Loading…
A new redox-based and stepwise synthetic strategy lead to an unprecedented mixed-valence Keggin-type tungstovanadophosphate (WVI/VIV) bi-capped by vanadium(VIII)-complexesElectronic supplementary information (ESI) available: Additional Fig. S1-S7 and Tables S1 and S2 as described in the text. CCDC 1580600. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8nj00714d
To achieve improved properties such as lower biotoxicity and better biocatalytic performances, the preparation of low oxidation state (+3) vanadium (V)-organic framework compounds (V III -OFCs) is an important research area. Additionally, the incorporation of V III -OFCs into a polyoxometalate (POM)...
Saved in:
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | To achieve improved properties such as lower biotoxicity and better biocatalytic performances, the preparation of low oxidation state (+3) vanadium (V)-organic framework compounds (V
III
-OFCs) is an important research area. Additionally, the incorporation of V
III
-OFCs into a polyoxometalate (POM) is challenging due to the high standard reduction potential of V
III
ions and the POM's innate sensitivity to oxidation. A new targeted and redox-based synthetic strategy has been devised to generate a V(
iii
)-oxyanion by reducing a precursor in a pH-value controlled redox step. The V(
iii
)-oxyanion is designed to coordinate with organic ligands for further forming an intermediate in which the metal node V(
iii
) connects both organic units and oxygen-atoms. By employing a suitable stepwise synthesis strategy, we successfully obtained an unprecedented Keggin-type tungstovanadophosphate, (H
3
DETA)
3
(DETA){Na{[V
III
(DETA)]
2
[W
VI
8
V
IV
4
O
36
(PO
4
)]}
2
}·2H
2
O (abbreviated as V
III
-POWV) (DETA = diethylenetriamine, C
4
H
13
N
3
), bi-capped by V
III
-OFCs. Its structure has been further characterized by means of powder-XRD, EDS, elemental analysis, FT-IR, XPS, thermal analysis, and SQUID magnetic measurements,
etc.
The seven-coordination mode (VO
4
N
3
) of V
III
in V
III
-POWV is uncommon and interesting. The novel structural compound, which contains mixed-valence vanadium (V
III
/V
IV
), has better thermostability than most of the common organic POMs and shows the expected paramagnetic properties, accompanying antiferromagnetic exchange interactions under higher temperatures.
A new POM-based V
III
-organic coordination compound has been prepared using a redox-based and stepwise synthetic strategy. |
|---|---|
| ISSN: | 1144-0546 1369-9261 |
| DOI: | 10.1039/c8nj00714d |