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Vanadyl sulfates: molecular structure, magnetism and electrochemical activity

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journal contribution
posted on 01.11.2018, 11:27 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 Redshaw
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(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 Transactions

Volume

47

Issue

44

Pages

15983-15993

Citation

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 Chemistry

Version

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/c8dt03626h

Acceptance date

21/10/2018

Publication date

2018-10-22

Copyright date

2018-10-22

ISSN

1477-9226

eISSN

1477-9234

Language

en

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