Vanadyl sulfates: molecular structure, magnetism and electrochemical activityElectronic supplementary information (ESI) available: Alternative views of 1-6; crystallographic experimental; CV, DPE and BE scans for 2, and CV for 5. CCDC 1574239-1574245. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt03626h
Reaction of differing amounts of vanadyl sulfate with p-tert -butylthiacalix[4]areneH 4 and base allows access to the vanadyl-sulfate species [NEt 4 ] 4 [(VO) 4 (μ 3 -OH) 4 (SO 4 ) 4 ]·½H 2 O ( 1 ), [HNEt 3 ] 5 [(VO) 5 (μ 3 -O) 4 (SO 4 ) 4 ]·4MeCN ( 2 ·4MeCN) and [NEt 4 ] 2 [(VO) 6 (O) 2 (SO 4 ) 4 (...
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| Main Authors | , , , , , , , , , , |
|---|---|
| Format | Journal Article |
| Published |
13.11.2018
|
| Online Access | Get full text |
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| Summary: | Reaction of differing amounts of vanadyl sulfate with
p-tert
-butylthiacalix[4]areneH
4
and base allows access to the vanadyl-sulfate species [NEt
4
]
4
[(VO)
4
(μ
3
-OH)
4
(SO
4
)
4
]·½H
2
O (
1
), [HNEt
3
]
5
[(VO)
5
(μ
3
-O)
4
(SO
4
)
4
]·4MeCN (
2
·4MeCN) and [NEt
4
]
2
[(VO)
6
(O)
2
(SO
4
)
4
(OMe)(OH
2
)]·MeCN (
3
·MeCN). Similar use of
p-tert
-butylsulfonylcalix[4]areneH
4
,
p-tert
-butylcalix[8]areneH
8
or
p-tert
-butylhexahomotrioxacalix[3]areneH
3
led to the isolation of [HNEt
3
]
2
[H
2
NEt
2
]
2
{[VO(OMe)]
2
p-tert
-butylcalix[8-SO
2
]areneH
2
} (
4
), [HNEt
3
]
2
[V(O)
2
p-tert
-butylcalix[8]areneH
5
] (
5
) and [HNEt
3
]
2
[V
IV
2
V
V
4
O
11
(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 O
2
/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 V
4+
species, facilitated by protons generated in the water discharge process.
Use of different calixarenes with vanadyl sulfate/base under N
2
affords different polyoxovanadates. Molecular structures, electrochemical activity and magnetism are reported. |
|---|---|
| Bibliography: | CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 2 Electronic supplementary information (ESI) available: Alternative views of 5 1574239-1574245 1-6 crystallographic experimental; CV, DPE and BE scans for and CV for 10.1039/c8dt03626h |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c8dt03626h |