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 |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Sproules, Dr Stephen and Moiras, Professor Haralampos and Long, Dr Deliang and Cronin, Professor Lee |
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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