Design and assembly of covalently functionalised polyoxofluorovanadate molecular hybrids

Nicolaou, M., Papanikolaou, M., Tsipis, A., Kabanos, T., Keramidas, A., Sproules, S. and Miras, H. N. (2018) Design and assembly of covalently functionalised polyoxofluorovanadate molecular hybrids. Chemistry: A European Journal, 24(15), pp. 3836-3845. (doi:10.1002/chem.201705730) (PMID:29319211)

Nicolaou, M., Papanikolaou, M., Tsipis, A., Kabanos, T., Keramidas, A., Sproules, S. and Miras, H. N. (2018) Design and assembly of covalently functionalised polyoxofluorovanadate molecular hybrids. Chemistry: A European Journal, 24(15), pp. 3836-3845. (doi:10.1002/chem.201705730) (PMID:29319211)

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Abstract

Mixed-valent polyoxometalate (POM) clusters are one of the most interesting host species showing a wide range of structural features and properties. We report the facile preparation and functionalization of a mixed-valent polyoxofluorovanadates where two electrons are trapped to antipodal sites of the clusters. The first members of this family of clusters with the general formula, [VV12VIV2O16(μ-O)10(μ3-O)10(μ3-F)2(L)2]6-, where L: py = pyridine (1); pyr = pyrazine (2); im = imidazole (3), are unique organic-inorganic hybrids with the addition of a N-donor ligand at either end of the polyoxofluorovanadate. The composition and connectivity of 1 - 3 were characterized by single-crystal X-ray diffractometry and electrospray ionization mass spectrometry. Electron paramagnetic resonance spectroscopy revealed the two well-separated VIV ions in each cluster are fully uncoupled with J = 0 giving a degenerate singlet-triplet ground state. This attenuation of the exchange interaction is probed with density functional theoretical calculations that detail the inclusion of the fluoride ion in the cluster produces a bond pathway biased toward destructive interference between competing ferromagnetic and antiferromagnetic interactions. These robust molecular materials are the ideal combination of desirable electronic properties with an organic handle with which they can be integrated into spintronic circuitry for molecular devices.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen and Moiras, Dr Charalampos
Authors: Nicolaou, M., Papanikolaou, M., Tsipis, A., Kabanos, T., Keramidas, A., Sproules, S., and Miras, H. N.
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:10 January 2018
Copyright Holders:Copyright © 2018 Wiley-VCH Verlag GmbH & Co.
First Published:First published in Chemistry: A European Journal 24(15): 3836-3845
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY