Supplemental data
Two new halide-containing polyoxometalate-based compounds
LA-MEI WANG, HAI-YANG GUO, SU LI, YANG-YANG HU, YAN WANG, LI-NA XIAO, DE-CHUAN ZHAO,
ZHONG-MIN GAO, DA-FANG ZHENG, XIAO-BING CUI*, YONG FAN and JI-QING XU
Compound 1
25000
20000
simulated
experimental
Intensity
15000
10000
5000
0
5
10
15
20
25
30
35
40
Two theta (degree)
12000
Compound 2
Simulated
Experimental
10000
Intensity
8000
6000
4000
2000
0
5
10
15
20
25
30
35
40
Two theta (degree)
Figure S1. Experimental and simulated XRD patterns of 1 (a) and 2 (b). XRD patterns for 1
and 2 are in good agreement with the ones simulated based on the data of single-crystal X-ray
structures (figure S1), indicating the purity of synthesized products. The differences in
reflection intensity of XRD patterns for 1 and 2 are probably due to preferred orientations in
the powder samples of 1 and 2.
1
80
Compound 1
1607
1489
1431
515
3220
70
2999
2887
3454
1244
75
893
389
T%
65
1079
976
60
55
803
50
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber(cm )
88
Compound 2
1592
1513
80
880
793
1426
78
1062
956
76
74
4000
504
388
2939
2866
2380
T%
82
1342
1222
1143
1102
84
3787
86
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber(cm )
Figure S2. IR spectra of 1 (a) and 2 (b). The infrared spectrum of 1 shows four characteristic
vibrations resulting from the Keggin anion: 1079 cm-1 typical of ν(P-Oc), 976, 893 and 803
cm−1 of ν(W-Ot), ν(Ob-W-Ob) and ν(Oc-W-Oc), respectively. In addition, absorptions at 1244
to 1607 cm-1 are the proof of existing 4,4’-bpy and 1,10-Phen molecules (figure S2). The
infrared spectrum of 2 is similar to that of 1, which also exhibits four characteristic bands of
the Keggin anion: 1062 cm-1 typical of ν(P-Oc), 956, 880 and 793 cm−1 of ν(W-Ot),
ν(Ob-W-Ob) and ν(Oc-W-Oc), respectively. Absorptions at 1102 to 1592 cm-1 are the proof of
existing 4,4’-bpy and 1,10-Phen molecules in 2 (figure s2).
2
26000
37.55
Compound 1
24000
35.4
22000
20000
18000
CPS
16000
14000
12000
10000
8000
6000
4000
2000
0
46
44
42
40
38
36
34
32
30
28
Binding energy (eV)
45000
40000
232.95
Compound 2
35000
236.05
30000
25000
20000
15000
10000
5000
0
245
240
235
230
Binding energy (eV)
Figure S3. the W4f XPS spectrum (a) of 1 and the Mo4f XPS spectrum (b) of 2. The XPS
spectrum of 1 gives two peaks at 37.6 eV and 35.4 eV in the W4f region being ascribed to
W6+ (figure S3). The XPS estimation of valence-state values seems to be in reasonable
agreement with those calculated from bond valence sum calculations. The results further
confirm the valence of W6+ atoms in 1. The XPS spectrum of 2 gives two peaks at 236.1 eV
and 233.0 eV in the Mo4f region due to Mo6+ (figure S3). The XPS estimation of the
valence-state values seems to be in reasonable agreement with those calculated from bond
valence sum calculations. The results further confirm the valence of the Mo6+ atoms in 2.
3
1.8
Compound 1
1.5
Absorbance
1.2
0.9
0.6
0.3
0.0
300
350
400
Wavelength (nm)
2.0
1.8
Compound 2
1.6
Absorbtion
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
300
350
400
Wavelength (nm)
Figure S4. UV-Vis spectra of 1 (a) and 2 (b). The UV-Vis spectrum in the range of 260-600
nm of 1 is presented in figure S4, which displays a wide medium intense absorption peak at
about 267 nm and a shoulder peak at 295 nm, assigned to O→W charge transfer in the
polyoxoanion structure. The UV-Vis spectrum of 2 is similar to that of 1 (presented in figure
S4), which also displays a wide medium intense absorption peak at about 267 nm and a
shoulder peak at 295 nm, assigned to O→Mo charge transfer in the polyoxoanion structure.
4
0.010
Compound 1
III
I
0.005
II
I (mA)
0.000
I'
-0.005
II'
-0.010
-0.015
III'
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
E (V)
0.006
Compound 2
II
I
0.004
III
0.002
I (mA)
0.000
-0.002
I'
-0.004
II'
III'
-0.006
-0.008
-0.010
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
E (V)
Figure S5. The cyclic voltammograms of 1 and 2 in 0.3 M H2SO4 at a scan rate of 100 mV·s-1.
5