Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids Mixed‐valent polyoxometalate (POM) clusters are one of the most interesting host species, showing a wide range of structural features and properties. The facile preparation and functionalisation of a mixed‐valent polyoxofluorovanadates is reported, 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 characterised by single‐crystal X‐ray diffraction and electrospray ionisation mass spectrometry. Electron paramagnetic resonance spectroscopy revealed that 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 reveal that 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry - A European Journal Wiley

Design and Assembly of Covalently Functionalised Polyoxofluorovanadate Molecular Hybrids

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0947-6539
eISSN
1521-3765
D.O.I.
10.1002/chem.201705730
Publisher site
See Article on Publisher Site

Abstract

Mixed‐valent polyoxometalate (POM) clusters are one of the most interesting host species, showing a wide range of structural features and properties. The facile preparation and functionalisation of a mixed‐valent polyoxofluorovanadates is reported, 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 characterised by single‐crystal X‐ray diffraction and electrospray ionisation mass spectrometry. Electron paramagnetic resonance spectroscopy revealed that 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 reveal that 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.

Journal

Chemistry - A European JournalWiley

Published: Jan 12, 2018

Keywords: ; ; ; ;

References

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