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Vanadyl sulfates: molecular structure, magnetism and electrochemical activity
journal contribution
posted on 2018-11-01, 11:27 authored by Anna Ignaszak, Nigel Patterson, Mariusz Radtke, Mark ElsegoodMark Elsegood, Josef W.A. Frese, Joah L. Lipman, Takehiko Yamato, Sergio Sanz, Euan K. Brechin, Timothy J. Prior, Carl RedshawReaction 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(μ3-OH)4(SO4)4]·½H2O (1), [HNEt3]5[(VO)5(μ3-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.
Funding
The EPSRC is thanked for an Overseas Travel Grant (to CR). EKB thanks the EPSRC for funding grants EP/N01331X/1 and EP/P025986/1.
History
School
- Science
Department
- Chemistry
Published in
Dalton TransactionsVolume
47Issue
44Pages
15983-15993Citation
IGNASZAK, A. ... et al, 2018. Vanadyl sulfates: molecular structure, magnetism and electrochemical activity. Dalton Transactions, 47 (44), pp.15983-15993.Publisher
© The Royal Society of ChemistryVersion
- AM (Accepted Manuscript)
Publisher statement
This paper was accepted for publication in the journal Dalton Transactions and the definitive published version is available at https://doi.org/10.1039/c8dt03626hAcceptance date
2018-10-21Publication date
2018-10-22Copyright date
2018-10-22ISSN
1477-9226eISSN
1477-9234Publisher version
Language
- en