Supporting Information
A sensitive colorimetric and ratiometric chemosensor for trivalent metal cations
Xu Zhao1,2, Guohui Yin1,2, Di Jin1,2, Xilong Yan1,2, Yang Li1,2, Ligong Chen1,2*
1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China
2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), P. R. China
Corresponding author:
Email: lgchen@tju.edu.cn, Tel/Fax: +86-22-27406314
Table of contents
Fig. S1-S6: 1H NMR, 13C NMR and HR-MS spectra of compound 3 and the target compound.
Fig. S7: UV-visible spectra responses of the probe (10-5 M) towards Fe3+ in 3:7 ethanol-water mixed solution.
Fig. S8: UV-visible spectra responses of the probe (10-5 M) towards Al3+ in 3:7 ethanol-water mixed solution.
Fig. S9: Plot of A760/678 against the ratio of Fe3+ and Al3+to probe (10-5 M) in 3:7 ethanol-water solution.
Tab. S1: Selectivity coefficients of probe towards Cr3+, Fe3+ and Al3+ over other metal ions.
110
100
90
80
70
ppm (t1)
50
40
Fig. S2 13C NMR spectrum of compound 3 in CDCl3.
30
20
14.026
2.0
20.738
28.148
26.522
32.201
40.579
60
49.317
61.315
102.000
111.194
122.218
125.446
128.160
128.847
140.868
141.804
144.428
150.639
170.768
172.366
3.0
6.40
120
4.0
11.72
130
5.0
2.29
140
6.0
4.21
4.13
7.0
4.37
150
3.97
160
2.00
8.0
2.08
170
2.08
2.14
2.10
2.49
180
2.14
2.00
9.0
ppm (t1)
2.10
2.49
7.500 7.450 7.400 7.350 7.300 7.250 7.200
ppm (t1)
1.0
0.0
Fig. S1 1H NMR spectrum of compound 3 in CDCl3.
10
0
7.266
7.253
7.242
7.289
7.303
7.316
7.384
7.372
7.392
7.418
7.405
1.722
1.188
1.176
1.164
2.781
2.771
2.761
1.998
1.988
1.978
1.968
2.954
2.943
2.932
4.627
4.616
4.605
4.098
4.086
4.074
4.062
6.414
6.390
7.316
7.303
7.289
7.266
7.253
7.242
7.418
7.405
7.392
7.384
7.372
8.365
8.342
100
75
50
Fig. S4 13C NMR spectrum of the target compound in CDCl3.
25
14.090
0.50
21.659
1.00
24.789
29.051
29.676
1.50
30.963
2.00
31.664
2.50
39.306
3.00
48.096
3.50
54.468
4.00
61.339
95.844
109.167
110.654
122.374
124.235
123.778
140.103
128.391
141.139
142.101
145.046
168.522
170.867
4.50
6.67
5.00
12.13
2.07
125
5.50
4.06
6.00
6.44
4.64
6.50
2.36
3.95
4.47
150
7.00
3.95
7.50
1.92
175
ppm (t1)
8.00
4.19
2.14
2.15
2.00
8.50
ppm (t1)
0.00
-0.50
Fig. S3 1H NMR spectrum of the target compound in MeOD.
0
2.818
2.807
2.796
2.777
2.590
2.579
2.568
1.900
1.890
1.879
1.873
1.869
1.702
1.191
1.179
1.168
3.918
3.834
3.825
3.816
2.963
4.104
4.100
4.093
4.081
4.069
4.358
4.348
4.337
6.050
6.028
7.374
7.361
7.348
7.176
7.164
7.153
7.739
7.717
7.443
7.430
Fig. S5 HR-MS spectrum of compound 3.
Fig. S6 HR-MS spectrum of the target compound.
0.8
0.7
0.7
Absorbance
0.6
0.5
Absorbance
A760 nm
0.6
0.5
0.4
0.3
A678 nm
0.2
0.1
0.4
0
2
4
6
8
10
equiv. of Fe3+
0.3
0.2
10 equiv.
0.1
Fe3+
0.0
0.1 equiv.
300
400
500
600
700
800
900
1000
Wavelength (nm)
Fig. S7 UV-visible spectra responses of the probe (10 -5 M) upon addition of different equiv. of Fe3+ in 3:7 ethanol-water
mixed solution. Inset: changes in the absorbance at 678 nm and 760 nm with incremental addition of Fe3+.
0.8
0.7
0.6
Absorbance
0.5
Absorbance
0.7
A760 nm
0.6
0.5
0.4
A678 nm
0.4
0.3
0
2
4
6
8
10
equiv. of Al3+
0.3
10 equiv.
0.2
Al3+
0.1
1 equiv.
0.0
300
400
500
600
700
equiv. of Al
800
900
1000
3+
Fig. S8 UV-visible spectra responses of the probe (10 -5 M) upon addition of different equiv. of Al3+ in 3:7 ethanol-water
mixed solution. Inset: changes in the absorbance at 678 nm and 760 nm with incremental addition of Al 3+.
2.0
2.2
1.8
2.0
1.6
R = 9.9548
1.4
1.2
Y = 0.5123 X + 0.4844
1.4
1.2
Y = 0.221 X + 0.565
1.0
R = 0.9937
1.0
R = 0.9451
0.8
0.8
0.6
Y = 0.035 X + 1.548
1.6
Y = 0.03286 X + 1.6143
R = 0.8964
A760 /678
A760 / 678
1.8
0.6
0
2
4
6
Equiv. of Fe
8
0
10
2
3+
4
6
equiv. of Al
8
10
3+
Fig. S9. Plot of A760/678 against the ratio of Fe3+ and Al3+to probe (10-5 M) in 3:7 ethanol-water solution. (A) The ratio of Fe3+
to probe are 0.6, 0.7, 0.8 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, respectively; (B) The ratio of Al 3+ to probe are 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, respectively.
Tab. S1 Selectivity coefficients of probe towards Cr3+, Fe3+ and Al3+ over other metal ions.
Metal ions
Selectivity coefficients of Fe3+
Selectivity coefficients of Cr3+
Selectivity coefficients of Al3+
Ba2+
2.75
2.64
2.61
Ca2+
3.03
2.91
2.87
Co2+
2.97
2.85
2.81
Cu2+
2.26
2.17
2.14
Mg2+
2.97
2.85
2.81
Mn2+
2.95
2.84
2.8
Ni2+
2.92
2.81
2.77
Zn2+
2.86
2.75
2.71
Fe3+
1
0.96
0.99
Cr3+
1.04
1
0.95
Al3+
1.06
1.01
1
Ag+
2.91
2.79
2.75
Na+
2.87
2.76
2.72
K+
2.96
2.84
2.8