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Vanadyl sulfates: molecular structure, magnetism and electrochemical activity

Ignaszak, Anna; Patterson, Nigel; Radtke, Mariusz; Elsegood, Mark R.J.; Frese, Josef W.A.; Lipman, Joah L.Z.F.; Yamato, Takehiko; Sanz, Sergio; Brechin, Euan K.; Prior, Timothy J.; Redshaw, Carl


Anna Ignaszak

Nigel Patterson

Mariusz Radtke

Mark R.J. Elsegood

Josef W.A. Frese

Joah L.Z.F. Lipman

Takehiko Yamato

Sergio Sanz

Euan K. Brechin

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Dr Tim Prior
Senior Lecturer in Inorganic Chemistry

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Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry


Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(3-OH)4(SO4)4]∙1/2H2O (1), [HNEt3]5[(VO)5(3-O)4(SO4)4]∙4MeCN (2∙4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]∙MeCN (3∙MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2] (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1-3 in the T = 300 - 2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10-4 s-1 and 6.44 × 10-6 (mmol O2 / mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process.


Ignaszak, A., Patterson, N., Radtke, M., Elsegood, M. R., Frese, J. W., Lipman, J. L., …Redshaw, C. (2018). Vanadyl sulfates: molecular structure, magnetism and electrochemical activity. Dalton Transactions : an international journal of inorganic chemistry, 47(44), 15983-15993.

Journal Article Type Article
Acceptance Date Oct 21, 2018
Online Publication Date Oct 22, 2018
Publication Date Nov 13, 2018
Deposit Date Oct 23, 2018
Publicly Available Date Oct 23, 2019
Journal Dalton Transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 47
Issue 44
Pages 15983-15993
Keywords Inorganic Chemistry
Public URL
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