Anna Ignaszak
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
Authors
Nigel Patterson
Mariusz Radtke
Mark R.J. Elsegood
Josef W.A. Frese
Joah L.Z.F. Lipman
Takehiko Yamato
Sergio Sanz
Euan K. Brechin
Dr Tim Prior T.Prior@hull.ac.uk
Senior Lecturer in Inorganic Chemistry
Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry
Abstract
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.
Citation
Ignaszak, A., Patterson, N., Radtke, M., Elsegood, M. R., Frese, J. W., Lipman, J. L., Yamato, T., Sanz, S., Brechin, E. K., Prior, T. J., & Redshaw, C. (2018). Vanadyl sulfates: molecular structure, magnetism and electrochemical activity. Dalton Transactions : an international journal of inorganic chemistry, 47(44), 15983-15993. https://doi.org/10.1039/c8dt03626h
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 |
DOI | https://doi.org/10.1039/c8dt03626h |
Keywords | Inorganic Chemistry |
Public URL | https://hull-repository.worktribe.com/output/1125676 |
Publisher URL | https://pubs.rsc.org/en/Content/ArticleLanding/2018/DT/C8DT03626H |
Contract Date | Oct 23, 2018 |
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©2018 The authors
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