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Supporting Information
Alpha and Beta Isomers of Tetrahafnium(IV) Containing Decatungstosilicates,
[Hf4(OH)6(CH3COO)2(x-SiW10O37)2]12- (x = α, β)
Awatef S. Assran,a,b Sib Sankar Mal,a,c Natalya V. Izarova,a,d Abhishek Banerjee,a Andreas Suchopar,a Masahiro Sadakane,e and Ulrich Kortza,*
a Jacobs University, School of Engineering and Science, P.O. Box 750 561, 28725 Bremen, Germany;
b Permanent address: South Valley University, Faculty of Science at Qena, Chemistry department, 83523 Qena, Egypt;
c Current address: Center For Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, K1N 6N5, ON, Canada;
d Permanent address: Nikolaev Institute of Inorganic Chemistry, Prospekt Lavrentyeva 3, 630090 Novosibirsk, Russia;
e Chemisty and Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, 739-8527, Japan.
E-mail: [email protected]; Fax: +49 421 200 3229; Tel: +49 421 200 3235
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T= 60CpH
= 4.8
T= 50C
pH= 3.6
T= 70-90C
[-SiW10O37]10- [-SiW10O37]10-
[-SiW10O36]8-
T= 60CpH
= 4.8
T= 50C
pH= 3.6
T= 70-90C
[-SiW10O37]10- [-SiW10O37]10-
[-SiW10O36]8-
Figure S1. Representation of three dilacunary decatungstosilicate Keggin isomers and the experimental
conditions for irreversible transformation. Color code: SiO4 yellow tetrahedra, WO6 red octahedra. The
WO6 polyhedra of the rotated triads are highlighted in green.
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Figure S2. Thermogram of K-1 (top) and K-2 (bottom).
Colour legend: TGA, green line; DTA, blue line.
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Figure S3. IR spectra of K-1 (blue) and K-2 (pink).
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Figure S4. Room temperature 183W NMR spectrum of K-2 redissolved in 1M CH3COOLi buffer (pH =
5).
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0
0.4
0.8
1.2
1.6
2
200 250 300 350 400wavelength nm
A
pH3
pH3.5
pH4.0
pH4.5
pH5.0
pH5.5
Figure S5. UV-vis spectrum of K-1 (3 10-5 M) in 1 M CH3COOLi solutions at different pH.
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0
0.1
0.2
0.3
0.4
200 250 300 350 400wavelength nm
A
pH3pH3.5pH4pH4.5pH5.5pH5.0
Figure S6. UV-vis spectrum of K-2 (3 10-6 M) in 1 M CH3COOLi solutions at different pH.
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0 -200 -400 -600 -800 -1000 -1200
0
-20
-40
-60
-80
-100
Cur
rent
[A
]
Potential [mV]
(a)
0 -200 -400 -600 -800 -1000 -1200
0
-20
-40
-60
-80
(b)
Curr
ent
[A
]
Potential [mV]
Figure S7. Cyclic voltammogram of 1 in 0.5 M LiOAc (pH 4.0) (a) and 2 in 0.5 M LiOAc (pH 4.8).
Scan rate: 25 mV/s. The color code is Black line: scan until -1300 mV, red line: scan until -1000 mV,
blue line: scan until -1300 mV without polyoxometalates (blank only electrolyte).
