Directed self-assembly, symmetry breaking, and electronic modulation of metal oxide clusters by pyramidal heteroanions

Miras, H. N. , Sartzi, H., Long, D.-L. , Sproules, S. and Cronin, L. (2018) Directed self-assembly, symmetry breaking, and electronic modulation of metal oxide clusters by pyramidal heteroanions. Chemistry: A European Journal, 24(17), pp. 4399-4411. (doi:10.1002/chem.201705711) (PMID:29315925)

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Abstract

Mixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species showing the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein, the incorporation of different pyramidal EO32- heteroanions (E = PH, S, Se, Te) which are responsible not only for directing the templated assembly of a family of mixed-metal POMs but also for the symmetry-breaking of the traditional Dawson architecture and modulation of the electronic characteristics of the cluster's shell. The isolated family of POMs consists of four members: (Me2NH2)5Na2[Mo11V7O52(HPO3)]·MeOH·5H2O (1), (NH4)7[Mo11V7O52(SO3)]·12H2O (2), K7[Mo11V7O52(SeO3)]·31H2O (3), (Me2NH2)6Na[Mo11V7O52(TeO3)]·15H2O (4), and were characterized by X-ray structural analysis, electrospray ionization mass spectrometry (ESI-MS), thermogravimetric analysis (TGA), UV-vis, IR, elemental and flame atomic absorption spectroscopy (FAAS) analysis, and inductively coupled plasma optical emission spectroscopy (ICP-OES). Cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) spectroscopic studies in concert with density functional theoretical (DFT) calculations elucidate the effect of the heteroatom on the electronic properties of the cluster.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen and Moiras, Dr Charalampos and Long, Dr De Liang and Cronin, Professor Leroy
Authors: Miras, H. N., Sartzi, H., Long, D.-L., Sproules, S., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Publisher:Wiley
ISSN:0947-6539
ISSN (Online):1521-3765
Published Online:09 January 2018
Copyright Holders:Copyright © 2018 Wiley-VCH Verlag GmbH & Co.
First Published:First published in Chemistry: A European Journal 24(17): 4399-4411
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
503291Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular LimitLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/H024107/1CHEM - CHEMISTRY
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
685741SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467CHEM - CHEMISTRY