewandte Chemie (International ed. in English)
Boulay AG
(2012)
Morphogenesis of polyoxometalate cluster-based materials to microtubular network architectures.
in Chemical communications (Cambridge, England)
Quesada Cabrera R
(2012)
Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure
in Journal of Solid State Chemistry
Lydon C
(2012)
Nanoscale growth of molecular oxides: assembly of a {V6} double cubane between two lacunary {P2W15} polyoxometalates.
in Angewandte Chemie (International ed. in English)
Miras HN
(2012)
Engineering polyoxometalates with emergent properties.
in Chemical Society reviews
Cronin L
(2012)
From serendipity to design of polyoxometalates at the nanoscale, aesthetic beauty and applications.
in Chemical Society reviews
Gabb D
(2012)
Organic-soluble lacunary {M2(P2W15)2} polyoxometalate sandwiches showing a previously unseen aßßa isomerism.
in Dalton transactions (Cambridge, England : 2003)
Thiel J
(2012)
Insights into the Self-Assembly Mechanism of the Modular Polyoxometalate "Keggin-Net" Family of Framework Materials and Their Electronic Properties
in Crystal Growth & Design
Miras HN
(2012)
Oscillatory template exchange in polyoxometalate capsules: a ligand-triggered, redox-powered, chemically damped oscillation.
in Journal of the American Chemical Society
Lydon C
(2012)
Directed assembly of nanoscale Co(II)-substituted {Co9[P2W15]3} and {Co14[P2W15]4} polyoxometalates.
in Chemical communications (Cambridge, England)
Yin P
(2013)
Exploring the programmable assembly of a polyoxometalate-organic hybrid via metal ion coordination.
in Journal of the American Chemical Society
Chen W
(2013)
0D to 1D Switching of Hybrid Polyoxometalate Assemblies at the Nanoscale by Using Molecular Control.
in ChemPlusChem
Vilà-Nadal L
(2013)
Polyoxometalate {W18O56XO6} clusters with embedded redox-active main-group templates as localized inner-cluster radicals.
in Angewandte Chemie (International ed. in English)
Jing B
(2013)
Polyoxometalate macroion induced phase and morphology instability of lipid membrane
in Chemical Science
Molina PI
(2013)
Exploring the assembly of supramolecular polyoxometalate triangular morphologies with Johnson solid cores: [(Mn(II)(H2O)3)2(K?{a-GeW10Mn(II)2O38}3)]19-.
in Inorganic chemistry
Winter RS
(2013)
Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Robbins PJ
(2013)
Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.
in Chemical communications (Cambridge, England)
Zang HY
(2013)
Template-directed assembly of polyoxothiometalate scaffolds into nanomolecular architectures.
in Angewandte Chemie (International ed. in English)
Winter RS
(2014)
Controlling the minimal self assembly of "complex" polyoxometalate clusters.
in Journal of the American Chemical Society
Zhan C
(2014)
Time-resolved assembly of cluster-in-cluster {Ag12}-in-{W76} polyoxometalates under supramolecular control.
in Angewandte Chemie (International ed. in English)
Sans V
(2014)
Non-equilibrium dynamic control of gold nanoparticle and hyper-branched nanogold assemblies
in Chemical Science
Sartzi H
(2015)
Trapping the d Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand
in Angewandte Chemie
Sartzi H
(2015)
Trapping the d Isomer of the Polyoxometalate-Based Keggin Cluster with a Tripodal Ligand.
in Angewandte Chemie (International ed. in English)
Zheng Q
(2015)
Following the Reaction of Heteroanions inside a {W 18 O 56 } Polyoxometalate Nanocage by NMR Spectroscopy and Mass Spectrometry
in Angewandte Chemie
Zhang B
(2015)
Self-assembly of triangular polyoxometalate-organic hybrid macroions in mixed solvents.
in Chemical communications (Cambridge, England)
Zhan CH
(2015)
Assembly of Tungsten-Oxide-Based Pentagonal Motifs in Solution Leads to Nanoscale {W48}, {W56}, and {W92} Polyoxometalate Clusters.
in Angewandte Chemie (International ed. in English)
Chen JJ
(2015)
High-Performance Polyoxometalate-Based Cathode Materials for Rechargeable Lithium-Ion Batteries.
in Advanced materials (Deerfield Beach, Fla.)
Zhan C
(2015)
Assembly of Tungsten-Oxide-Based Pentagonal Motifs in Solution Leads to Nanoscale {W 48 }, {W 56 }, and {W 92 } Polyoxometalate Clusters
in Angewandte Chemie
Points LJ
(2016)
An all-inorganic polyoxometalate-polyoxocation chemical garden.
in Chemical communications (Cambridge, England)
Takashima Y
(2016)
Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.
in Chemical communications (Cambridge, England)
| 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 |